Semiconductor Measurements

and Instrumentation
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'Semiconductor Measurements
and Instrumentation

W. R. RUNYAN
Special Circuits Department
Texas Instruments Incorporated

McGRAW-HILL BOOK COMPANY

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Library of Congress Cataloging in Publication Data

Runyan, W R
Semiconductor measurements and instrumentation.
(Texas Instruments electronics series)
Bibliography: p.
1. Semiconductors. I. Title.
QC6l1.24.R86 537.6'22 75-19035
ISBN 0-07-054273-2

Copyright © 1975 by Texas Instruments Incorporated. All rights

reserved. Printed in the United States of America. No part of
this publication may be reproduced, stored in a retrieval system,
or transmitted, in any form or by any means, electronic, mechanical,
photocopying, recording, or otherwise, without prior written per-
mission of Texas Instruments Incorporated.

1234567890 HDBP 784321098765

Information contained in this book is believed to be accurate

and reliable. However, responsibility is assumed neither for
its use or infringement of patents or rights of others which
may result from its use. No license is granted by implication
or otherwise under any patent right of Texas Instruments or
others.

The editors for this book were Tyler G. Hicks and Lester Strong,
and the production supervisor was George Oechsner.
It was set in Times Roman by York Graphic Services, Inc.
It was printed by Halliday Lithograph Corporation and bound by
The Book Press.
 Contents

Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . : . .. ix

Chapter 1. Crystal Orientation.

1.1 Crystallography
1.2 Orientation. . ..... 8
References . . . 18

Chapter 2. Crystallographic Defects and Their Observation ........... 21

2.1 Point Defects . 21

2.2 Dislocations . . 25
2.3 Stacking Faults 36
2.4 Twins . . . . . . 40
2.5 Lineage..... 41
2.6 Grains and Grain Boundaries. 42
2.7 Inclusions . . . . . . . . . . . 43
2.8 Lattice Stress and Strain ... 44
2.9 Mechanical Surface Damage 49
2.10 Shape Defects . . . 52
2.11 Radiation Damage 52
References . . . . . 54

Chapter 3. Resistivity and Carrier-Concentration Measurements 65

3.1 General Considerations . . . . . . . . . . . . 65
3.2 Basic Methods. . . . . . . . . . . . . . . . . . 67
3.3 Two- and Four-Point Probe Instrumentation 75
3.4 Errors in Two- and Four-Point Measurement. 79
3.5 Spreading Resistance . . . . . . : . . 82
3.6 Noncontacting Resistivity Methods .. 84
3.7 Carrier Concentration . . . . . . . 85
3.8 Resistivity Profiling .. .88
References . . . . . . . 93

Chapter 4. Lifetime . .... 105

4.1 Introduction · 105
4.2 Photoconductive Decay. . . .. · 107
4.3 Alternate Injection Methods .. · 113
4.4 Photoconductivity Modulation. · 114
4.5 Photoconductivity ... · 114
4.6 Surface Photovoltage . · 115
4.7 PEM Effect . . . . . . · 117

v
vi Contents

4.8 Diffusion-Length Measurements ... · 118

4.9 Drift . . . . . . . . . . . · 120
4.10 Miscellaneous Methods. 121
References . . . . . . . . · 121

Chapter 5. Mobility, Hall, and Type Measurements .... 131

5.1 Mobility . . . . . . . . . . . . . . . . . · 131
5.2 Hall Effect . . . . . ... · 133
5.3 Conductivity Type 144
References . . . . . . . . · 147

Chapter 6. Thickness Measurements . . . . . . . . . . . . . . . . . . . 153

6.1 Introduction........... · 153
6.2 Micrometers and Other Gages · 154
6.3 Absorption Methods · 156
6.4 Ellipsometry........... · 158
6.5 Interference Effects . . . . . . . 165
6.6 Bevel Measurements by Interferometry and Other Methods · 175
6.7 Step-Height Measurements . . . . . . . . . . . . . · 181
6.8 High Power Microscope plus Visible Boundaries. · 181
6.9 Weight Differential . . . . . . . . . . . . . . · 181
6.10 Crystallographic Methods . . . . . . . . . . 182
6.11 Miscellaneous Methods for Metallic Films 183
References . . . . . . . . . . . . . . . . . . . 183

Chapter 7. Preparation of Samples for Microscopic Examination .... 187

7.1 Sectioning....... · 187

7.2 Chemical Treatments. · 196
7.3 Delineation .200
References . . . . . . . · 214

Chapter 8. Microscopy and Photography 217

8.1 Basic Optics . . . . . . . . . .. · 217

8.2 Optical Image Quality . . . . . · 221
8.3 Specialized Optical Equipment .228
8.4 Photography ... .235
References . . . . . . . . . . . . . . . . · 241

Chapter 9. The Electron Microscope and Other Analytical Instruments 243

9.1 Electron Microscopy, General . . . . .243

9.2 Transmission Microscopy .244
9.3 The Scanning Microscope .246
9.4 Electron Diffraction. . .252
9.5 X-Rays . . . . . . . . . .254
9.6 Electron Spectroscopy .259
9.7 Optical Spectroscopy . .262
9.8 Mass Spectroscopy .. .265
9.9 Ion Backscattering .. .266
9.10 Radioactive Methods . .267
References . . . . . . . .268

Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 275
 Preface

In the course of twenty years, since the introduction of the first commercial silicon
transistor, semiconductor evaluation has progressed from some rather simple lifetime,
Hall, and resistivity measurements and quite insensitive chemical analyses to very
elegant analytical procedures and extremely sophisticated equipment for measuring
the various electrical properties. In addition, the ability to detect and to appreciate
the myriads of crystallographic defects which may appear in semiconductors has
improved manyfold in that same twenty years. Keeping pace with this has been
the literature, which regularly reports new methods or refinements of older ones
and has by now reached major proportions.
My hope in preparing this book is that it will provide a guide through that maze
of literature and methods that have accumulated so that the most appropriate
technique for a particular problem may be chosen, and that the directions will
be precise enough for most bulk measurements to be made without difficulty. It
was written principally for semiconductor process engineers, failure analysis labora-
tory personnel, and university students faced with measuring the properties of
semiconductors. However, many of the procedures are applicable to other materials
as well. The depth of treatment varies from topic to topic, depending not only on
its importance to the business of semiconductors, but also on the availability of
background reading and how dependent some particular method is on techniques
that develop only with usage, but which are seldom written down. In addition, there
are hopefully enough references provided about the more important device-oriented
measurements to direct the reader to them as well.
I wish to express my appreciation to the many people who helped in the prepara-
tion of this book. Mr. Stacy Watelski (Texas Instruments) coauthored Chap. 7,
supplied various photographs, and generally provided useful comments. Dr. Murray
Bullis (NSB), Dr. Lyndon Taylor (Oniv. of Texas), Dr. W. F. Keenan, and G. P.
Pollack, and Messrs A. N. Akridge, Andreas Niewold, and A. F. Polack (all of Texas
Instruments) critically read various chapters. Mrs. Hettie Smith typed the manuscript
as it went through its many iterations, and my daughter Kay assisted with the
. proofreading.

Dallas, Texas W. R. Runyan

vii
 1
Crystal Orientation

The values obtained when the various measurements discussed in later chapters
are made may depend on the orientation of the crystallographic face on which
measurements are being made and the direction in which some stress (voltage, force,
temperature, etc.) is applied. Because of these dependencies, and because many of
the semiconductor processes are dependent on orientation, considerable emphasis
must be placed on crystal orientation. Some of the more common properties and
their behavior are summarized in Table 1.1. Table 1.2 summarizes the orienta-
tion-dependent processes that might be expected. In general, if a property is any-
thing other than a scalar, it will be direction-sensitive in most crystalline materials. 1
Those properties which are described by a second-rank tensor, and this includes
almost all the properties of common interest in the semiconductor industry (resistiv-
ity, thermal conductivity, diffusion coefficients), are independent of direction in cubic
crystals (which encompasses the majority of present commercially important semi-
conductors).
There are, however, some problems in trying to predict behavior a priori. They
arise when it is difficult to determine the defining equation of the property (e.g.,
hardness and etch rate) or because an apparently simple measurement of one
property may in some subtle way involve additional phenomena. Resistivity should
be independent of the direction of the electric field for cubic crystals, but for the
specific case of spreading-resistance measurements, different values are obtained with
the same equipment when measurements are made on different faces of silicon.
Also, even though the diffusion coefficient should be independent of direction, it
is observed that under the same condition of surface ambient, temperature, and time,
the diffusion-depth of phosphorus can be different in the [111] and the [100] direc-
tions. Further, there may be physical constraints, e.g., very thin layers, in which
the crystal is no longer three-dimensional. Under such circumstances, properties
normally isotropic may become directionally dependent. It is this phenomenon
which causes orientation differences in the carrier mobility of silicon inversion layers.

1.1 CRYSTALLOGRAPHY

Before the various means for determining crystallographic orientation are dis-
cussed, a brief survey of the appropriate crystallographic nomenclature will be given.
Plane Indices. The various planes that pass through a crystal may be described
in terms of the reciprocal of the intercepts of that plane with the crystallographic
axes. These reciprocals are usually expressed as the smallest possible integers having
the same ratio and, for those crystal systems with three axes, are written as (hkl).
For the hexagonal crystal system, in which there are three coplanar axes as well
as one perpendicular to the plane of the first three, the indices are hkil. h, k, and
2 Semiconductor Measurements and Instrumentation

Table 1.1. Partial Listing of Directional Properties of Crystals

Tensor
rank Property Symbol Relates Form of relation Isotropic in

0 Density 8 Mass to volume A scal ar to a scalar All classes

Heat capacity C Heat transferred to
temperature changes

I Pyroelectric Pi Electrical polariza- A vector to a scalar None

coefficient tion to temperature
change

2 Electrical (Jil< Current density to

conductivity applied field
Electrical ILik Current density to
mobility applied field and
number of carriers A vector to a vector All cubic
Thermal ki; Heat transferred to
temperature gradient
Diffusion Di; Current density to
coefficient concentration
gradient

Thermal expansion ail Elongation to A scalar and 2d-

temperature change rank tensor

3 Piezoelectric dijk Polarization to A vector to a 2d- None

coefficient applied stress rank tensor

4 Elastic constants Cjjkl Stress to elongation Two 2d-rank tensors None

Piezoresistance 'lTijkl Change of resistivity
to applied stress

Adapted from J. F. Nye, "Physical Properties of Crystals," Oxford University Press, New York, 1960.

Table 1.2. . Orientation-Dependent Semiconductor Processes and Parameters

Wet etch (will depend on etchant) Important aspect of dielectrically isolated Si

ICs
Diffusion depth Not expected. See, for example, L. E. Katz,
"Orientation Dependent Diffusion Phenom-
ena," Paper 23, National Bureau of Stand-
ards, Spec. Pub. 337, 1970, for a discussion
Depth of ion implant
Buried-layer pattern wash out Effect minimized when growth surface slightly
misoriented from low-index plane
Vapor-phase epitaxy Best growth when surface slightly misoriented
from low-index plane. Growth surface rate
may depend on orientation
Scribe and break Scribe lines for good scribe-break operation
must be accurately aligned with predeter-
mined orientation
Mechanical polish Also reflected in depth of damage after me-
chanical polish or abrasion. See, for example,
A. W. Fisher and J. A. Amick,J. Electrochem.
Soc., 113:1054-1060 (1966)
Channel mobility in Si MOS devices
Surface-charge density of Si MOS devices
 Crystal Orientation 3

i are the reciprocals of the intercepts of the plane in question with the three coplanar
axes, and from the geometry it can be readily shown that h + k = - i. Since h
and k together completely determine i, it is not necessary to write all four indices,
but some method of indicating the hexagonal system is required. One common
notation is hk: I. Examples of various planes are shown in Fig. 1.1. A complete
family, composed of all possible planes resulting from permuting a given set of
indices (including negative values), is denoted by braces; e.g., {Ill} represents the
eight planes (111), (11 1), (111), (l IT), (Ill), (1 II), (Ill), (III). The bar over an
index number indicates a negative intercept.
The indices of a direction through a crystal are written as [hklJ. A complete set
of equivalent directions is written as (hkl). For a cubic system, the direction indices
will always be perpendicular to a plane with the same indices, but in other systems
this is not generally true.
Angles between Planes. Expressions for calculating the angle between any two
planes (hkl) and (h'k'l') are available. 2 Except for cubic crystals, dimensions of the
unit cell are involved and, since these numbers will be different for different mate-
rials, the angles between given planes can be determined only independent of the
material when the structure is cubic. Table 1.3 lists angles between low-index
cubic-crystal planes; it is very useful in the identification of facets.
Relative Position of Planes. Probably the easiest way to visualize the positions
of the various planes is by means of a model. Figure l.2a is a photograph and
plans of a very convenient one for cubic crystals. The pattern has been reduced
for publication, and unless one is very dexterous, it will probably need to be enlarged
before construction. If a small magnet is glued to the inside of one face, the model

(111) o (110)

-02

(1210) (0001)

Fig. 1.1. Examples of low-index planes.

4 Semiconductor Measurements and Instrumentation

Table 1.3. Angles between Crystallographic Planes (and between Crystallographic

Directions) in Crystals of the Cubic System

{HKL} {hkl} Values of angles between HKL and hkl planes (or directions)

100 100 0.00 90.00

110 45.00 90.00
III 54.74
210 26.56 63.43 90.00
211 35.26 65.90
221 48.l9 70.53
310 18.43 71.56 90.00
311 25.24 72.45
110 110 0.00 60.00 90.00
III 35.26 90.00
210 18.43 50.77 71.56
211 30.00 54.74 73.22 90.00
221 19.47 45.00 76.37 90.00
310 26.56 47.87 63.43 17.08
311 31.48 64.76 90.00
III III 0.00 70.53
210 39.23 75.04
211 19.47 61.87 90.00
221 15.79 54.74 78.90
310 43.09 68.58
311 29.50 58.52 79.98
210 210 0.00 36.87 53.13 66.42 78.46 90.00
211 24.09 43.09 56.79 79.48 90.00
221 26.56 41.81 53.40 63.43 72.65 90.00
310 8.13 31.95 45.00 64.90 73.57 81.87
311 19.29 47.61 66.14 82.25
211 211 0.00 33.56 48.19 60.00 70.53 80.40
221 17.72 35.26 47.l2 65.90 74.21 82.18
310 25.35 40.21 58.91 75.04 82.58
311 10.02 42.39 60.50 75.75 90.00
221 221 0.00 27.27 38.94 63.61 83.62 90.00
310 32.51 42.45 58.19 65.06 83.95
311 25.24 45.29 59.83 72.45 84.23
310 310 0.00 25.84 36.87 53.13 72.54 84.26
311 17.55 40.29 55.10 67.58 79.01 90.00
311 311 0.00 35.10 50.48 62.96 84.78

A more complete listing may be found in R. J. Peavler and J. L. Lenusky, "Angles between Planes
in Cubic Crystals," Spec. Rept. 8, American Institute of Mining, Metallurgical and Petroleum Engineers.

can be stored by sticking to metal wall paneling. The shape is not a standard
crystallographic form but rather is comprised solely of the complete sets of {IOO},
{llO}, and {Ill} planes. Crystal models such as those shown in Fig. 1.2b are also
helpful, and paper patterns for a great number of them are available. *
The relative positions of the various planes may also be indicated by stereo-
graphic-projection charts. 3 't These projections are made by surrounding the crystal
with an imaginary sphere and drawing lines from its center to the spherical surface
*Arthur J. Gude, "Three Dimension Models of the Basic Crystal Forms," cut-out kit available from
Polycrystal Book Service, Pittsburgh, Pa.
tBecause the angles between planes for noncubic crystals vary with cell dimensions, projections are
normally used only for the cubic system, and the following discussion assumes cubic crystals.
 Crystal Orientation 5

(IIo) (010)

(b 1
Fig. 1.2. Paper models. (a) Pattern and photograph of a figure comprised of {Ill},
{lIO}, and {IOO} faces. (b) Dodecahedron.

in such a manner that they are normal to the planes of interest. If an hkl projection
is desired, the crystal is oriented so that its (hkl) plane is normal to the "north pole"
of the imaginary sphere and the equatorial (projection) plane which divides the
sphere into an upper and lower hemisphere is parallel to the (hkl) plane. Lines
are then drawn connecting the "south pole" with the intersection of the various plane
normals and the northern hemisphere.
The points where the lines pass through the projection plane represent the planes
in question. This is illustrated in Fig. 1.3 for the specific case of a (111) plane
6 Semiconductor Measurements and Instrumentation

all

Fig. 1.3. Development of a stereographic

projection.

projection onto a (100) plane. Note that all dots on the periphery of the projection
plane represent planes perpendicular to the plane of projection and their angles
relative to each may be obtained graphically by drawing tangents to the circle as
shown in Fig. 1.4a.
The traces* of other planes (i.e., those represented by the interior dots) on the
projection plane may be found by drawing a line through the appropriate dot and
perpendicular to the line connecting the dot with the center of the projection as
in Fig. l.4b. However, angles between the planes themselves can be found only
by superimposing a nonlinear gridwork over the projection. Because of this, it is
more convenient to use tables (e.g., Table 1.3) for angles between planes,t but angles
between traces are most easily obtained from the projections just described. Projec-
tions for several of the more common planes are shown in Figs. 1.5 to 1.7. It is
very helpful to be able to mark on the projection; so it is suggested that a sheet
ofthin, clear plastic (e.g., a viewgraph jacket) be kept handy for laying on top of
the page. A grease pencil can then be used for nondestructive sketching.
In the event that it is desired to calculate trace angles rather than obtain them
from the projections (or for planes not on the projections), the direction cosines u,
v, and w of the line of intersection of a plane h'k'l' with plane hkl are given by

*The line formed by the intersection of two planes.

tSimilar gridworks are used in interpreting x-ray diffraction patterns and for that purpose are most
useful.

100

:tf 031

(a) (b)

Fig. 1.4. Standard projection interpretation. (a) The (100)

and (110) planes are both perpendicular to the (001) plane
and intersect at a 45 angle. (b) The traces of the (211)
0

and (031) planes on the (001) reference surface make an

angle of 63.5 with each other.
0
 Crystal Orientation 7
ioo

0301
.371 .311
0321 0321
.201
.331 .271 ·211 .331
.221 0312 0312 .221
0231

0 121
.Ti 212 313
•
213
0
• •
iOI 313
••212
0213
eT11
_0
231

°121
.i31 0112 oT02 °112 .i31
0132•0122
__ 0--
123 .'13 oT03 .113 i;'3 ·~220i32
133 .133

eoTI • .031
021

.131
0 213 0121
313
• 212
0312 0 31 2 .221
0211 .211 .331
.201 0321
.3TI .311
0301 110

100
Fig. 1.5. Standard (001) projection for a face-centered cubic crystal.

123 il2 213

113
023
• 012
• _
102
203
•
o o
Or3· 312
001
121
173
• • 113
• 112
o

2130
113
e
1~2
0120

0123
0023
~
•
0302 03~~12 III 1220 ~3 0032
TIO -312 tit 132- e021 .131 110

100. 210 .010

-
0130
.
120

310-
• 320
0 .110 0 I~O 0130
230

3010 311. 321 0 0237 0031

.13i
201 0
021
• 2110 221 0121 0
312 302 0 0312

212
0313
0 •
III 132-
1~2 133
•
0032 132

Fig. 1.6. Standard (111) projection for a face-centered cubic crystal.

8 Semiconductor Measurements and Instrumentation
001

103 013
213
e
• i23
e el02 eOl2 e
ell3
e203 e023 133 i22
212 313
• e e213 e 112 .123
• • e

312
•
•
101 .313
.212
122
•
133
•
011
032
e
132
e
e211 • 302 132
.312 ."1 e ·121
e e021
331 -321 e311
201 e el21 el31
•
301 e 21~321e221 231 .131
-031
311 e331 e
310210 110 230 120 130 i20 230
liD
320210310
• e • .100 • e '320. - e el30 .010 • • e 110

ooT
Fig. 1.7. Standard (110) projection for a face-centered cubic crystal.

The angle between the two lines is then given by the same equation used to compute
the angle between planes.

1.2 ORIENTATION

There are numerous ways in which the orientation of crystals can be determined
(see Table 1.4), but they can be broken down into the two broad categories of visual
observation of distinguishing features such as growth facets or etch pits, and x-ray
diffraction. All the visual methods require prior knowledge of growth, etch, or

Table 1.4. Orientation Methods

Method Comments

Visual observation of gross features Must show natural growth faces, poor accuracy
Microscopic observation of minute growth Accuracy medium, usually restricted to low-
facets index planes
Examination of fracture characteristics May be destructive, poor accuracy
Visual or microscopic observation of etch pits Selective etches must be available-accuracy
medium, most appropriate to low-angle
planes
Optical refiectograms Accuracy quite good when orienting low-index
planes
Laue x-ray Applicable to any orientation
X-ray diffractometer Highest accuracy, but no ability to orient
azimuthally
 Crystal Orientation 9

fracture characteristics of the particular material being studied. The use of x-ray
orientation relieves the need for this additional information but requires specialized
equipment. In any event, it is assumed that the crystal structure of the semicon-
ductor being examined has already been determined, since those procedures are
considered outside the scope of this book.
Gross Features. When grown from an essentially pure melt, silicon, germanium,
GaAs, InSb, and many other materials have as their most slowly growing planes
the {Ill} family. Even though thermal gradients may offer severe growth con-
straints, it is virtually impossible to grow a crystal by Czochralski or fioat zone
without some trace of {Ill} planes being visible. Zone leveling and Bridgeman
growth, however, usually completely obliterate such features. Vapor-phase growth
of these materials also usually has (111) planes as the most slowly growing ones,
but this can change with both the choice of feedstock and the concentrations used.
For example, Te-transported Si has (l00) faces as the slow ones. Further, most
semiconductor vapor-phase crystal-growth conditions (e.g., for silicon epitaxy) are
chosen to give replicas of the seeding surface and to produce as few facets as possible.
When pulled crystals (Si, Ge, etc.) are grown in the [111] direction, and if the
top is quite fiat, the (111) plane perpendicular to the growth direction can develop
and large "flats" will be visible. If the crystal diameter is increased more slowly
as it is being grown so that the crystal grows out at an angle near 70° [the angle
between the (111) and the (111), (111), (llI) planes], flats will occur where the (111),
(111), and (llI) planes are tangent to the growing crystal. An example of this is
shown in Fig. 1.8. If the crystal starts growing in, i.e., reducing in diameter, and
if the angle is again near 70°, (111), (TIl), and (lII) facets will develop and will
be rotated 60° on the crystal from the previous set.
Ordinarily, regardless of the angle at which the top grows out, six ridges will be
visible at the point where facets should be found. When a straight-sided crystal
is grown, depending on specific growth conditions, it may have either three or six
marks extending down the sides. Three of these will be relatively flat; they are due
to the (111), (1TI), and (111) planes and will always show. The other three will
be raised and correspond to the (111), (111), and (TIl) planes.
When other orientations are grown, the same general features occur. That is, there
are marks where the various (111) planes intersect the growing periphery of the

Fig. 1.8. Silicon crystal grown in [111] direction and

showing pronounced (111) faceting.
10 Semiconductor Measurements and Instrumentation

crystal. Figure 1.9 shows typical tops for (111), (100), and (110) grown crystals and
also indicates the various crystallographic directions with respect to the ridges and
facets.
In looking for natural features, caution must be exercised, since they may be
confused with artificially induced growth constraints. For example, a zone-leveled
crystal grown in a boat with a smooth, flat surface and then subsequently broken
into several chunks could show an apparent facet on some of the pieces. If the history
ofthose pieces were unknown, an erroneous orientation might be assumed. Likewise,
if a crystal were observed which had a regular cross section but was long compared
with its cross-sectional dimension, it might be assumed that the crystal was hexagonal
or perhaps rhombohedral. However, if there were some unexpected growth condi-

( 111)

(110 )

( 100)

Fig. 1.9. Shape of silicon-crystal tops for various growth orientations.

 Crystal Orientation 11

tions, the crystal could, for example, be cubic, and growth in the (Ill) direction
then be enhanced by a vapor-liquid-solid (VLS) process. When several facets are
visible, a measurement of their relative angles will often allow the orientation to
be determined. If the crystal is sizable, a protractor may suffice, but for small samples
or small facets on a large sample, a vertically illuminated microscope coupled with
a precision goniometer4 ("microgoniometer") is required.
Cleavage Qr Fracture. Most brittle semiconductors exhibit cleavage planes, and
if these planes are known, they can be used for orientation. Silicon, germanium,
and diamond cleave most easily and most often between (111) planes, whereas for
the III-V compounds, (110) planes are most likely to separate.
If the semiconductor surface is sandblasted, it will usually chip out pieces in such
a manner that the cleavage planes are exposed. In this case optical orientation
techniques to be described later can be used without the requirement for first etching
the surface. Thin samples such as silicon can be broken by placing them on a resilient
backing such as a stack of absorbent paper and pressing down in the center with
a blunt probe (e.g., a pencil eraser) until they shatter.
Typical fracture patterns for the low-index planes (Ill) and (100) are shown in
Fig. 1.10. If azimuthal orientation within the pieces is desired, it can be determined
by remembering that the traces of the cleavage planes for materials which break
along (111) planes are identical with those of the exposed planes of a (111) etch
pit, so that the directions of Fig. 1.11 * can be used. While it might at first be
considered that fracture for orientation is destructive and very wasteful, it can
sometimes be used with little or no additional loss or damage over that which
normally occurs. For example, the seeding tip of Bridgeman crystals can be broken
off to determine the approximate orientation, and a slight increase in the chipping
of the edges of silicon slices is often observed where the traces of (111) planes are
tangent to (100)-oriented slices. Further, under some circumstances, it may be less
expensive to break a slice than to use some of the more elegant methods to be
mentioned later.
Twin Planes. If the material in question has only a single twinning plane, and
if that plane is known, visible twins can be used to establish directions. Si, Ge,
diamond, and most III -V compounds twin only on a (Ill) plane.
Etch Pits. 5 The etch-pit shape can be observed in a microscope and used to make
*See the discussion of etch pits below.

[11 oJ [010J
/ /

(111) (100)

Fig. 1.10. Fracture patterns of (111)- and (lOO)-oriented silicon slices.

12 Semiconductor Measurements and Instrumentation

1 1.15

10 1
1
(100)
~ 1
(111) Z
(110)

1320t n 1 1.1
(112) (221 )

(a)

[011J ['-ioJ [110J

11 /[OOU \ i [111J
[112J
!
[OllJ ~~~[011J
I I t£ ~[10il
<[>-.1001
I
/1
[011J

(100) (111) (110)

(b)
Fig. 1.11. Stacking-fault and etch-pit geometry and orientation. These
drawings are applicable to cubic crystals (a) having a (Ill) stacking-fault
system and (b) when using a {Ill} selective etch. Well-formed (110)
etch pits are hard to generate in Si. Overetching may change their
character and produce serious error.

a rough determination of plane, but the most useful aspect is that it allows directions
in the plane of a thin slice to be rather easily determined (a thing not readily done
otherwise). The use of etch pits depends on the availability of a very selective etch
which preferentially exposes a given orientation. For diamond and zinc blende
structures, etchants specifically for (111) planes are readily available and commonly
used. For this class of etchant, if the surface were originally near a (111) plane,
there would be little three-sided inverted pyramids (tetrahedra) etched in the sur-
face. For a (100) plane, four-sided pyramids will result. In the case of (110),
a diamond-shaped aperture is formed. The surface patterns are shown in Fig.
1.11 along with azimuthal directions and relative dimensions. 6 Etchants that
are suitable for dislocation etch-pit studies are also applicable to orientation work,
since well-developed pits (whatever their source) are the prime requirement. Nu-
merous specific etch formulations are tabulated in Chap. 2, and the reader is referred
to them as well as to the etchants used specifically for optical orientation. In addition
to the more usual aqueous etchants, many molten metals produce sharp, well-defined
pits. If contacts are removed from devices, it is often found that enough micro-
alloying occurred to allow the original slice orientation to be determined. Slow
evaporation (thermal etching) and various high-temperature vapor-phase reactions
 Crystal Orientation 13

Silicon 100 Silicon 110

Silicon 111

Fig. 1.12. Optical-orientation patterns for materials which develop

(lll)-bounded etch pits. (Micromech Manufacturing Co.)

also can give etch figures useful for orientation. In any case, care must be taken
to ensure that only known planes are exposed. Most etchants, after prolonged time,
either round off comers or show higher-order planes. In some circumstances the
original shape of the pit may be so changed that the initial planes are no longer
recognizable. Germanium (110) surfaces in particular are quite susceptible to a
change in apparent orientation because of overetching. In some materials, the
etch-pit geometry can be radically changed by the etchant. For example, diamond
may develop either (111) or (100) pit faces, depending on etch composition. There-
fore, when using etch pits whose history is unknown, considerable caution in inter-
pretation is indicated.
If stacking faults are available, they too can be used for orientation purposes.
In the diamond and zinc blende structures such faults occur along (111) planes, and
hence their intersection with the surface produces the same pattern as that of an
etch pit. Stacking faults are prevalent in epitaxial layers and may sometimes be
seen directly with the aid of a phase- or interference-contrast microscope. Otherwise
etching is required (see Chap. 2 for details). Even if etching is required, they have
the advantage of not rounding off as etch pits often do. Thus, accurate measurements
of the side lengths can be made and deviations from symmetry used for determining
a small amount of misorientation. For very small misorientations from the (111)
plane, Ref. 7 gives directions for converting relative lengths into the amount of
misorientation.
If the etch-pit geometry is unknown, the angles between the exposed planes can
be determined, and by assuming that they are low-index, an assignment can often
be made by comparing the measured angle with those in Table 1.3. For some cases,
a graduated rotatable stage combined with a metallurgical microscope will suffice
for making the measurements, but usually a microgoniometer is required.
Optical Reflecfograms. 8 - 18 More accurate optical orientation can be accomplished
by observing the pattern which etch or fracture pits reflect back from a beam of
collimated light impinging normal to the surface. The little facets act as mirrors
and return the light in well-defined patterns. Typical reflectograms for
14 Semiconductor Measurements and Instrumentation

{ 111 }-bounded etch pits in cubic crystals are shown in Fig. 1.12 along with directions
in the plane of the crystal. Two slightly different optical systems as shown in Fig.
1.13 may be used for producing the light figures. When constructing the shape of
expected reflections from geometrical considerations, it should be remembered that
because of the sidewall angle of most pits, a beam must suffer an additional reflection,
as shown in Fig. 1.13, before emerging. If the physical surface is slightly misoriented
from the crystallographic plane, the image will be asymmetrical. By measuring the
amount of tilt necessary to produce a symmetrical pattern, the amount of misorienta-
tion of the crystal lattice from the physical surface is directly determined. The
azimuthal position of the spots relative to the sample also allows directions in the
plane to be uniquely determined.
The success and accuracy of the reflectogram method depend on both the equip-
ment used and the generation of sharp, well-defined pits. Table 1.5 lists both aqueous
and molten-metal etches which are suitable. The former are easier to use than the
others but provide less accuracy than the metals. The pits may also be formed by
abrasive cleaving, i.e., lapping or sandblasting, but ifthe cleavage planes are different
from slow etching planes, a different interpretation from Fig. 1.12 is required. 16 In
addition, the mechanism used for holding the slice or crystal and changing its
orientation relative to the screen must be sturdy and have precision-measuring
capability if any but the very crudest orientation is to be done.
Polarity Differentiation. For crystals of the diamond family, the (111) and (111)
faces appear identical, but for crystals with zinc blende structure, this is not true,
since each double layer of the stacking sequence consists of one sheet of component
A atoms and one sheet of component B atoms. Thus, depending on whether the
crystal is traversed in the [111] or a [111] direction, A atoms or B atoms will first
be encountered. A similar disparity exists between the [0001] and the [0001] direc-
tions ofwurtzite crystals; so in either case differences in such characteristics as etching
behavior and x-ray scattering are to be expected.
For an original determination, anomalous x-ray dispersion is most applicable. 20 - 22
This method makes use of the fact that x-ray reflections from (111) and (111) or
(0001) and (0001) faces of noncentrosymmetric crystals will have slightly different

Reflection
from main Spat diameter
surface

(a) ( b)

(c)

Fig. 1.13. Optical-orientation geometry.

 Crystal Orientation 15

Table 1.5. Etches for Optical Reflectograms

Semiconductor Etch Reference

Silicon 5% sodium hydroxide in water at 85°C for 5 min

50% sodium hydroxide (by weight) solution or
19
50% potassium hydroxide (by weight) solution at 65°C for 5 min
Molten indium at 600°C, remove indium with HCI 12
Molten Ga at 500°C, remove Ga with HCl 12

Germanium I part (volume) hydrofluoric acid (49%) 19

1 part (volume) hydrogen peroxide (30%)
4 parts (volume) water at 25°C for I min
Molten indium at 450°C, remove indium with HCI 12
Molten Ga at 137"C, remove Ga with HCI 12

GaAs I part (volume) HN0 3 (60%), 1 part water 18

Molten Ga at 800", remove Ga with HCI 12

InSb Molten indium at 350°, remove indium with HCl 12

GaSb Molten Ga at 500°, remove Ga with HCl 12

lnAs Molten indium at 600°, remove indium with H 2 SO 12

A1Sb Molten aluminum at 800°, remove aluminum with NaOH 12

intensities which can be calculated from scattering factors. If the crystal is electrically
active, the sign of the piezoelectric voltage can be used for face determination. 23
After a unique determination is once made, differences in etching characteristics
may be used. 23 - 27 Table 1.6 lists some appropriate etches, but most of them are
somewhat technique-oriented; so care should be exercised in their use and inter-
pretation.
For some materials, e.g., GaAs, one set of (111) planes may grow more slowly
than the other. When this occurs, a crystal grown in the [111] direction will have
a shape distinctly different from one grown in the [TTT] direction. If the shape is
not completely symmetrical, optical reflectograms can also be used for face determi-
nation if the original growth direction is known. 16 This is because etch or fracture
pits developed on the two faces will be rotated 60° (for cubic crystals) from each
other in the plane of the surface and thus the reflection pattern and the sample
outline will bear a different relation to each other depending on which face is
reflecting.
X-Ray Goniometer. If the wavelength of the x-rays used and the spacing of the
desired plane are known, the angle at which coherent scattering, or "reflection," is
expected can be calculated. The source and detector may be set at the proper angles
and the surface of the crystal rocked until a maximum occurs. It follows that the
desired crystallographic plane makes an angle () with the beam and thus lies along
the reference plane of Fig. 1.14. If the surface of the crystal does not also lie in
this plane, it is misoriented by the difference between the two. The angle () for a
given plane is found from
. ()
sm = nA.
2d

where A. is the x-ray wavelength being used and d the spacing between the planes
16 Semiconductor Measurements and Instrumentation

Table 1.6. Etches for Polarity Determination

Material Etch" Comments References

AISb I H 20 2 + I conc. HF + I water for 26

I min, followed by I conc. HCI +
I conc. HN0 3 for 2 s

CdS 6 fuming HN0 3 + 6 glacial acetic Sulfur film forms on Cd surface. 24

{OOOI } acid + I H 20 for 2 min Hexagonal pits on sulfur surface

{OOOI } I conc. HCI + I conc. HN03 Cd surface grainy, sulfur surface 24

develops conical etch pits

CdSe 30 conc. HN0 3 + 0.1 conc. HCI + Cd surface develops hexagonal-shaped 24

{Ill} 10 glacial acetic acid + 20 of 18N pits, both surfaces develop
H 2S0 4 for 8 s at 40°C selenium films

CdTe 3 HF + 2 H20 2 + I H 20 for 2 min Triangular etch pits on tellurium 24

{1I1 } surface

GaAs 2 HCI + I HN0 3 + 2 H 2O Ga face has etch pits, As face none 25

{Ill}

I HN0 3 +2 H 2O Ga face has pits, As face none 23

GaSb 2 conc. HN0 3 + I conc. HF + Etch pits on Ga face 26

I glacial acetic acid for IS s

HgSe 6 conc. HCI + 2 conc. HN0 3 + 3 H 2O, Se surface develops triangular etch 24
{Ill} 2-5 min intervals at 25°C, remove figures, Hg surface develops
film in 50 HN0 3, 10 acetic, I HCI, craterlike structure
20 of 18N H 2SO 4

HgTe I conc. HCI + I conc. HN0 3 I-min Mercury surface develops triangular 24
{Ill} intervals after chemical polishing etch pits, Te surface has fiat, grainy
in 6 conc. HN0 3 , I conc. HCI, appearance
I H 2O

InAs O.4N Fe3+ in conc. HCI for 30 min Etch pits on In face 26

InP O.4N Fe3+ in conc. HCI for 1.5 min 26

InSb 2 conc. HN0 3 + I conc. HF + I Etch pits on In (111) face 26

{Ill} glacial acetic acid, 4 s

0.2N Fe3+ in 6N HCI Hexagonal etch figures on In face 29

triangular figures on Sb face

SiC 6% CI2 + 26% 02 in argon at Etch pits on {1I1} Si face 27

{Ill} 850-900°C, fused 75% NaOH, 25%
Na20 2 at 700°C

{OOOI } Molten Na 20 2 + NaN0 2 Smooth Si surface, rough carbon 28

surface

ZnS O.5m K 2 Cr 20 7 in 16N H 2S0 4 for Sulfur surface irregular, triangular 24

{Ill} 10 min at 95°C etch figures on zinc surface

ZnTe 3 HF + 2 H 20 2 + 1 H 2 0 for 2 min Film on zinc surface, triangular 24

{Ill} etch figures on tellurium surface

" All parts by volume. Conc. HN0 3 = 70%. Conc. HF = 48%.

 Crystal Orientation 17
X-ray
detector

X-ray Reference
source plane

Crystal (which must be

Fig. 1.14. X-ray orientation. rotated about point A)

in question. The d value may in turn be calculated from the equations of Table
1.7 if the lattice spacing is known. Table 1.8 gives the angles for GaAs, Ge, and
Si when using the eu KG' line. Some care must be taken at this juncture, since more
than one plane can sometimes have the same lattice spacing and hence the same
8 value. An example is the (333) and (511) planes. In order to prevent misin-
terpretation, more than one order can be checked; for example, also look for a (111)
reflection. Depending on the actual atomic positions, reflections from some planes
may be very weak and difficult or impossible to find. Therefore, before wasting time
looking for a particular plane, one should determine whether or not reflections are
really expected. For the diamond lattice, they are expected only when

Table 1.7 dValues for Cubic Crystals

Cubic d= _ _ _a _ __

Tetragonal

Hexagonal

Orthorhombic

Si Ge GaAs

d100 5.43A 5.66 5.65

duo 3.83 3.99 3.99
dU1 3.13 3.26 3.26
d 123 1.56 1.63 1.62

Table 1.S. Bragg angles 8, for X-Ray Diffraction of CuK", Radiation

(Wavelength i\ = 1.54178 A)

Silicon, Germanium, GaAs,

Reflecting Planes a = 5.43073 A a = 5.6575 A a = 5.6534 A
(hkl) (± 0.00002 A) (± 0.0001 A) (± 0.0002 A)

III 14°14' 13°39' W40'

220 23°40' 22°40' 22°41'

311 28°05' 26°52' 26°53'

400 34°36' 33°02' 33°03'

331 38 ° 13' 36°26' 36°28'

422 44°04' 41 °52' 41 °55'

18 Semiconductor Measurements and Instrumentation

h2 + k 2 + [2 = (4n - 1) for n = any odd integer

h2 + k 2 + [2 = 4n for n = any even integer
Various manufacturers make equipment expressly designed for orientation work.
In these, the detector may be set at twice the Bragg angle, and the crystal holder
slowly rotated (usually by hand) about one axis only. If the crystal is badly mis-
oriented, it is conceivable that the x-ray maximum cannot be found, since no amount
of adjustment about one axis can bring a randomly oriented plane into position
to reflect into the detector. Some latitude is built into the machines, however, in
that the detector usually has a slit or line aperture so that if the beam is deflected
slightly to the side, it may still be found. The observed angle will not, however,
be exactly correct. Normally, an auxiliary holder is added which allows the crystal
to be rotated about two axes so that a true maximum can be found and the alignment
can be more accurately performed. Because of these difficulties of aligning the
specimen with the beam, the x-ray goniometer is used only if the approximate
orientation is already known; otherwise a Laue pattern must first be made.
Laue Method. If a wide band of wavelengths is used instead of monochromatic
radiation, reflection spots will occur on the film for the same conditions as before,
i.e.,
nil. = 2dsin 8
but 8 can now be fixed and an appropriate II. from the "white" source will give rise
to the various maxima. The interpretation of this method is somewhat involved,
and the reader is referred to Refs. 2 and 3 for detailed instructions. Despite a greater
complexity, it does allow any orientation to be determined without prior knowledge
of growth features or etching characteristics.
Sawing to Orientation. Orientation for sawing can be done either by building
a combination crystal jig which can be used in both the orienting machine and the
saw, and the crystal transferred back and forth, or by having a sawing jig only.
The latter is simpler to construct but requires cutting a test slice, checking the
orientation of that slice, and then making the required corrections. If lapping to
orientation is required, fixtures with adjustable stops can be used. 30,31

REFERENCES

1. F. F. Nye, "Physical Properties of Crystals," Oxford University Press, New York, 1960.
2. Charles S. Barrett, "Structure of Metals," McGraw-Hill Book Company, New York, 1952.
3. Elizabeth A. Wood, "Crystal Orientation Manual," Columbia University Press, New York,
1952.
4. Tadami Taoka, Eiichi Furubayashi, and Shin Takeuchi, Gonio-Microscope and Its
Metallurgical Application, Japan J. Appl. Phys., 4:120-128 (1965).
5. Arthur P. Honess, "The Nature, Origin and Interpretation of the Etch Figures on
Crystals," John Wiley & Sons, Inc., New York, 1927.
6. S. Mendelson, Stacking Fault Nucleation in Epitaxial Silicon on Variously Oriented
Silicon Substrates, J. Appl. Phys., 35:1570-1581 (1964).
7. M. P. Diment, Orientation Dependence ofStl!-cking Fault Geometry, Solid State Electron.,
11:1177-1178 (1968).
8. R. H. Wynne and Colman Goldberg, Preferential Etch for Use in Optical Determination
of Germanium Crystal Orientations, J. Metals, 5:436 (1953).
9. J. W. Faust, Jr., "Etches for Imperfections in Silicon and Germanium," Electrochemical
Society Meeting, May 1955.
 Crystal Orientation 19

10. G. A. Wolff, J. M. Wilbur, Jr., and J. C. Clark, Etching and Orientation Measurements
of Diamond Type Crystals by Means of Light Figures, Z. Elektrochem., 61:101-106
(1957).
11. G. H. Schwuttke, Determination of Crystal Orientation by High Intensity Refiectograms,
J. Electrochem. Soc., 106:315-317 (1959).
12. J. W. Faust, Jr., A. Sagar, and H. F. John, Molten Metal Etches for the Orientation of
Semiconductors by Optical Techniques, J. Electrochem. Soc., 109:824-828 (1962).
l3. R. Dreiner and R. Gamache, Precision Orientation of Germanium in the [111] Direction
Using Alloy Pits, J. App!. Phys., 33:888-891 (1962).
14. John G. Gualtieri and Albert J. Kerecman, Analysis ofEpitaxially Grown Semiconductor
Layers by Means of Light Figures, Rev. Sci. Instr., 34:108-110 (1963).
15. J. W. Edwards, The Orientation of Cubic Semiconductor Crystals by X-Ray and Optical
Measurements, Pt. 2, Semiconductor Products, 6:34 (June 1963).
16. G. R. Cronin, Polarity Determination of GaAs Wafers, Rev. Sci. Instr., 34:1151-1154
(1963).
17. G. A. Wolff, J. J. Frawley, and J. R. Hietanen, On the Etching of II-VI and III-V
Compounds, J. Electrochem. Soc., 111 :22-27 (1964).
18. Isamu Akraski and Hiroyuki Kobayasi, Etching Characteristics and Light Figures of
the (111) Surfaces of GaAs, J. Electrochem. Soc., 112:757-759 (1965).
19. ASTM F 26-66, "ASTM Book of Standards," Part 8, American Society for Testing and
Materials, Philadelphia, 1968.
20. D. Coster, K. S. Knol, and J. A. Prins, Z. Physik, 63:345 (1930).
21. R. W. James, "Optical Principles of the Diffraction of X-Rays," G. Bell & Sons, Ltd.,
London, 1958.
22. E. P. Warekois and P. H. Metzger, X-Ray Method for the Differentiation of (Ill) Surfaces
in AIIIBv Semiconductor Compounds, J. Appl. Phys., 30:960-962 (1959).
23. M. S. Abl~hams and L. Ekstrom, Etch Pits, Deformation and Dislocations in GaAs, in
Harry C. Gatos (ed.), "Properties of Elemental and Compound Semiconductors," Inter-
science Publishers, Inc., New York, 1960.
24. E. P. Warekois, M. C. Lavine, A. N. Mariano, and H. C. Gatos, Crystallographic Polarity
in II-VI Compounds, J. Appl. Phys., 33:690-696 (1962).
25. S. G. White and W. C. Routh, Polarity of Gallium Arsenide Single Crystals, J. Appl.
Phys., 30:946-947 (1959).
26. H. C. Gatos and M. C. Lavine, Characteristics of the {Ill} Surfaces of the III-V
Intermetallic Compounds, J. Electrochem. Soc., 107:427-433 (1960).
27. Robert W. Bartlett and Malcom Barlow, Surface Polarity and Etching of ,B-Silicon
Carbide, J. Electrochem. Soc., 117:1436-1437 (1970).
28. Karl Brack, X-Ray Method for the Determination of the Polarity of SiC Crystals, J. Appl.
Phys., 36:3560-3562 (1965).
29. H. C. Gatos and M. C. Lavine, Etching and Inhibition of the {III} Surface of the III-V
lntermetallic Compounds-lnSb, Phys. Chem. Solids, 14:169-174 (1960).
30. S. Ipsen Mathiesen, L. Gerward, and O. Pedersen, Preparing Polished Crystal Slices with
High Precision Orientation, Rev. Sci. Instr., 45:278-279 (1974).
31. R. Butz, B. Krahl-Urban, and K. Mench, A Precision Goniometer Polishing Jig, Rev.
Sci. Instr., 44:485-487 (1973).
 2
Crystallographic Defects
and Their Observation

There are numerous crystallographic defects that may occur during growth and
subsequent processing of crystalline semiconductors. Many of them are undesirable
at any level, some are helpful in moderation, and some, such as foreign doping atoms,
are absolutely necessary. Table 2.1 summarizes these defects (both the good and
the bad) and lists some of the methods of detection. The ensuing discussions expand
on that table and in many cases give explicit directions for their observation.
Occasionally some mention may be made regarding the cause and/or cure of some
particular defect, but defect control is not the theme of this chapter. The shape
defects, while not reflecting crystallographic imperfections, can still be serious enough
to subsequent processing to demand some attention.

2.1 POINT DEFECTS

The first several defects listed in Table 2.1 belong to the category of point defects.
Such defects are all local in nature and are characterized by the fact that the
imperfect region can be removed and a perfect section substituted without additional
lattice distortion.
Vacancies. The simplest point defect is the vacancy (sometimes called a Schottky
defect) in which a single atom is missing from the lattice. If the crystal has a zinc
blende structure (III-V), there can be two kinds of vacancies, one for each compo-
nent. Further, they may be in various charge states. Vacancies are thermodynami-
cally stable and will therefore be present in all crystals. The equilibrium number
N may be calculated from

where No is the number of atomic sites, Ev is the energy required to create a vacancy
and is in the order of 2 to 2.5 eV for Ge and 2.5 to 3 eV for Si, k is Boltzmann's
constant, and T is the temperature. 1 Such calculations are not very helpful in
determining the actual number present, since by rapid cooling after crystal growth,
a greater than equilibrium ilUmber can be quenched in,2 and by interactions with
various impurities, the equilibrium number can be depressed. 3
For high-melting-point materials which can be used for field-emission tips in
21
22 Semiconductor Measurements and Instrumentation

Table 2.1. Summary of Material Defects

LATTICE DEFECTS

Defect Method of detection

LOCAL
(Minimum of Long-Range Disorder)

Vacancies Density measurements, inference from electrical measurements

Interstitial Inferred from electrical properties
Antistructure Inferred from electrical properties
Foreign atom-vacancy EPR, indirect inference, optical spectra
complexes
Foreign atoms (singly) Electrical properties, spectrographic or wet analysis
Dislocations Etching, x-ray, electron microscopy
Stacking faults Etching, x-ray, electron microscopy
Twins Etching, x-ray, electron microscopy
Lineage Etching, x-ray, electron microscopy
Single grain boundary Etching, x-ray, electron microscopy

AGGREGATE

Polycrystalline regions Etching, x-ray, electron microscopy

Voids Microscopic examination
Cracks Selective etching
Inclusions (separate Birefringence, x-ray, electron microscopy
phase)
Inclusions (composi- X-ray, electron microscopy, microprobe, etching, Tyndall scattering
tional variation)

MISCELLANEOUS

Residual lattice strain X-ray, birefringence, etch rate, electrical properties, mechanical
displacement
Mechanical surface Etch rate, dislocation density, decoration, electrical measurements,
damage x-ray

SHAPE DEFECTS
(No Atomic Misplacement)

Faceting Visual
Habit change Visual
Variation in surface Profilometer, Light scattering
contour

SURFACE DAMAGE

Cracks See Table 2.10

Strain Bowing, x-ray
Dislocation networks See Dislocations above
Stacking faults Etching, x-ray, electron microscope

RADIATION DEFECTS

Point defects See vacancies, etc., above

Amorphous layers Electron diffraction, atomic backscattering
 Crystallographic Defects and Their Observation 23

field-ion'microscopes, vacancies can be directly observed,4 but there is no way to

estimate their density. If large numbers are present, very precise density measure-
ments can indicate vacancy fiuctuations,5 For example, PbS may have up to 10 19
vacancies per cubic centimeter. Silicon and germanium, however, even near their
melting points, have only about 10 18 per cubic centimeter and at room temperature
have far less. Nevertheless, careful density measurements made on dislocation-free
silicon do indicate a considerable variation in vacancy density.6 The diffusion rate
of many impurities depends on the number of vacancies present and may thus be
used to infer relative vacancy concentrations. 7 If it can be demonstrated that va-
cancies are electrically active and separable from other active defects, the measure-
ment of the Hall coefficient may allow the number to be estimated. This approach
must be used with caution, however, because there are a number of impurities having
activation energies close to those presumed to be due to vacancies. Indeed some
of the older data may very well have been obtained from deep-level impurities and
not from vacancies. Probably the most definitive way to study vacancies is by use
of electron paramagnetic resonance (EPR).8
As numbers of vacancies coalesce into clusters, they will eventually collapse and
form dislocation loops. These loops are more readily detected than either the single
vacancies or the clusters and can, for example, be seen either by etching, in which
case shallow depressions is the usual configuration, 9 by transmission electron micro-
scopy in which the complete loop is visible,IO or by copper-precipitation decoration.
Loops are more likely to occur in dislocation-free material, since if there were
dislocations, the vacancies could interact with them rather than form clusters.
Interstitials. An interstitial is an extra atom occupying space between the normal
lattice sites. For a zinc bien de crystal, four distinguishable interstitials are possible,
one for each component and each interstitial completely surrounded by group III
or V atoms. If an interstitial and a vacancy occur in close proximity, the pair is
called a Frenkel defect. A combination of optical and EPR spectra, electrical data,
and calculations has in the past been used to identify interstitials. However, in some
cases atoniic backscattering can be used to study them directlyp,12
Complexes. From single-atom defects a wide range of more complex multiple
defects can be built. There are, for example, two vacancies side by side (divacancy),
a vacancy with a trapped electron (referred to as an F center in alkali-halide crystals),
a vacancy beside a substitutional impurity (a vacancy-phosphorus atom pair in
silicon is an E center), and many more. The fact that most of them were observed
in silicon does not imply that it forms more kinds of defects but rather that it has
been more extensively studied than other materials. The detection methods are
similar to those of vacancies and interstitials. In addition, the rate of precipitation
of a fast diffuser can sometimes be used to estimate the number of defects which
promote nucleation. 13 ,14 Such a procedure has been used for Ge (lithium precipi-
tation), but it is not clear whether it is vacancies and/or vacancy-impurity complexes
being followed.
Foreign Atoms. Foreign atoms may occur either as interstitials or in the place
of normal atoms. In the latter case they are referred to as substitutional impurities.
In compound semiconductors, one component atom may occur on a site intended
for the other, e.g., in GaAs, As may be in a Ga position or vice versa. These are
called antistructure defects. Widely dispersed foreign atoms cause little lattice dis-
ruption and are commonly detected indirectly through their effect on the electrical
properties of the semiconductor. These methods are discussed in Chap. 3. In
24 Semiconductor Measurements and Instrumentation

Table 2.2. Nonelectrical Methods for Impurity-Concentration Determination

Method Advantages Disadvantages

Emission spectroscopy More readily available Limited sensitivity

equipment
Solid mass spectroscopy Great sensitivity Very susceptible to surface
contamination
Ion mass spectroscope Combines mass-spectrometer Equipment complex, calibra-
sensitivity with spatial tion difficult
resolution of x-ray micro-
probe
Neutron activation Great sensitivity Special equipment, not very
useful for III-V compounds
Charged-particle activation Light-element sensitivity More difficult than neutron
activation
Radio tracer Great sensitivity Special equipment, impurity
to be studied must be
available as a radioactive
isotope. Not applicable to
routine evaluation
X-ray microprobe Nondestructive, can be Limited accuracy
used to examine very
small volumes
Optical absorption Equipment widely available Limited sensitivity,
limited applicability,
requires special sample
preparation

addition, a number of analytical techniques are available which, while not ordinarily
as sensitive as resistivity-based measurements, are generally specific to a given atomic
species. These are summarized in Table 2.2 and discussed in Chap. 9.
Internal friction, or mechanical damping, is often dependent on defects in the
lattice and thus may be used to study them. However, interpretation is difficult and
application is limited. 15,16
Optical-absorption spectra are applicable in some instances. For wavelengths less
than those corresponding to the band edge, the attenuation is very high and little
data relating to impurities can be obtained. However, for very high impurity con-
centration, there is some smearing of the tail, as indicated by the shaded portion
of Fig. 2.1. For wavelengths longer than A, the general background level of absorp-
tion as shown by the dotted line depends on the free carrier density and may be
used to estimate shallow donors or acceptor concentrations. Superimposed on that

Fig. 2.1. Optical-absorption coeffi-

cient vs. wavelength. The rapid
drop at A occurs when the band
edge is reached, while the peaks at
-- B, C, D, etc., may be due to either
impurity or host lattice absorption.
The level of the dotted line changes
with the number of carriers present,
B 0 and in general increases as the
Wavelength square of wavelength.
 Crystallographic Defects and Their Observation 25

background are absorption peaks, e.g., B, C, and D, which may be due to either
the lattice itself or some impurity. For the more common semiconductors, the band
edge occurs in the 1- to 2-/Lm range and the region of possible usable spectra extends
to at least 20 or 30 /Lm. Applications have been primarily to impurities which are
not electrically active but which may occur in concentration of several parts per
million. Examples of these are oxygen in Si and Ge, carbon in Si, and radiation-
induced defects in Si and Ge. In the infrared region, the absorption frequencies
are primarily a function of the atomic species and their bonding. Thus, isotopes,
e.g., 12C and 14C, are readily separable, and if a carbon-oxygen complex forms, the
frequency will shift and it too can be distinguished. There is, of course, the problem
of initial identification of a given line. Remember that like other optical spectra,
there may be more than one line per impurity, and that with multiple impurities
there may be interference between them or between them and the host lattice. For
example, one of the Si-Si lines lies very close to one for O-Si and reduces sensitivity.
Sometimes by cooling the sample, the offending peak can be shifted or reduced in
amplitude relative to the one of interest.
Before such spectra can be used for quantitative analysis, calibration must be done
by using samples with known levels of impurities. These calibrations should be
approached with caution, since the independent measurement required may respond
to the impurity in a different form. For example, a chemical analysis for carbon
might detect interstitial and substitutional carbon and the carbon in precipitated
silicon carbide, whereas the particular optical-absorption line being studied may be
due only to substitutional carbon. Experimental procedures will vary with the
material, but ASTM procedure F 121 for determining oxygen in silicon can be used
as a guide.
Careful measurement of lattice changes can be used to deduce the amount of
impurity present. Such measurements do not, however, distinguish between impur-
ities. Ion scattering can be used, although sensitivity is not very good and impurities
must have appreciably higher atomic mass than the hostP

2.2 DISLOCATIONS

There are several varieties of dislocations, 18-22 one of which is shown schematically
in very simple form in Fig. 2.2h. It occurs at the termination of a sheet of extra
atoms and is an edge dislocation. If the crystal is subjected to shear as in Fig. 2.2a,
the crystal will be deformed by bonds along the shear-line shifting, and dislocations
will be formed. Dislocations already present will move by glide in a direction
perpendicular to the dislocation line and along a slip plane. There will be crysta1-
lographically preferred glide and slip directions, so that dislocations so formed will
not be random but will be in orderly arrays as indicated in Fig. 2.3.

A B C

2 3 4J 5
Fig. 2.2. Edge dislocation. The disloca-
tion can be formed by shearing which
I
causes (a) bonds A-2, B-3 to change to
(b) bonds A-I, B-2. (0 1 ( bl
26 Semiconductor Measurements and Instrumentation

Fig. 2.3. The intersection of edge dislocations with the surface

Surface A of a crystal. In this case they all lie along slip planes.

Figure 2.4 is a photograph of a slice in which the intersection of the dislocations

with a (111) slice surface has been defined by small etch pits (this procedure is
described below). In this case three sets of intersecting slip planes are indicated.
As can be deduced from their geometry, they are all (111 )s, and indeed the {111}
family is the most active one in the diamond and zinc blende structures. Such
pronounced slip is common and can occur if a slice, or a long crystal ingot for that
matter, is nonuniformly heated or cooled so that differential thermal expansion can
cause the necessary shear force.
The dislocation could also move by adding or removing a row of atoms at the
edge of the extra sheet, as shown in Fig. 2.5. Motion of this kind is perpendicular
to the slip plane; it is called climb and can occur only by transporting additional
atoms or vacancies by diffusion to the dislocation. Typical of this process is the
gold-induced climb in silicon. Gold will diffuse interstitially very rapidly and can
then become substitutional at the dislocation. Figure 2.6 is a photograph of a portion
of a (111) silicon surface which was etched once before the dislocation moved and
once afterward. Motion was parallel to the (111) glide planes and therefore due
to glide and not climb. The velocity of dislocation travel in semiconductors has been
studied by using this same technique, i.e., by carefully polishing a sample, giving
it a dislocation etch to show the dislocations, stressing it, e.g., by three-point loading,
and again etching. 23
High-temperature annealing of a crystal which has plastically deformed leads to
polygonization. The edge dislocations move to planes perpendicular to the glide
plane so that they are arrayed in tilt boundaries which separate near perfect regions
of crystal, as illustrated in Fig. 2.7. Polygonization is often observed in silicon after
prolonged heat treatments, e.g., after an epitaxial deposition. Based on the previous

Fig. 2.4. A (Ill )-oriented silicon slice in which the

severe slip has been delineated by etching to show
the emergence of dislocations. The lines lie along
the intersection of other (Ill) slip planes with the
viewing surface.
 Crystallographic Defects and Their Observation 27

-- Additional
atom added
Fig. 2.5. Movement of a dislocation by the diffusion
1
of atoms to the end of the "extra plane." The disloca-
tion could have traveled in the opposite directions by
atom 1 diffusing away from its site.

discussions of glide, one might suppose that the orderly alignment of dislocations
in rows as was shown in Fig. 2.3 would always indicate the trace of a slip plane.
Such lines might, however, be tilt boundaries instead. If the material being studied
is a previously well-evaluated one, the etch pits used to demonstrate the dislocation
can be used to determine the orientation of the dislocation arrays. (See etch-pit
geometry in Chap. 1.) Figure 2.8 shows a close-up view of rows of etch pits along
(1 1I)-plane slip lines and another along polygonization boundaries which run
perpendicular to the slip surfaces. Note that if the outline of the etch pit is used
as a guide, the fact that the two rows run in different crystallographic directions
is readily apparent.
Should a segment of an edge dislocation be pinned at each end and the center
move by glide, it can keep expanding, eventually give a loop of dislocations, and
still retain the segment. More movement will cause the first loop to grow larger
and the segment to be again distorted and continue to generate loops. The additional
dislocations continually generated from the original segment in this way have been
observed in silicon and germanium. 25 ,26

\ / (111) Traces
[ ]
110 ~-V~
1\
Fig. 2.6. Movement of dislocations in silicon caused by thermal-induced stress. The
large pits were formed by high-temperature vapor etching before movement, the small
ones by a later room-temperature etch. The sides of the etch pits are traces of (111)
planes intersecting the (111) surface of the crystal and are parallel to the slip direction.
Hence motion of the dislocation was along a slip direction and therefore not induced
by climb. (Courtesy of Dr. Lawrence D. Dyer, Texas Instruments Incorporated.)
28 Semiconductor Measurements and Instrumentation

Fig. 2.7. Effect of polygoniza-

tion. Initially the crystal was
deformed as in (a) and had many
dislocations lying in the slip
plane. After polygonization in
(b), the dislocations have coa-
lesced into low-angle grain boun-
daries separating slightly mis-
oriented regions of perfect crystal.
(From F. R. N. Nabarro, "Theory
of Crystal Dislocations," Oxford
University Press, London, 1967.)

There are a variety of other sources which will also generate loops, spirals, and
other geometries. For example, loops are produced from a pinned-edge dislocation
by climb. If only one end is fixed, spirals will grow, and if the dislocation has both
edge and screw character, climb will produce helices (which are found in germanium
and silicon24 and sometimes are mistaken for screw dislocation). The screw disloca-
tion, however, is very local in nature, whereas a helix may have diameter and pitch
of micrometer dimensions. The collapse of a large vacancy cluster will give a
dislocation loop; they are found in silicon and germanium. 1O,27-30
The edge dislocation just described is not the only type of dislocation to be found.
There are, for example, screw dislocations, more complex edge dislocations involving
two extra planes, and several varieties of partial dislocations which occur at the
boundaries of stacking errors. 31
Occurrence. Dislocations can be introduced at nearly every stage of processing.
In initial crystal growth, dislocations in the seed will propagate into the new growth
as each succeeding atomic layer is added. Should sudden growth-rate changes occur,
extra dislocations will generally occur. Misfit dislocations will be generated at the
boundary between new and old growth if the new growth is of different lattice
spacing from the old. Such circumstances occur during heterocrystal growth, e.g.,
germanium on gallium arsenide, or even for the same materials if the doping is
radically different, as in the case of a lightly doped silicon layer on a heavily doped
substrate. Initial growth onto unclean surfaces will lead at best to a higher dislocation
density but more often will also produce stacking faults and, in some cases, gross
polycrystallinity.
Dislocations introduced after crystal growth are all associated with the SUbjection
of the crystal to excessive mechanical stress. Such stress can originate from unequal
heating or cooling, from the diffusion of impurities into the lattice, or from forces
applied externally during shaping operations such as sawing, lapping, and polishing.
Should precipitation of a second phase occur during either the initial crystal cool-
down or subsequent annealing cycles, dislocations are likely to be formed because
of differential thermal contraction. In silicon, for example, Si0 2 precipitation can
cause dislocation networks, loops, and stacking faults. 32 Also, prismatic loops have
 Crystallographic Defects and Their Observation 29

.... :.
..,
~... ..~.
"..
,w··"
-...."'. "...... ;
.......
,. ..... ~

.... - .... ..... "'1';,: ......:w .........

'

(a)

( b)
Fig. 2.8. Etch-pit orientation (a) along slip lines and (b) along polygoniza-
tion walls. (Photographs courtesy of Dr. Kenji Morizane, Texas Instruments
Incorporated. )

been reported in erbium-doped (ZnCd)S33 which presumably arise from inclusions

of an erbium compound.
Dislocation Detection by Etch-Pit Formation. The region near a dislocation line
usually etches more rapidly than the rest of the crystal and thus develops etch pits,
as indicated schematically in Fig. 2.9. 34 - 37 Depending on the etch, the pit may be
conical and rather featureless, or it may reflect the crystallographic structure. These
pits afford a simple method of determining the number of dislocations which intersect
the surface (dislocations per square centimeter). It is the one most commonly used,
and indeed "etch pit" and "dislocation density" are often used synonymously.
The success of a particular etchant can be very much dependent on its exact
composition and on a great many other conditions such as surface cleanliness, initial
etchant temperature, and the ratio of volume of etchant to semiconductor surface
area. Surface damage will also produce etch pits, but they will usually become
flat-bottomed as etching proceeds and the damage is removed. Dislocation pits,
however, continue to etch rapidly for the length of the dislocation and thus usually
maintain pointed bottoms. Because of this shape, a true dislocation pit will appear
dark under a bright-field-microscopic examination, since the sloping sides will not
reflect incident light back into the objective. The flat-bottomed surface-damage
pit will reflect light back and will appear bright. Examples of both types of pits
can be seen in Fig. 2.10. The flat-bottomed pits trace out the path of scratches
30 Semiconductor Measurements and Instrumentation

44'V
I

I 1

1 :
Fig. 2.9. Etch pits formed at the inter-
I
) / :I
(a) (b) section of dislocations with a surface. The
shape of the pit is a function of the
Dislocations
etchant and crystal orientation.

generated during slice polishing. Sometimes a stair-stepped or terraced pit is ob-

served. This has on occasion been described as indicative of screw dislocations 38
but in actuality is probably due to other effects.24 To minimize the effect of the
surface, i.e., to clean it and to remove surface damage which might complicate
interpretation, it is best first to polish the surface and then to subject it to the
dislocation etch. 39 Either chemical or mechanical polishing may be used. Ordinarily
a surface would not be mechanically polished specifically in preparation for disloca-
tion etching, but if it is already available, it may be used. Chemical polishing is
much simpler and in general is recommended. See Chap. 7 for polish formulations
and procedures. One exception to not using mechanical polishing occurs if it is
desired to look at the density as a function of depth. In that case, angle lapping
may be used, followed by a good mechanical polish. This procedure has been applied
to the study of extra dislocations generated at epitaxial-substrate interfaces,4o and
to depth-of-damage studies. The latter is discussed in Sec. 2.9.
Silicon has been extensively studied, and reasonably foolproof etchants and
techniques have been developed, but even with them there are resistivity ranges
which do not satisfactorily respond, and really dependable counting can be done
only on (111) faces. For III-V compounds, a dislocation terminating in a group
III atom may etch differently from one ending in a group V atom. Further, either
type of dislocation can intersect either (hkl) or (lifT) planes, and depending on
the value of hkl may not develop etch pits at all. For example, InSb dislocation
pits develop only for In dislocations intersecting (110) and (111) surfaces [and not
(TTT) surfaces]. In addition, a variety of non-dislocation-associated etch figures can
develop on the various surfaces; so interpretation in terms of dislocations is more
difficult than for Si and Ge.

Fig. 2.10. Etch pits from dislocations and

from scratch damage. The black ones are
due to dislocations.
 Crystallographic Defects and Their Observation 31

Under most circumstances, the (111) planes of diamond and zinc blende crystals
are the slowest to etch, so that the pits are bounded by them. Thus, on a (Ill)
surface the pits will be triangular. (For more details on orientation see Chap. 1.)
However, some etchants may etch most slowly in (100) directions. In that case, a
(111 )-plane etch pit will still be triangular in cross section, but the sidewalls will
make different angles with the face and the outline will be oriented differently as
in Fig. 2.11a. If either pit occurred on a round (111) slice, they would be indis-
tinguishable, but on a crystal which showed natural faces there could be differences.
For example, in Fig. 2.11h a tetrahedron is shown with both sketched in. In one
case the pit mirrors the face. In the other it appears rotated 60 It is also occa-
0
•

sionally possible to have peaks rather than pits. Such peaks can arise for at least
two separate reasons. One is that small amounts of masking material may remain
on the surface and prevent etching in that region. If the mask is small, it will soon
undercut and give a very small peak which will look under a microscope much like
a pit. Usually they can be distinguished by using pseudo-Becke-picture framing
(see Chap. 8). Another major reason for raised regions is the fact that impurities
insoluble in the dislocation etch may precipitate at dislocations and impede etching.
In this case, of course, the dislocation is still being delineated, although for a different
reason.
While etching procedures are available for the more common materials, and it
is therefore usually unnecessary to consider whether the pits which develop actually
occur at dislocation terminations, that problem must be faced with either new
materials or new etchants. Such correlation may be made in a variety of ways.
The one used originally35 was to examine the grain boundary between two slightly
misoriented regions of a germanium bicrystal. The orientation difference can be
accurately determined by x-ray spectrometry, and the number of dislocations ex-
pected because of that difference can be calculated. The surface can then be etched,
and if the etchant is really delineating edge dislocations, a row of pits spaced
accordingly should be observed. If suitable bicrystals are not available, dislocations

( 100) planes
etching most
slowly
- + [110]

(111) planes
etChing most
slowly

(a)

( 111)

(100)

Fig. 2.11. Etch-pit orientation on a (111) surface. (b)

32 Semiconductor Measurements and Instrumentation

can also be introduced in known amounts by bending. However, without extensive

annealing the dislocation distribution is uneven, and not really as predicted. There-
fore, before bending is used as a method for introducing a known and calculable
amount of dislocations, the sample must be thoroughly annealed. 41 The dislocations
generated by bending can also be used to study the effects of etchants on dislocations
terminating specifically in either constituent of a compound semiconductor.42 -44
If a crystal is cleaved, and each face etched, there should be a correspondence
of pits if only dislocations are being displayed,24 since the dislocation pierces both
faces. As a variation, a surface can be polished, dislocation-etched, photographed,
have more material removed, and be dislocation-etched again. If the etchant is
showing dislocations, there should be good correlation, although if the dislocations
are not normal to the surface, the pits from the two levels will be laterally displaced.
This procedure can be repeated numerous times on the same face and a whole
sequence of photographs taken which will trace the path of the dislocations through
the crystal. If the photographs are converted to slides, the dislocations will show
as dots on a clear background. Then if equal thicknesses are removed each time
and if the slides are stacked in sequence, a striking three-dimensional model results. 45
Unfortunately, while this correspondence method can show that spurious pits are
not produced, it will not show whether all dislocations are being etched. X-ray
topography, which was not in use when the early etching work was done, can be
used to demonstrate a one-to-one correspondence and is probably the best method,
though also the one requiring the most specialized equipment and operators. A
scanning electron microscope (SEM), using the signal generated from shallow dif-
fused silicon p-n junctions, has enough sensitivity to observe diffusion-induced
dislocations, and thus allows a correlation between surface etch pits and the emer-
gence of dislocations. 46,47 (It is of interest to observe, however, that in Ref. 47,
etching was used as the standard with which to evaluate the SEM.) Table 2.3
summarizes etchants that have been reported for Si. Of these, Dash and Sirtl are
good general-purpose etchants, but for special cases such as (100) faces or heavily
doped crystals the others may prove more effective. If the reader is not satisfied
with the results of a particular etch, he should by all means try others, always
remembering that if he deviates too far in composition, it may not be dislocations
which are being delineated. In general, the etchants, unless otherwise noted, will
give pits bounded by either (111) planes or some nearby ones having a [llO]-zone
axis. Overetching in general tends to produce more rounding and distortion. By
carefully noting the exact shape of the pit, the direction of the dislocation can
sometimes be determined.
Misfit dislocations formed during heavy-concentration planar emitter diffusions
into (111)-oriented slices will lie primarily parallel to the surface rather than intersect
it as shown by Fig. 2.3. However, etched grooves caused by them can sometimes
be seen after several minutes of etching in ultrasonically agitated Dash etch. 56
Dislocations lying deep beneath the surface, either misfits at an epitaxial-substrate
junction or the result of contamination, can be seen by angle beveling and looking
at their intersection with the bevel surface.
Table 2.4 summarizes the etchants used for Ge. Better results are usually obtained
if a polished surface is used, but CP-4, one of the more common etch polishes, will
also produce dislocation etch pits. When it is used directly, a 600-grit lapped surface
is acceptable. If a chemical prepolish is used with some of the other etchants, the
 Crystallographic Defects and Their Observation 33

Table 2.3. Silicon Dislocation* Etchants

Etch Face Comments Reference

Sirt! (111), (110) 1-7 min 48

Modified Sirt! (111) Works better on low-resistivity material
than Sirt!. Made by mixing 110 ml of
Sirt! with 25 ml HF, 30 ml HN03 ,
100 mlH 2 0
Dash etch (Ill), (110) 4 h, works moderately well on (100) faces. 25
Reduce to few min for thin layer
Copper etch (Ill) Most of the metal-ion etch ants were developed 49, 50
No. I in an attempt to produce sharper, better-
defined pits
Copper etch (Ill) 51
No.2
Sailor's etch (111) 2 h ultrasonic, will also show Shockley 52
partials but not stair-rod dislocations
ASTM (lll) 4 h (described in full detail below) ASTM F47
Mercury (Ill), (100) 2 min 53
Dow (lll), (110), (100) 5 min with ultrasonic agitation. Works 54
("Secco") reasonably well on (100). Gives circular pits

* See Ref. 55 for a general discussion of the different kinds of dislocations to be found in Si.

amount of oxide left on the surface will affect the size and number of pits. The
removal of the oxide by an HF dip just prior to the dislocation etch allows the
formation of numerous very small pits apparently not associated with dislocations. 62
Etching too long will cause some pits to grow larger and will obliterate others, thus
giving a false number. Hence normal times may need to be reduced when heavily
dislocated material is examined. ASTM standard procedures are available for
dislocation etchlng (ASTM F 47) which are particularly useful in defining the sort
of sampling plans that should be used to ensure that representative pit densities
are reported.
Dislocation Detection by Decoration. A wide variety of elements will segregate
along dislocations. In some cases, they are easier to detect than the dislocation itself.
Such procedures are not without pitfalls, however. For example, copper, which is
widely used for decorating silicon dislocations,25 will precipitate along regions of
high oxygen content in the form of needles and platelets,63 and presumably there

Table 2.4. Dislocation Etchants for Germanium

Etchant Comments Reference

CPA Gives conical pits on (100), (1l0), and (lll) surfaces 34,36
Superoxol Develops considerable structure in pits. Diluted I: 1 with H 2 0,
will develop spiral terraced pits and very small pits in
addition to those normally associated with edge dislocations 57, 58
Cyanide 100°C for 3-4 min (1l1) surface 59
WAg 60
Dash
Russian Room temperature for 8-12 min shows edge dislocations and spiral 61
pits on (100), (110), and (lll) surfaces
34 Semiconductor Measurements and Instrumentation

are other impurities that will behave similarly. Should its concentration become
too high, it is quite possible to precipitate enough copper to cause additional dislo-
cations. 64 The general procedure when deliberately decorating is to choose a fast-
diffusing material, saturate the sample at some relatively high temperature, and then
rapidly cool it so that the diffusant solubility decreases rapidly. It will then differ-
entially precipitate at dislocations and can be seen optically. The exact procedure
will vary with the material, but for Si25,63,64 involves heating it along with a source
of copper for up to an hour in order for the copper to diffuse through the sample.
Care must be taken to ensure that the sample is free of oxide; otherwise entry of
the copper will be blocked. The source can be elemental copper in a closed tube
with the silicon, but more often it is a few drops of copper nitrate solution allowed
to dry on the surface. Note that the diffusion furnace will in most cases become
contaminated with copper and therefore cannot be used for normal semiconductor
processing. The more common semiconductors are all opaque to visible light; so
some form of infrared image converter is required. For silicon, the widely available
I-JLm image converters can be used, but germanium requires wavelengths in the
vicinity of 1.8 JLm. Imaging is much more difficult in that region but vidicons and
line-scanning equipment are available which will work with reasonable sensitivity.
Dislocation Detection by X-Ray and Electron Microscope. There are several x-ray
methods that have been used for studying dislocations and other crystal defects.
Double-crystal spectrometry was one of the earliest of these. 65 -69 It depends on the
fact that departures from a perfect crystal should make the line width broader, and
for randomly located dislocations, the width is proportional to the square root of
the dislocation density. For dislocation densities in the 103 to 106 per square centi-
meter range, the double-crystal spectrometer is usable, although the sensitivity is
not adequate, and other approaches are more rewarding.
Topography70-87 has developed as the most useful and powerful x-ray method
for studying semiconductor defects. There are several forms of topography, but all
map local deviations from crystal perfection onto photographic film or an x-ray
imaging tube and can show single dislocations* and lattice strain due to impurities,
precipitates, etc. Its application to dislocation counting is in the low-concentration
region as opposed to the rather high concentrations required if double-crystal
spectrometers are to be useful. If topography is used for highly dislocated samples,
two deleterious results occur. One is that spatial resolution on the film is not
sufficient to separate them, and the other is that if they are too close together, the
region between them is also strained and contrast is reduced. The transmission Lang
topographic method was the first one applied to semiconductors and was used to
show single dislocations in silicon.
To make visualization of the dislocation portrayed by topography somewhat easier,
stereo pairs can be taken and viewed conventionally,73 or the two photographs can
be superimposed and printed in separate colors,e.g., red and blue. Then viewing
is done with one eye covered with a red filter and the other with a blue fiIter. 88
For Lang photographs, orientations of (hkl) and (lifT) for the reflection plane are
normally used, but it is possible to make them by taking one photograph, rotating
the crystal a few degrees around the normal to the diffraction planes, and taking

*Actually, copper decoration has comparable or better resolution than x-ray topography, but it has
the disadvantage of being destructive and of being applicable to a much narrower range of materials
than x-ray topography.
 Crystallographic Defeds and Their Observation 35

another. Such a procedure has the advantage that different angles can be chosen
to enhance the effect89 and that it is applicable to Borrmann's topography.90
The continuous x-ray spectrum can be used for crystallographic studies. In this
case, rather than varying the angle to give a diffraction maximum for a given
wavelength and crystal spacing, the polychromatic radiation is allowed to fall on
the crystal, and the position(s) of the diffracted maximum are determined photo-
graphically. If a similar arrangement is used, but with monochromatic radiation
(Debye-Scherrer), a few spots will occur for a single crystal, but if the sample has
many randomly oriented crystallites, a continuum of spots arranged in circular
patterns will result. As the crystallites become less randomly oriented, the circles
reduce to shorter and shorter arcs, so that they can be used as some measure of
perfection, although it is much more gross than any of the other methods discussed.
It is of some use, however, in determining whether vapor-deposited layers have any
ordering. It has been suggested that if a source is chosen that has both a sharp
high-intensity line and good continuous background, a single-crystal sample will give
well-defined Laue spots, while a randomly oriented composite will give a Debye-
Scherrer powder pattern. Varying degrees of distortion will then give patterns
intermediate between the two extremes. While such a procedure is not very sensitive,
it was used to characterize silicon crystals in their early stages of historical develop-
ment. 91 A similar procedure has been used in metal studies in which rings of widely
separated spots are observed using monochromatic radiation in well-annealed sam-
ples. After cold working, the individual grains which originally gave spots are
distorted and the spots tum into areas which really are a smear of smaller spots
and which can sometimes be interpreted in terms of the amount of plastic flow which
took place. 92 Even without the continuous-wavelength radiation, crystal imperfec-
tions will cause the spot shape to change and in some cases to elongate along certain
directions. These "diffuse" reflections are indicative of structural defects such as
stacking faults and twinning and have been used in the study of diamonds 93 and
radiation-damaged Si. 94
Transmission electron diffraction can be used in a fashion similar to x-rays to
observe dislocations and other defects, and interpretation is similar. It does have
the disadvantage of requiring a very thin sample, which usually implies a destructive
measurement.
References 95 to 103 are a collection of articles covering x-ray and electron-
diffraction studies as they directly relate to silicon. There are also scattered refer-
ences to Ge, GaAs, and other materials, but the preponderance of journal entries
involve Si.
Dislocation Detection for Other Materials. Dislocations in diamond may be de-
tected by x-ray topographyl04 or etching in fused KN0 3 or a hot 02 atmosphere.105
GaAs dislocations have been studied by both etching106-108 and x-ray topo-
graph. 80,109-113 Schell etch will produce dislocation pits on Ga (111) faces. Grocker
etch will show pits on both (111) surfaces. The arsenic pits will be triangular and
the gallium pits conical. On (111) surfaces, if the etch pits are triangular, they will
be roughly bounded by (111) planes. A-B etch develops pits on the arsenic surface
and W-R etch only on Ga surfaces.
Hg",Cd(1_",le 114 can be studied with an etch of Hn0 3, H 2 0, HCl, and Br2.
Etching, decoration, and x-ray topography have been used for GaP. 109, 115 For
the etch, use a concentrated methanol solution of iodine with a trace of bromine.
Decoration can be by either copper or zinc precipitation.
36 Semiconductor Measurements and Instrumentation

Modified CP-4A (2-1-1) will show InSb dislocations terminating on In (111) faces,
while O.2N ferric ion in 6NHCI works on (111) faces. 1l6,117
Seventy-five percent NaOH, 25 percent Na 20 2 at 700°C or 6 percent CI, 26 percent
O 2,68 percent argon at 850°C gives dislocation pits on (111) faces (Si) of ~ Sic. 118
Etch pits have been observed in ZnS crystals after etching in diluted H 20 2 at
80°C, but a one-to-one correspondence to dislocations has not been demonstrated. 119
For PbSe and PbSeTe dislocation etchant, use a KOH, H 20, glycerol, and H 20 2
mixture. 120, 121
Etching in hot HCI for 2 to 6 h defines dislocations (probably both edge and
screw)122 in GaP.

2.3 STACKING FAULTS

Stacking faults,123-144 as the name implies, are due to errors in the stacking of
layers and can occur only when the succeeding layers are different. Figure 2.12a
is the standard schematic of a stacking fault. It shows one originating when a layer
is omitted (intrinsic) and when an extra layer has been inserted (extrinsic). The
intrinsic form could presumably form by the collapse of a vacancy cluster as shown
in Fig. 2.12b and either the extrinsic or intrinsic by a number of crystal-growth errors.
For example, in some regions the atoms might nucleate wrong or there might be
a thin foreign platelet which when overgrown produces a stacking fault. Further,
some kinds ofline defects, coupled with climb, can act as sources of extra (or missing)
planes. One example is the Bardeen-Herring source, which is thought to contribute
to some of the faults observed in silicon. If the fault formed as in Fig. 2.12b or
from a source like Bardeen-Herring, the outline will be hexagonal or circular (Fig.

c c c c

-
b b
b b

---
a a
...... a 0

'--...L-/"
./
a
.........
c
b i [111]
~
b
a b 1
[111]

-
a b a
./ ......... c ~
b
...... b b b
a a a
a
(a)

·• .......
•••••••
. Intrinsic
stacking fault

~
•• ••
• ••••••• _c_ \ a I_c_
• ••••••• b \
_a_,
-- \
c
b
I
1--
1_0_
b

c \ 0 I c
•••••••• b
a
\
, __
c
b_1
/ b
a
••• •••••••
•••••••
• •• c \ a I
- - - " - - - \ - - I --~
b \ c I
c
b
a L-;-.J ----"a-
• •••••••
(b) (c)
Fig. 2.12. Stacking-fault description.
 Crystallographic Defects and Their Observation 37

Fig. 2.13. Circular stacking fault in Si. The

surface is (Ill). It was Sirtl-etched and photo-
graphed with Nomarski interference. The crystal
had been annealed at 1200°C for 4 h. (Photo-
graph courtesy of Dr. Lawrence D. Dyer, Texas
Instruments Incorporated.)

2.13).138 For faults introduced during growth, the region around them usually does
not deform as shown in Fig. 2.12a but rather propagates during any additional crystal
growth as a differently stacked region separated by additional faults on various (Ill)
planes as illustrated in Fig. 2.12c. Their traces intersecting the surface will give the
stacking-fault outlines shown in Fig. 2.14. Should two of the same type be nucleated
close together, the boundary will disappear where they touch and will produce the
pattern shown in Fig. 2.1Sa. Should the two be of opposite type, an overlap of the

(100) ( 110) ( 1 11 )
Fig. 2.14. Outline of silicon stacking faults on various planes. All were formed
during initiation of epitaxial overgrowth and were delineated by Sirtl etch. (Photo-
graphs courtesy of Kenneth E. Bean, Texas Instruments Incorporated.)
38 Semiconductor Measurements and Instrumentation

pattern will appear as in Fig. 2.15b. Stacking faults can also be linear; e.g., they
can be very thin and comprised of two closely spaced faults which, when viewed
on edge, appear as a line.
Occurrence. Stacking faults in semiconductors are commonly observed in epitaxial
growths 40,124-133,144 and are occasionally seen in bulk melt-grown material which
has been annealed32,136-138 and in surfaces which were mechanically damaged and

(0)

j'#;( Thl. 00' ;. of dlffmot typ'

1\\
\

(b)

(c )

Fig. 2.15. Composite patterns produced by multiple stacking faults

growing together. When epitaxial layers are thick and/or the density
is high, very complex outlines composed of many faults can occur.
(a) The same type combining. (b) Two of one type and one of the
other. (c) Photograph showing these combinations.
 Crystallographic Defects and Their Observation 39

subsequently annealed. In the latter case they are predominantly line faults rather
than the closed-figure forms widely seen in epitaxial material. In some cases such
faults occur after oxidation but without previous mechanical damage. The origin
of these faults is possibly the strain arising from either oxygen or fluorine 123 com-
plexes formed during heat treatment. Faults observed in epitaxial layers can nucleate
at slip lines, scratches, and regions of impurity segregation, and from particulate
matter on the initial growth surface. Most of them originate at the initial growth
surface, and because of their well-defined geometric growth behavior, they will all
be the same size when viewed from the top surface provided that the layer thickness
is uniform. If smaller-sized faults are also visible, additional nucleation occurred
during the growth cycle, probably from particulate matter in the feed stream.
Observation. Stacking faults may be observed by x-ray topography, by surface
etching, or in many cases, by direct viewing of a natural growth surface using some
form of interference contrast. *,129,144 The latter is possible because of small step-
height differences and has the advantage of being completely nondestructive. There
is, however, the possibility that some of the faults will anneal out during subsequent
heat cycling. In that case the outline will still be present and might be counted. 145
Etching would not define them and would not give an erroneous number. Next
to interference contrast, etching is the handiest and most commonly used method
of examining stacking faults. It produces grooves where the fault planes intersect
the surface, and thus gives the outlines which were shown in Fig. 2.14. Table 2.5
summarizes the most appropriate etchants. Usually they just define the outline, but
Sailor's etch appears to be sensitive to the type of partial dislocation at the corner
of the fault and hence can assist in interpretation. The stair-rod dislocations %<110)
at the corners of the conventional stacking faults are not delineated, but the 1~ <112)
dislocations which terminate the linear faults are enhanced. 127 Occasionally a
triangular etch figure will be observed which will have an etch pit at each corner.
It is possible that the figure is not really defining a triangular stacking fault but
'Such as the Nomarski interference attachment available for most microscopes.

Table 2.5. Etchants for Stacking Faults

Application Etch Notes Reference

Si (lll) Dash 15-20 min at room temp 127

Sirt! 15-30 s 147
Iodine 127
Sailor's Up to 4 h at room temp enhances 127
delineation of a/6 (112) partial
dislocations

(100) Dash, Sirt! 127

(110) Dash 127

Ge (Ill) WAg 40

GaAs 2 ml H 20, 1 ml HF, 8 mg AgNOa,

(Ill) both faces 1 g CrOa, 10 min at 65°C 108
(100)
(110)

~-SiC (Ill) Fused salt 146

40 Semiconductor Measurements and Instrumentation

rather the intersection of linear faults and the etch pit delineates the dislocations
associated with them. Square faults in (100) material apparently cannot have stair
rods at all four corners, but the dislocations that are there usually etch along with
the fault outline. Thus the (100) outlines usually show dislocation pits at the cor-
ners.134
X-ray topography and transmission electron-beam diffractions are both applicable
to stacking faults.

2.4 TWINS

When two contacting regions are of different orientation but still are oriented so
that at the interface each portion shares the same crystallographic plane, the two
regions are twins and the interface between them is the twin plane. Nearest-neighbor
positions are maintained for the atoms on each side of the interface but next-nearest-
neighbor positions are violated. Crystal symmetry and energy considerations dictate
which planes will serve as twin planes. For diamond and zinc blende structures
(111) tWin planes are experimentally observed, although from symmetry alone, (112)s
would also be possible. Should a crystal twin, and then twin again, the additional
boundaries are sometimes planar and are referred to as higher-order twinS. 148,149
The (221) in particular has been observed in Si. These boundaries, of course, have
more lattice distortion associated with them than do the original twins.
Occurrence. Twins usually develop in semiconductors during growth as a result
of temperature fluctuations or chance contamination. Metals quite often show twins
owing to mechanical deformation, but the brittle semiconductors will only occa-
sionally twin in that manner, and then only after deformation followed by heat
treatment.
Detection. When twin planes intersect the surface, the lines can often be directly
observed because of slightly different rates of growth of the two orientations.
Sandblasting will usually produce an easily discernible difference, because as the
material fractures, the cleavage planes make different angles with the surface when
the crystallographic orientation changes. This in turn produces a sharp change in
the reflectivity as the twin plane is crossed. A similar effect is produced by a selective
etch which will provide etch pits, since the pits will have different orientations and
will then reflect differently. Examples are shown in Fig. 2.16. Etches suitable for
crystal orientation are thus useful for the optical differentiation of twinned regions.

(a) (b)
Fig. 2.16. Germanium block with a twin boundary. The
(a) side was given a selective etch and is very clear. Side
(b) was ground with a 120-grit wet paper and requires a
more grazing light to show the boundary. In the latter case,
wetting the surface will make the effect more noticeable.
 Crystallographic Defects and Their Observation 41

Table 2.6. Etchants for Twin Definition

Si CP4A

Ge CP4, Superoxol, white-etch, aqueous solution of 10% KOH, and 10% potassium ferri-
cyanide. Etching will ordinarily give either a step or a groove, depending on whether
there is only one, or a multiplicity of twins. If optical microscopy does not have
the resolving power to separate grooves, replication-transmission microscopy can be
used
InSb I HF, 3 HN0 3 , 6 H 2 0
GaSb I HF, 3 HN0 3 , 6 H 2 0

Etches recommended for dislocation definition will produce grooves or steps at twin
boundaries which can then be used for boundary delineation. For very closely spaced
twins such as occur in dendrites, cleavage will usually produce steps at the twin
planes which can then be observed optically or by replication and electron-beam
microscopy.150 Etchants suggested for some of the more common materials are listed
in Table 2.6. If required, the orientation on each side of the line can be determined
by the methods discussed in Chap. 1. If such orientations are consistent with the
presence of a twin plane (see Fig. 2.17), it can be inferred. When the separation
plane (and not just its trace on the surface) is well defined, its orientation may be
determined to see whether or not it is consistent with the allowable twin planes for
the material in question. From a practical standpoint, any long, straight boundary
is probably a twin, * since otherwise the boundary tends to be jagged or curved.
It might, however, be a grain or lineage boundary, or even a long scratch. In the
latter two cases surface roughening or etching will not give a change of reflectivity
upon crossing the boundary. Etching a grain or lineage boundary will produce
myriads of etch pits along the boundary which can be interpreted in light of ASTM
F 47 (discussed in Secs. 2.5 and 2.6).

2.5 LINEAGE

Lineage is used to describe a mosaic of regions with small angular deviations from
one another. It now is seldom observed in silicon and germanium because of the
close control of growth conditions.
Occurrence. The origin of lineage is not well understood, but in growth from
*It may not be a first-order plane, however.

First order Second order

{Ill} ~ {lIS} {1l4} ~ {1l4}
{IlO} ~ {IlO}, {1l4} {221} ~ {221}
{lOa} ~ {22I}

Fig. 2.17. Possible sets of diamond-lattice orienta-

tions having twin relationship. Neither list is all-
inclusive, but they do include the more commonly
observed one. The photograph shows a slice from
a silicon boule which started growing in the [100]
direction and simultaneously twinned at four posi-
tions to (221) planes. These grew together to pro-
duce the second-order twin boundaries shown criss-
crossing the slice. (Courtesy of K. E. Bean, Texas
Instruments Incorporated.)
42 Semiconductor Measurements and Instrumentation

the melt it is assumed that if the growth front is dendritic the dendrites may be
rather easily bent because of their high temperature. Then, when the space between
them fills in, a mosaic occurs. Crystals grown from defective seeds will continue
to show lineage, and thick epitaxial growths onto an elastically deformed substrate
can ultimately cause misorientation of the layer.
Detection. When the deviations are minimal, a double-crystal spectrometer or
other x-ray technique may be required, but for most purposes, standard dislocation
etching will suffice. The intersection of two slightly misoriented blocks will give a
line of dislocations which increases in linear density as the misorientation increases.
Therefore, the dislocation etch ants listed in Sec. 2.2 can be used to search for lineage.
ASTM F 47 for silicon has defined "lineage" as being present when the density of
dislocations as indicated by etch pits exceeds 25 per millimeter along a line of 0.5 mm
minimum length. When the density increases to the point where the etch pits
are no longer individually distinguishable, it is common to refer to it as a "grain
boundary." Slip may give similar dislocation.. densities but is due to an entirely
different set of misfortunes. When the geometric pattern of the dislocations is in
accord with the expected slip pattern, slip should of course be suspected. In the
case of heteroepitaxy, if the lattice spacings of the overlayer and the host are not
identical, as the various regions which were nucleated at different localities on the
surface grow together, there will be a high density of dislocations even when each
region is identically oriented with its neighbors.

2.6 GRAINS AND GRAIN BOUNDARIES

Grain boundaries occur where regions with gross differences in orientation join.
These various orientations can arise when randomly nucleated regions grow together
or when regions again come in contact after several intervening twinning steps. The
existence of grains or their boundaries can be inferred from the presence of the other,
so that detection may be based on finding either of them.
Detection. Because of the large differences in orientation there will be high
dislocation densities, as was just described for the junction of mosaic blocks. Thus,
if the surface is subjected to a dislocation etch, grooves at the boundary will result.
The orientation of the etch pits over the surface should also be examined, and if
they show different orientation at different places, grains or twins are indicated.
On a gross scale, large areas of etch pits will reflect light differently depending on
their orientation, and will facilitate locating individual grains. Most solutions used
for chemically polishing a given semiconductor will also reveal grain boundaries,
Table 2.7. Etchants for Delineating Grain Boundaries

Material Etchant* Time, min Temp

Si Sirtl 0.5 Room

\-3-6 6 Room
1-3-10 60 Room

Ge 1-1-1 1.5 Room

CP4 2 Room
WAg 5 Room
0.1 ferricyanide 20 80"

* See Chap. 7 for etch formulations and safety precautions.

 Crystallographic Defects and Their Observation 43

Fig. 2.1 8. Grain boundaries of a silicon boule

delineated by selective deposition of SiO as the
boule was held above the melt for a few minutes
before cooling. Magnification approximately 2 X.

but delineation can be enhanced by a proper etchant applied after the chemical
polishing. Specific directions are given in Table 2.7 for the more common semi-
conductors.
Thin layers suspected of having grain boundaries must be treated with care;
otherwise the whole layer may be removed during the delineation process. If the
thickness is known, it can be reconciled with the etch rate to give a maximum
allowable etch time. When this is not possible, one should start with one-tenth to
one-fourth of the recommended times and see if definition is adequate.
Polycrystalline areas may also be delineated by lapping the surface in an aqueous
slurry of 1,800-grit abrasive, or by sandblasting the surface with an abrasive whose
particle size is less than 5 p.m. Either preparation will present a surface in which
the variously oriented areas appear as different shades of gray. It may be necessary
to vary the way the light is reflected from its roughened surface in order to see the
polycrystalline areas. Grain boundaries are also sometimes decorated by selective
depositions. As an example, Fig. 2.18 shows the bottom ofa silicon polycrystal with
an accumulation of SiO along the boundaries. When the density of grains becomes
large, the x-ray techniques for observing high densities of dislocations are applicable,
as well as the changes in optical constants. 215

2.7 INCLUSIONS

Inclusions are small volumes of a separate phase included in a matrix. They may
be either a separate phase but identical composition, e.g., cubic SiC in hexagonal
SiC, or separate compositions, such as silicon phosphide in silicon.
Occurrence. Inclusions may be introduced during crystal growth, diffusion, an-
nealing, irradiation, or bombardment with high-energy particles. The determination
of how a particular inclusion originated must be made based on its content and
when first observed. Small regions of a-SiC in /J-SiC crystals can logically be
assumed to originate in crystal growth, but SiP platelets in Si observed after a
phosphorus diffusion probably grew during diffusion. 151
It is also possible to have a second phase present which originated during growth
from the melt and propagates as long columns parallel to the growth axis. Such
inclusions are found in some metallic systems, and have been reported in AISb. 152
Detection. Inclusions can usually be made visible by etching, which will leave
them standing out in relief, after which their composition can be identified by x-ray
microprobe analysis and/or electron diffraction. Cathodoluminescence combined
with an electron-beam scan can also be used to map out inclusions which are very
close to the surface. Thin samples may be examined by electron-transmission
44 Semiconductor Measurements and Instrumentation

microscope. Note that thinning operations necessary for electron microscopy often
leave residual surface deposits which may be mistaken for precipitates. Tyndall
scattering (ultramicroscopy) can be used to visually observe included particles smaller
than the resolution limits of ordinary microscopes. If the material to be examined
is transparent, commercially available oil-immersion ultracondensers and standard
microscopes can be used. 153 For the more common nontransparent semiconductors,
infrared instrumentation must be used and the resolution obtained with high-quality
visible optics will not be realized. However, the scattering can still be a measure
of the number of particles in a large volume. 155 Tyndall scattering is ordinarily
viewed at right angles to the incident light beam, but it is also possible to use other
optical arrangements to keep the direct beam separate from any scattered light.
When one phase is birefringent and the other not, examination in polarized light
will allow separation. For materials such as ZnS which may grow in a layered
structure with the hexagonal and cubic forms interleaved, the relative amount of
hexagonal type can be estimated by the degree of birefringence observed in a light
beam traversing the crystal perpendicular to the layers. 156 Cross sectioning and
etching can be used to delineate these and other gross inclusions. The sample may
be powdered when high enough concentrations of the second phase are present and
examination may be done by standard x-ray powder techniques. In some materials,
e.g., diamond, impurities precipitate in the form of oriented platelets and may be
so numerous that separate diffraction peaks corresponding to the structure of the
oriented precipitate can be observed during x-ray topography.157 X-ray topography
can also be used to search for precipitates by detecting the microstrain associated
with deformation around the precipitate. In general, such strain will produce contrast
which is independent of the plane of observation, whereas if there is no precipitate,
the contrast will be strongly dependent on the reflection plane used. 158 Opaque
inclusions can be observed by infrared microscopy. Should the material be trans-
parent in the visible range (e.g., CdS 159), observation is much easier, since ordinary
optical microscopy can be used. Viewing should be from several aspects so that
the true shape and orientation of the preCIpitates are determined.
Particles of materials which alloy with the semiconductor at low temperatures may
move about in thermal gradients in the same manner that traveling solvent-crystal
growth occurs and leave distinctive tracks. 160,161 Since the Seebeck coefficient will
be different for materials of different composition, a heated probe similar to those
described in Chap. 5 can be used to map out large included grains if fine resolution
is not required.1 62
Inclusions should be suspected if a diffusion concentration profile based on ana-
lytical measurements (rather than electrical) shows an abrupt increase as the surface
is approached. Table 2.8 summarizes the application of these methods to various
materials.

2.8 LATTICE STRESS AND STRAIN

Stress and strain can arise from work damage on the surface; from internal forces
due to dislocations, excess vacancies, and impurities of radii different from the host
material; from growth around included foreign material; from thermal gradients;
and from dissimilar materials bonded together (e.g., Si0 2 on Si). Crystals grown
from the melt sometimes have large stresses because the outer layers cooled before
the interior and partially relieved the resulting stresses by plastic flow. Then after
 Crystallographic Defects and Their Observation 4S

Table 2.8. Guide to Inclusion Detection

Matrix Inclusion Mode of observation Reference

Si Au Electron diffraction 169, 170

As X-ray topography 164
B,O,Cu X-ray topography 158, 167
SiP X-ray topography lSI, 164
Oxygen Light scattering 154, ISS
Unidentified Transmission electron microscopy 166, 167

Ge GeAs X-ray powder diffraction 163

GaAs Te Cathodoluminescence 165

Zn Infrared microscopy 168, 171

CdS Optical microscopy 159

Diamond Ni X-ray topography 157

ZnS Hex ZnS Birefringence 156

PbSnTe Metallic Surface etching 172

the whole crystal has equilibrated, the interior is in tension and the outer layer in
compression. 59 Vapor-deposited layers, whether amorphous, polycrystalline or
single-crystal, often develop severe internal stresses during depositionY3 Sawing,
grinding, and lapping cause surface stresses which in turn cause appreciable bowing
in thin slices unless the damage is approximately uniform on both sides. 174 Structures
involving semiconductor-dielectric-metal sandwiches such as in device fabrication
are particularly susceptible to differential-expansion-induced stress because of the
great disparity of expansion coefficients often encountered. Of special interest is
the case of partial covering of the semiconductor by a layer of different properties.
At the layer edge severe strain can occur, as shown in Fig. 2.19. This is typical
of behavior at the oxide windows of silicon planar devices. 176 When concentrations
of impurities are diffused into the surface, strain occurs and will sometimes propagate
damage well away from the diffused region.11 7,178
Direct quantitative values for strain can be obtained from lattice-spacing changes
or from birefringence measurements. Qualitative values can be surmised from
etch-rate behavior. Stress is calculable from a variety of stress-deflection measure-
ments, and rough estimates of its value if caused by thermal mismatch can sometimes
be made by observing the sample temperature required to change the sign of
Amountof differential

Film

Fig. 2.19. Effect of an expanding film on the

substrate lattice spacing. Region under tension
46 Semiconductor Measurements and Instrumentation

deflection. Once either stress or strain is determined, the other can be obtained by
using appropriate stress-strain relationships. For single-crystal materials the problem
is somewhat complicated because those relations will depend on the crystallographic
direction in which the stress is applied. Should only approximate values be desired,
some intermediate value of the appropriate constants can be used and calculations
greatly simplified. Most cases of interest to the semiconductor technologist will
involve isotropic glassy layers on single-crystal substrates, but polycrystalline layers
(e.g., aluminum metallization) may also be of interest. For the case of polycrystalline
layers, strain associated with variously oriented anisotropic grains will be different
for each grain and for special cases can be calculated,175 but ordinarily such calcula-
tions are not required.
X-Ray Observation.176-183 Since the Bragg angle () is given by nA. = 2d sin (), where
d is the lattice spacing, A. the x-ray wavelength, and n the order, changes in the lattice
spacing can be determined from changes in (). In order to get maximum sensitivity,
the highest order possible should be used and the equipment must be well aligned.
Two modes of operation are possible. In one, the observed lattice spacing in the
material being studied is compared with spacings in presumably unstrained samples.
In the other, spacings of different planes of some particular (hkl) family are com-
pared in the same sample. In either method geometrical errors will be introduced
which might be interpreted as residual stress. Reference 181 discusses methods for
estimating and minimizing these errors. Should the sample have been subjected
to plastic flow, some microregions will be under compression and others under
tension. If the flow was unidirectional, error can be introduced in that the overall
stress (macrostress) can be zero, but the x-ray contribution from the small local
microstressed regions will produce a line shift.180 Heavily faulted regions will also
cause some line shift unless measurements are made by the second method. The
position of contrast in x-ray topographs can be used to determine whether the strain
is compressive or tensile 182 and has been widely used to study diffusion-induced
strain in silicon. 176, 177, 178, 183
The first method is in principle quite simple and is often used for thin polycrystal-
line layers. A diffractometer can be used with the surface of the layer aligned to
the instrument. A quick scan can be made to check the preferred orientation of
the sample and see which planes have enough intensity to be used, after which careful
measurements can be made about the chosen () position. The measurement of ()
for an unstrained sample should if possible be made on the same equipment to be
used for strain measurements, but regardless, care must be taken to ensure that the
reference sample really is unstrained. Data taken from powder samples should not
be used, since appreciable strain is introduced during the powdering unless it was
prepared without any mechanical grinding by direct precipitation or deposition. A
very pure reference sample should also be used because a high concentration of
impurities can cause considerable lattice strain. For this reason all old data for
semiconductors are suspect and should be used with caution. Figure 2.20 shows
typical data for an aluminum film on a Si-Si0 2 sandwich and illustrates the variations
in () to be expected.
After measuring () and finding d, the strain Sz is given by

S - dunstrained-dmeas
z- (2.1)
dunstrained
This S is the strain perpendicular to the surface, and before it is translated into
 Crystallographic Defects and Their Observation 47

IStressed
I film
I I
60 --+--+--+--1- 28", =38.57° -+I--+--+--f--
S = 28.2 X 10- 4
--+--j---+---+- T = 2.9 X 10 9 dyn/cm"t--t----t-

50--+--+--+--1--+-~-r--1--+-~-~

(\
f40--r-r-~r-~~~f~\+-+-+-+-~
~
;
~30--+-~-+---t--H~~-~--+--+--+--f--
tF\ rStressed
o
&1 Unstressed - - I\

20 \~+--+---
1\
~-t--+--+---ft---I--++Jt----+t----l

10 ~+__+___--t-;I-J-Hj~\--\--+-
\r--+--+---
MIIIIi" I \\..
1 3~O I I T
- - - 3 8 . 5 - 2 8 .... 39.0
Fig. 2.20. X-ray diffraction traces of stressed and unstressed
aluminum films deposited over a thermally grown Si0 2 layer.
Intensity ranges for the two samples were adjusted to permit
easy comparison of peak position. (Adaptedfrom P. B. Ghate,
"Failure Mechanism Studies on Multilevel Metallization Sys-
tems for LSI," RADC F30602-70-C-0214, 1971.)

applied stress, some boundary conditions must be known. For example, if the sample
is long and thin, and the only stress TIlJ is in the long direction,

T = E,Sz
IlJ v, (2.2)

v,
where E, and are Young's modulus and Poisson's ratio* for the film. Should the
stress be uniform in the surface plane, Eq. (2.2) becomes 184
E,Sz
TIlJ = - - (2.3)
2v,
For film stresses in circular samples (e.g., metallization on a silicon slice) arising
from differential thermal expansion, and assuming no shearing forces, Eq. (2.3) is
appropriate.
Observation by Mechanical-Deformation Measurements. If the material to be
measured is glassy, as, for example, an oxide grown or deposited on a silicon slice,
x-ray methods are restricted to studying the substrate strain only, but from that,
stress in the film can also be estimated. 185 A method more appropriate to thin-film
technology and to the problems relating to stresses developed during device proces-
sing involves the deposition of the film in question onto a relatively thick substrate
*v can be assumed equal to 0.3 and will lead to errors of only a few percent for most materials.
48 Semiconductor Measurements and Instrumentation

with known properties. Then, for small deflections, no plastic flow in the substrate,
no slippage between layer and substrate, and both materials isotropic in their elastic
properties, the deflection of the composite (Fig. 2.21) is given by
d = 3wf r T,(1
2 - II f )
(2.4)
EWs2

when the sample is a circular disk and d~ws' w f is the film thickness and is much
less than the substrate thickness ws ' Tf is the stress in the film, Es and lis are,
respectively, Young's modulus and Poisson's ratio for the substrate, and r is the
distance from the center to the point of measurement. 187 Equation (2.4) can be
rewritten as
d= Kr2 (2.5)
and shows that the surface becomes a paraboloid of revolution. The deflection can
be measured by direct mechanical profiling using either point-by-point microscope
examination, a profilometer, or optical methods. Of the latter, the Newton-ring
interferometer is probably the simplest to use and will also show whether or not
the stress is uniform. If the substrate and film are both truly isotropic and the stresses
uniform over the surface, the rings should be circular and centered with respect to
the slice. Should thev not be, and such circumstances often occur, the substrate
probably had residual stress ~ in it. In any event, the simple expression ofEq. (2.4)
cannot be used, and such samples should ordinarily be rejected. Sensitivities of
2.5 X 108 dyn/cm 2 for Si substrates are possible. 188 Should a cubic single-crystal
slice be used whose orientation is other than (111), Young's modulus will show
periodic azimuthal variations which if large enough will prevent radial symmetry
of the deflection. When the surface is highly reflective, its parabolic shape will
produce a mirror whose focal length can be calculated in terms of Eq. (2.4).189 Thus,
by measuring f of the mirror, T, can be calculated.
Instead of circular wafers (slices) it is sometimes more convenient to use long,
narrow strips. In that case the stress is given by 186
Ew 2
T,= s (2.6)
6 wf R(1 - 11)

where R is the radius of curvature of the strip (the deflection is now cylindrical
instead of parabolic).

(0 ) (b)

Fig. 2.21. Bowing of a bimaterial disk.

 Crystallographic Defects and Their Observation 49

Displacement

f Film to be studied

(TI
Hole etched in
substrate

Fig. 2.22. Method of measuring deflection of thin unsupported

films.

The stresses to be expected in deposited films are generally due either to differences
in expansion coefficients between the film and its substrate or to intrinsic stress
developed during deposition. Since most films are deposited at elevated tempera-
tures and measurements are made near room temperature, contributions from both
usually occur.
For a film or thin diaphragm with no backing and having a uniform pressure
applied to deflect it, the tensile stress can be calculated from the deflection.208 If
Ii is zero, the pressure-deflection curve is parabolic; otherwise there will be a
straight-line portion near zero with a slope proportioned to Ii. An experimental
arrangement for these measurements is indicated in Fig. 2.22. If the pressure is
increased until rupture, breaking strength may be calculated. 209 Depending on the
diameter, the rupture may be explosive; so adequate shielding should be used.
Etch Rate. The rate of attack of etchants is usually dependent on lattice strain,
but such rates are difficult to calibrate. It is, however, often used to detect the
presence or absence of strain. (The lattice strain associated with dislocations makes
certain etchants effective as dislocation delineants.) Similarly, the strain caused by
cracks and other mechanical damage allows the depth of damage to be ascertained
by etching until the rate slows down and becomes constant. If there is residual stress
in a brittle semiconductor at room temperature, heating the material to a high enough
temperature to allow stress relief will generate dislocations which can be delineated
by an appropriate etchant.

2.9 MECHANICAL SURFACE DAMAGE

Surface damage, like beauty, is dependent on the eyes of the beholder and will
vary according to the methods of detection. The exact nature of the damage is still
the subject of some controversy, but it is substantially as shown in Fig. 2.23. Surface
damage might then be measured in terms of surface roughness, misorientation of
the surface due to the cracks, the number of dislocations, or the amount of residual
elastic strain. Further, since electrical effects are introduced by the mechanical
disruption, they too can be used to measure damage. Table 2.9 summarizes the variety
of measurements that have been used, and while there is reasonable agreement

Fig. 2.23. Nature of mechanical damage in semi-

conductor materials. (a) The rough surface as
depicted by a profilometer. (b) Region of cracks.
(c) Dislocation networks. (d) Elastic strain.
50 Semiconductor Measurements and Instrumentation

Table 2.9. Methods of Determining Depth of Damage

Method Reference

Constancy of etch rate 205

Angle section combined with selective etch 190
Incremental polish combined with selective etch 191
Electron microscope 192
Open-circuit photomagnetoelectric voltage 193
X-ray topography 109
X-ray double crystal spectrometer linewidth 194, 195
Diode reverse leakage current 193
Solar cell open-circuit voltage
J- V curves of electrolyte-semicol)ductor barrier 196
Infrared reflection coefficient 197
Electron paramagnetic resonance 198
Diffusion-length measurement (Morton-Haynes geometry) 199
Filament lifetime by photoconductive decay 194
Impurity precipitates 64
Residual elastic stress 200
Ion backscattering 200

among the methods, in many instances there may be substantial differences. Those
directly related to device performance [such as photoelectromagnetic (PEM) and
diode reverse leakage] have usually been considered to be better indexes, but because
of the likelihood that the dislocations of reglOn c of Fig. 2.23 will interact deleteri-
ously with impurities introduced during subsequent processing steps, the dislocations
themselves are good indicators. Surface damage occurs as the result of mechanical
abrasion during such operations as sawing, lapping, polishing, and cavitroning. It
can also be generated by careless handling with mechanical implements such as
tweezers.
Constancy of Etch Rate. The etch rate of an abraded semiconductor surface is
higher than that of a "damage-free" one and thus can be used (and indeed was
one of the earliest reported methods 205 ) to measure depth of damage. The thickness
removed before the etch rate becomes constant is taken as the depth of damage.
One disadvantage of this method arises from the fact that the damage is not uniform,
and thus the initial etching is also uneven, since it will quickly etch out deep grooves
where the damage was deepest. However, the amount of material removed is usually
calculated by assuming uniform material over the whole surface, taking the weight
loss after each etch step, and converting it to an, equivalent thickness. Such a
procedure thus gives only an average depth and underestimates the maximum
damage depth. Some precautions to be observed are: the back and sides of the
slice must be protected during etching or else the study should be made simulta-
neously on both sides; a constant etch temperature should be maintained throughout
all etching; and if a fresh batch of etch is required during the study, the etch rate
between the two should be correlated.
Sectioning Methods. There are several sectioning methods for studying surface
damage. One is to bevel the surface using the same procedures as are common
in thickness measurements (see Chap. 6). The beveled surface is then carefully
polished to remove any damage resulting from the beveling operation. After that,
the surface can be subjected to the appropriate etches to delineate dam-
age. 195,201,202,203 A better way if relatively large areas of uniformly damaged material
are available is to break the sample into several pieces, mechanically polish or etch
 Crystallographic Defects and Their Observation 51

each piece for varying times in a polishing etch in order to remove different amounts
of material, and then subject them to a dislocation etch. An example of this proce-
dure is shown in Fig. 2.24. The amount removed can be determined by weighing,
direct thickness measurements, or masking a small section of the surface during
etching and subsequently measuring the step height. To minimize the effects of the
material removal required for sectioning, the damaged side of the slice can be
mounted face down and the reverse side mechanically polished. Removal and
examination then proceed from the back and progress into the damaged region. 204
Another method of obtaining a cross-sectional view of slice damage is to cleave
the slice along a plane perpendicular to the surface, and examine the cleaved region
by x-ray topography. In order to minimize distortion, the diffracting plane should
be chosen so that the diffracted beam is as near normal to the cleaved surface as

Sawed slice surface

After 30- min mechanical polish

0.1 mil silicon removed

After 90-min mechanical polish

0.3 mil silicon removed

Above surface after 1-3-6 etch

After ISO-min mechanical polish

0.6 mil silicon removed

After 270-min mechanical polish

1.0 mil silicon removed

Above surface after 1-3 - 6 etch

After 360-min mechanical polish

1.5 mil silicon removed

After 420- min mechanical polish

(1.7mil removed) and 1-3-6 etch

Fig. 2.24. Step sequence in damage-depth determination. Magnifi-

cation 32 X in all cases. (Photographs courtesy of Jimmie B. Sherer,
Texas Instruments Incorporated.)
52 Semiconductor Measurements and Instrumentation

possible. Further, the slice should be oriented so that the incident beam, the
diffracted beam, and the normal to the cleaved surface all lie in the same plane. 109
Effect on Current Carriers. Mechanical damage induces extra free carriers which
increase conductivity and affect reflectivity. It also provides recombination centers
which reduce lifetime and increase surface recombination velocity. Thus if any of
these properties are monitored as a function of material removal, damage depth
can be estimated (see Table 2.9 for reference).
Decoration. Copper decoration can be used to indicate residual damage remaining
after annealing.
Strain Measurements. Strain associated with mechanical damage may be detected
directly by x-ray, birefringence, or warping. *
Even a very carefully mechanically polished surface may leave residual strain
which is difficult to detect directly but upon subsequent heating will produce a variety
of readily observable secondary defects. For example, silicon surfaces, mechanically
polished and subsequently oxidized, when Sirtl-etched will show a large incidence
of line-stacking faults. Scratching or indenting will, upon heating, produce disloca-
tion loops which fan out from the damaged site. 24 A silicon slice subjected to an
800°C chlorine etch after a four-point-probe resistivity measurement will often have
holes etched through the slice where the probes contacted the slice even though prior
examination of similar areas showed no discernible damage. Germanium, and to
some extent silicon, will show "crow's feet" after damage by indenting, followed
by heat treating and etching.
EPR. Electron-paramagnetic-resonance lines have been observed which are related
to surface damage, but they have not been used extensively to study damage
depth. 19B

2.10 SHAPE DEFECTS

Crystal-shape defects are primarily of two kinds. Either they are unwanted
growths, usually polycrystallites or multiple twins which project above the surface
of otherwise planar layers of vapor-grown crystals, or else they are a nonplanar but
crystallographically perfect surface which did not faithfully reproduce the original
surface contour. The spurious growths can be traced to chance contamination either
left on the slice or brought in during the crystal-growing operation. The nonreplica-
tion or shift of steps, holes, hills, etc., due to natural growth processes can be
minimized by choice of growth conditions. 206,207 They may be detected by light
scattering (either visually from an intense source such as a microscope light, or by
instruments2l4 designed especially for the purpose) or, in the case of shifts ofledges
("pattern shift") of buried layers (epitaxy), by sectioning and staining. The non-
replication can be followed during growth by alternately producing n- and p-layers
which can later be exposed by sectioning and staining.

2.11 RADIATION DAMAGE210

Irradiation of semiconductors by x- and gamma rays, and particles such as neu-

trons, electrons, protons, and heavier ions produce a variety of damaging effects
to both the semiconductor itself and devices made from it. The reader may be faced
with the problem either of irradiating and then searching for damage or of examining
* See previous section.
 Crystallographic Defects and Their Observation S3

material or devices and deducing what environment they have seen.

The damage will be either bulk or surface, but the device performance will reflect
not only those effects but also the effects of the generation of excess carriers during
irradiating by x- or gamma rays. The bulk damage is atomic displacement caused
by the colliding incident particle and may be as minimal as a few vacancy-interstitial
pairs (and the interstitials usually anneal out rather rapidly) or as drastic as local
melting or amorphous-layer formation. These defects in turn introduce deep electri-
cal levels into the semiconductor, which causes the resistivity to increase and the
lifetime to decrease. Surface effects generally involve charge buildup in overlaying
insulating layers (thermal oxide of Si planar devices) and can cause heavy surface
inversion or accumulation. The bulk and surface charges are generally lasting,
though much of it can be annealed out, while the excess carrier generation is but
a transient effect and lasts after cessation of irradiation only as long as it takes the
carriers to recombine by normal processing.
The units in common usage are given in Table 2.lO. However, since the various
sources differ appreciably in both particle and energy spectrum, one of the major
problems is in correlating various investigators' results.
Observation. Once a radiation defect has been introduced, it is not different from
one produced by other means. Hence the methods described throughout this chapter
are appropriate, as well as those described in Chaps. 3 and 4. The more heavily
damaged regions, such as local melting, can be studied by etching techniques. 211
Since most defects are of the point variety, EPR and infrared-absorption spectra
are widely used. 212
To study the effects on finished devices, special test structures are often used.
For example, if a diode is constructed which has one side of the junction much
thinner than the diffusion length of the minority carriers, e.g., a solar-cell-type
structure, short-circuit current will be proportional to the diffusion length in the other

Table 2.10. Units Used in Describing Radiation

Type Descriptive units

Neutron Flux: in particles/(cm 2-s).

Fluence: (time integral of flux) in particles/cm 2
Integrated flux: same as fluence abbreviated as n/cm 2 or as nvt (from neutron
density X velocity X time)
Energy:' in MeV (million electron volts)

Electrons Flux: in particles/(cm2-s); or charge/(cm 2-s)

Fluence: in particles/cm 2, N/cm 2 ; or charge/cm 2
Energy: * in MeV

Protons Same as electrons

Heavy ions Same as electrons, plus atomic weight

X-ray Amount of ionization produced in air

Gamma 1 roentgen (R) = 2.09 X 109 /electrons/1.293 X 10-3 g of air (1 esu/cm 3 of air)
Amount of energy deposited in unit volume of a given material, cai/cm3
Amount of energy deposited in I g of a given material, cai/g
I rd = 100 cai/g
Rate(y): in rd/s, R/s, or cai/(cm 3 -s)

"If the particles are not monoenergetic, a graph of their number vs. energy is also required.
54 Semiconductor Measurements and Instrumentation

side. Therefore, lifetime can be continuously monitored during irradiation by x-

or gamma rays. Properly designed, diodes can be very sensitive to radiation damage.
For instance, with small-volume avalanche diodes, the electrical effect of a single
neutron collision has been reported. 213

REFERENCES

1. R. G. Rhodes, "Imperfections and Active Centres in Semiconductors," The Macmillan

Company, New York, 1964.
2. J. Melngailis and S. O'Hara, Diffusion of Vacancies during Quenching of Ge and Si,
J. Appl. Phys., 33:2596-2601 (1962).
3. R. A. Swalin, "Thermodynamics of Solids," John Wiley & Sons, Inc., New York, 1972.
4. Erwin W. Milller, Direct Observation of Crystal Imperfections by Field Ion Microscopy,
in J. B. Newkirk and J. H. Wernick (eds.), "Direct Observation of Imperfections in
Crystals," Interscience Publishers, Inc., New York, 1962.
5. W. W. Scalon, Stoichiometry in Compound Semiconductors, in Harry C. Gatos (ed.),
"Properties of Elemental and Compound Semiconductors," Interscience Publishers, Inc.,
New York, 1960.
6. National Bureau of Standards, personal communication.
7. James W. Gilpin and James C. Boatman, Vacancy Distribution in Silicon Ribbon
Material and Resultant Diffusion Anomalies, in RolfR. Haberecht and Edward L. Kern
(eds.), "Semiconductor Silicon," Electrochemical Society, New York, 1969.
8. James W. Corbett, Electron Radiation Damage in Semiconductors and Metals, Solid
State Phys., Suppl. 7, 1966.
9. J. R. Patel, R. F. Tramposch, and A. R. Chaudhuri, Growth and Properties of Heavily
Doped Germanium Single Crystals, in Ralph O. Grugel (ed.), "Metallurgy of Elemental
and Compound Semiconductors," Interscience Publishers, Inc., New York, 1961.
10. G. E. Brock and B. K. Bischoff, Arsenic Precipitation in Germanium, in Geoffrey E.
Brock (ed.), "Metallurgy of Advanced Electronic Materials," Gordon and Breach,
Science Publishers, Inc., New York, 1963.
11. E. Rimini, J. Haskell, and J. W. Mayer, Beam Effects in the Analysis of As-doped Silicon
by Channeling Measurements, Appl. Phys. Lett., 20:237-239 (1972).
12. J. A. Davies, J. Denhartag, L. Eriksson, and J. W. Mayer, Ion Implantation of Silicon,
Can. J. Phys., 45:4053-4061 (1967).
13. F. Morin and H. Reiss, Precipitation of Lithium in Germanium, Phys. Chern. Solids,
3:196-209 (1957).
14. R. Weltzin and R. A. Swalin, Application of Precipitation Techniques to the Study of
Defects in Germanium, J. Phys. Soc. Japan, 18(Suppl. III): 136-141 (1963).
15. P. D. Southgate, Mechanical Damping of Germanium and Silicon Containing Impurity
Oxygen, in M. Desirant and J. L. Michiets (eds.), "Solid State Electronics and Telecom-
munications," vol. 1, Academic Press, Inc., New York, 1960.
16. S. I. Tan, B. S. Berry, and B. L. Crowder, Elastic and Ane1astic Behavior of Ion-
implanted Silicon, Appl. Phys. Lett., 20:88-90 (1972).
17. S. Chau, L. A. Davidson, and J. F. Gibbons, Use of High Energy Ion Beams for the
Analysis of Doped Surface Layers, in Charles P. Marsden (ed.), "Silicon Device Proces-
sing," NBS Special Publication 337, 1970.
18. A. H. Cottrell, "Dislocations and Plastic Flow in Crystals," Oxford University Press,
Oxford, 1953.
19. W. T. Read, Jr., "Dislocations in Crystals," McGraw-Hill Book Company, New York,
1953.
20. John Price Hirth and Jens Lothe, "Theory of Dislocations," McGraw-Hill Book Com-
pany, New York, 1968.
 Crystallographic Defects and Their Observation 55

21. F. R. N. Nabarro, "Theory of Crystal Dislocations," Oxford University Press, London,

1967.
22. V. L. Indenbom, Dislocations in Crystals, Soviet Phys. Cryst., 43:112-132 (1958).
23. O. W. Johnson, High Stress Low-Temperature Dislocation Kinetics of Ge, J. Appl. Phys.,
36:3247-3250 (1965).
24. W. C. Dash, Dislocations in Silicon and Germanium Crystals, in Harry C. Gatos (ed.),
"Properties of Elemental and Compound Semiconductors," Interscience Publishers, Inc.,
New York, 1960.
25. W. C. Dash, Copper Precipitation on Dislocations in Silicon, J. Appl. Phys., 27: 1193-1195
(1956).
26. Eugene S. Meieran, Observation of Frank-Reed Sources in Silicon, J. Appl. Phys.,
36:1497-1498 (1965). See also J. Appl. Phys., 27:1193; 35:1956.
27. Mitsuru Yoshimatsu, Tetsuro Suzuki, Teruo Kobayashi, and Kazatake Kohra, Loop
Shaped Images Observed in X-ray Diffraction Micrographs of Silicon Single Crystals,
J. Phys. Soc. Japan, 17:583-584 (1962).
28. A. J. R. De Kock, Vacancy Clusters in Dislocation Free Silicon, Appl. Phys. Lett.,
16:100-102 (1970).
29. T. S. Plaskett, Evidence of Vacancy Clusters in Dislocation-free Float-Zone Silicon,
Trans. A/ME, 233:809-812 (1965).
30. Junji Matsui and Tsutomu Kawamura, Spotty Defects in Oxidized Floating-zoned
Dislocation-free Silicon Crystals, Japan. J. Appl. Phys., 11: 197-205 (1972).
31. J. Homstra, Dislocations in the Diamond Lattice, Phys. Chern. Solids, 5:129-141 (1958).
32. William J. Patrick, The Precipitation of Oxygen in Silicon, and Its Effect on Surface
Perfection, in Charles P. Marsden (ed.), "Silicon Device Processing," NBS Special
Publication 337, 1970.
33. M. S. Abrahams and A. Dreeben, Formation of Dislocations around Precipitates in
Single Crystals of (Zn, Cd)S:Er, J. Appl. Phys., 36:1688-1692 (1965).
34. F. L. Vogel, W. G. Pfann, H. E. Corey, and E. E. Thomas, Observation of Dislocation
in Lineage Boundaries in Germanium, Phys. Rev., 90:489-490 (1953).
35. F. L. Vogel, Jr., Dislocations in Low-Angle Boundaries in Germanium, Acta Met.,
3:245-248 (1955).
36. W. G. Pfann and F. L. Vogel, Jr., Observations on the Dislocation Structure of Ger-
manium Crystals, Acta Met., 5:377-384 (1957).
37. V. R. Regel, A. A. Urusovskaya, and V. N. Kolomiichek, Revealing the Emergence
of Dislocations on the Surface of a Crystal by the Etch Method, Soviet Phys. Cryst.,
4:895-917 (1960).
38. T. L. Johnston, C. H. Li, and C. I. Knudson, Spiral Etch Pits in Silicon, J. Appl. Phys.,
28:746 (1957).
39. J. W. Faust, Jr., The Influence of Surface Preparation on Revealing Dislocations in
Germanium, Electrochem.. Tech., 1 :377-378 (1963).
40. T. B. Light, Imperfections in Germanium and Silicon Epitaxial Films, in John B.
Schroeder (ed.), "Metallurgy of Semiconductor Materials," Interscience Publishers, Inc.,
New York, 1962.
41. F. L. Vogel, Jr., Dislocations in Plastically Bent Germanium Crystals, J. Metals, 8:946-
949 (1956).
42. J. D. Venables and R. M. Broudy, Dislocations and Selective Etch Pits in InSb. J. Appl.
Phys., 29: 1025-1028 (1958).
43. M. C. Lavine, H. C. Gatos, and M. C. Finn, Characteristics of the {Ill} Surfaces of
the III-V Intermetallic Compounds, J. Electrochern. Soc., 108:974-980 (1961).
44. Morio Inoue, Iwao Teramoto, and Shigetoshi Takayanagi, Cd and Te Dislocations in
Cd Te, J. Appl. Phys., 34:404-405 (1963).
45. Dr. Lyndon Taylor, personnal communication.
46. W. Czaja and G. H. Wheatley, Simultaneous Observation of Diffusion-induced Dis-
56 Semiconductor Measurements and Instrumentation

location Slip Patterns in Si with Electron Beam Scanning and Optical Means, J. Appl.
Phys., 35:2782-2783 (1964).
47. W. Czaja and J. R. Patel, Observation ofIndividual Dislocations and Oxygen Precipitates
in Silicon with a Scanning Electron Beam Method, J. Appl. Phys., 35:1476-1482 (1965).
48. E. Sirtl and A. Adler, Chromic-Hydrofluoric Acid as a Specific System for the Develop-
ment of Etch Pits on Silicon, Z. Metallk., 52:529 (1961).
49. D. Navon, R. Bray, and H. Y. Fan, Lifetime of Injected Carriers in Germanium, Proc.
IRE, 40:1342-1347 (1952).
50. R. V. Jensen and S. M. Christian, "Etch Pits and Dislocation Studies in Silicon Crystal,"
RCA Industry Service Laboratory, Bull. L13-1023, Mar. 5, 1956.
51. W. J. Feuerstein, Etch Pit Studies on Silicon, Trans. AIME, 212:210-212 (1958).
52. Allegheny Electric Chemical Co., Tech. Bull. 6, June 1958.
53. F. L. Vogel, Jr., and L. Clarice Lovell, Dislocation Etch Pits in Silicon Crystals, J. Appl.
Phys., 27: 1413-1415 (1956).
54. F. Secco d'Aragona, Dislocation Etch for (100) Planes in Silicon, J. Electrochem. Soc.,
119:948-951 (1972).
55. S. O'Hara and G. H. Schwuttke, Dislocation Reactions in Silicon Web-Dendrite Crystals,
J. Appl. Phys., 36:2475-2479 (1965).
56. M. L. Joshi and F. J. Wilhelm, Observation of Diffusion-induced Dislocation Lines in
Silicon through Optical Microscopy, J. Appl. Phys., 36:2593-2594 (1965).
57. S. G. Ellis, Dislocations in Germanium, J. Appl. Phys., 26:1140-1146 (1955).
58. H. A. Schell, Etch Figures on Germanium Single Crystals, Z. Metallk., 47(9):614-620
(1956).
59. E. Billig, Some Defects in Crystals Grown from the Melt, I. Defects Caused by Thermal
Stresses, Proc. Roy. Soc. London, A235:37-55 (1956).
60. R. H. Wynn and C. Goldberg, Preferential Etch for Use in Optical Determination of
Germanium Crystal Orientation, J. Metals, 5:436 (1955).
61. V. N. Vasilevskaya and E. G. Miselyuk, The Problem of Visualization of Dislocations
in Germanium by Etching, Soviet Phys. Solid State, 3:313-318 (1961).
62. J. W. Faust, The Influence of Surface Preparation on Revealing Dislocations in Ger-
manium, Electrochem. Tech., 1:377-378 (1963).
63. G. H. Schwuttke, Study of Copper Precipitation Behavior in Silicon Single Crystals,
J. Electrochem. Soc., 108:163-167 (1961).
64. D. J. D. Thomas, Surface Damage and Copper Precipitation in Silicon,Phys. Stat. Solids,
3:2261-2273 (1963).
65. Arthur H. Compton and Samuel K. Allison, "X-Rays in Theory and Experiment,"
D. Van Nostrand Company, Inc., Princeton, N.J., 1948.
66. A. D. Kurtz, S. A. Kulin, and B. L. Averbach, Effect of Dislocations on the Minority
Carrier Lifetime in Semiconductors, Phys. Rev., 101:1285-1291 (1956).
67. J. R. Patel, R. S. Wagner, and S. Moss, X-Ray Investigation of the Perfection of Silicon,
Acta Met., 10:759-764 (1962).
68. J. R. Carruthers, R. B. Hoffman, and J. D. Ashner, X-Ray Investigation of the Perfection
of Silicon, J. Appl. Phys., 34:3389-3393 (1963).
69. Boris W. Batterman, X-Ray Integrated Intensity of Germanium Effect of Dislocations
and Chemical Impurities, J. Appl. Phys., 30:508-513 (1959).
70. A. R. Lang, A Method for the Examination of Crystal Sections Using Penetrating
Characteristic X-Radiation, Acta Met., 5:358-364 (1957).
71. A. R. Lang, Direct Observation ofIndividual Dislocations by X-Ray Diffraction, J. Appl.
Phys., 29:597-598 (1958).
72. A. R. Lang, The Projection Topography: A New Method in X-Ray Diffraction Micro-
radiography, Acta Cryst., 12:249-250 (1959).
73. A. R. Lang, Studies of Individual Dislocations in Crystals by X-Ray Diffraction
Microradiography, J. Appl. Phys., 30:1748-1755 (1959).
 Crystallographic Defects and Their Observation 57

74. G. H. Schwuttke, X-Ray Diffraction Microscopy Study ofImperfections in Silicon Single

Crystals, J. Electrochem. Soc., 109:27-32 (1962).
75. A. R. Lang, Application of Limited Projection Topographs and Direct Beam Topographs
in Diffraction Topography, Brit. J. Appl. Phys., 14:904-907 (1963).
76. G. H. Schwuttke, New X-Ray Diffraction Microscopy Technique for the Study of
Imperfections in Semiconductor Crystals, J. Appl. Phys., 36:2712-2721 (1965).
77. Kazutake Kohra, Mitsuru Yoshimetsu, and Ikuzo Shimizu, X-Ray Observation of Lattice
Defects Using a Crystal Monochrometer, in J. B. Newkirk and J. H. Wernick (eds.),
"Direct Observations of Imperfections in Crystals," Interscience Publishers, Inc., New
York, 1962.
78. A. E. Jenkinson and A. R. Lang, X-Ray Diffraction Topographic Studies of Dislocations
in Floating-Zone Grown Silicon, in J. B. Newkirk and J. H. Wernick (eds.), "Direct
Observations of Imperfections in Crystals," Interscience Publishers, Inc., New York,
1962.
79. A. R. Lang, Crystal Growth and Crystal Perfection: X-Ray Topographic Studies,
Discussions Faraday Soc., No. 38, pp. 292-297, 1964.
80. Eugene S. Meieran, Reflection X-Ray Topography of GaAs Deposited on Ge, J. Elec-
trochem. Soc., 114:292-295 (1967).
81. N. Kato and A. R. Lang, A Study of Pendellosung Fringes in X-Ray Diffraction, Acta
Cryst., 12:787-794 (1959).
82. W. W. Webb, X-Ray Diffraction Topography, in J. B. Newkirk and J. H. Wernick (eds.),
"Direct Observations of Imperfections in Crystals," Interscience Publishers, Inc., New
York, 1962.
83. G. Borrmann and K. Lehman, X-Ray Wave Fields and Lattice Imperfections in Silicon,
in J. B. Newkirk and J. H. Wernick (eds.), "Direct Observations of Imperfections in
Crystals," Interscience Publishers, Inc., New York, 1962.
84. Volkmar Gerold, X-Ray Methods for Detection of Lattice Imperfections in Crystals,
in William M. Inveller, (ed.), "Advances in X-Ray Analysis," vol. 3, Plenum Press, New
York, 1960.
85. G. H. Schwuttke, Direct Observation of Imperfections in Semiconductor Crystals by
Anomalous Transmission of X-Rays, J. Appl. Phys., 33:2760-2767 (1962).
86. Volkmar Gerold, Direct Observation of Dislocations in Germanium by an X-Ray
Method, in J. B. Newkirk and J. H. Wernick (eds.), "Direct Observation of Imperfections
in Crystals," Interscience Publishers, Inc., New York, 1962.
87. Mitsuru Yoshimatsu, Atsushi Shibata, and Kazutka Kohra, A Modification of the
Scanning X-Ray Topographic Camera (Lang's Method), in Gavin R. Mallett, Marie
Fay, and William M. Mueller (eds.), "Advances in X-Ray Analysis," vol. 9, Plenum
Press, New York, 1966.
88. A. E. Jenkinson, Projection Topographs of Dislocations, Philips Tech. Rev., 23:82-88
(1961-1962).
89. Kyoichi Haruta, New Method of Obtaining Stereoscopic Pairs of X-Ray Diffraction
Topographs, J. Appl. Phys., 36:1789-1790 (1965).
90. F. W. Young, Jr., T. O. Baldwin, A. E. Merlini, and F. A. Sherrill, A Camera for
Borrmann Stereo X-Ray Topographs, in Gavin R. Mallett, Marie Fay, and William M.
Mueller (eds.), "Advances in X-Ray Analysis," vol. 9, Plenum Press, New York, 1966.
91. H. K. Herglotz, Simple Method of Determining Crystal Perfection, J. Electrochem. Soc.,
106:600-605 (1959).
92. See, for example, P. B. Hirsch and J. N. Kellar, A Study of Cold-worked Aluminum
by an X-Ray Micro-Beam Technique: I. Measurement of Particle Volume and Mis-
orientations, Acta Cryst., 5:162-167 (1953).
93. W. A. Wooster, "Diffuse X-Ray Reflections from Crystals," Oxford University Press,
New York, 1962.
94. Richard A. Coy and James E. Thomas, Jr., Observation of X-Ray Diffuse Scattering
58 Semiconductor Measurements and Instrumentation

from Neutron-irradiated Silicon, J. Appl. Phys., 42:1236-1239 (1971).

95. Dan A. Blech, Eugene S. Merran, and Harry Sello, X-Ray Surface Topography of
Diffusion-generated Dislocations in Silicon, Appl. Phys. Lett., 7: 176-178 (1965).
96. K. Akiyama and J. Yamarguchi, Dislocations of Silicon Single Crystals Grown by the
Floating Zone Method, in Marvin S. Brooks and John K. Kennedy (eds.), "Ultra-
purification of Semiconductor Materials," The Macmillan Company, New York, 1962.
97. J. K. Howard and D. P. Miller, Vacancy Related Defects in Antimony-doped Silicon,
in William M. Mueller, Gavin Mallett, and Marie Fay (eds.), "Advances in X-Ray
Analysis," vol. 7, Plenum Press, New York, 1964.
98. A. Authier and A. R. Lang, Three-Dimensional X-Ray Topographic Studies of Internal
Dislocation Sources in Silicon, J. Appl. Phys., 35:1956-1959 (1964).
99. M. L. Joshi and J. K. Howard, Defects Induced in Silicon through Device Processing,
in Charles P. Marsden (ed.), "Silicon Device Processing," NBS Special Publication 337,
1970.
100. P. Wang, F. X. Pink, and D. C. Gupta, Structural Faults in Epitaxial and Buried Layers
in Silicon Device Fabrication, in Charles P. Marsden (ed.), "Silicon Device Processing,"
NBS Special Publication 337, 1970; T. Kato, H. Koyama, T. Matsukawa, and R. Shimizu,
SEM Contrast Mechanism of Stacking Faults in an Epitaxial Silicon Layer, J. Appl.
Phys., 45:3732-3737 (1974); Masao Tamura and Yoshimitsu Sugita, Misfit Dislocations
in (100), (112), and (113) Homoepitaxial Silicon Crystals, J. App!. Phys., 44:3442-3444
(1973).
10 1. Mitsuru Yoshimatsu, Studies on Lattice Defects of a Pair of Rods and Platelets in Silicon
Single Crystals Observed by X-Ray Diffraction Micrography, J. Phys. Soc. Japan,
18(Suppl. 11):335-340 (1963).
102. Kazutake Kohra and Shigeru Nakano, X-Ray Studies on Lattice Defects in Silicon by
Diffraction Microscopy and Double Crystal Spectrometer,1. Phys. Soc. Japan, 18(Suppl.
11):341-346 (1963).
103. E. S. Meieran and K. E. Lemons, A Study of Defects Due to Surface Processing in
Silicon by Means of X-Ray Extinction Contrast Topography, in William M. Mueller,
Gavin Mallett, and Marie Fay (eds.), "Advances in X-Ray Analysis," vol. 8, Plenum
Press, New York, 1965.
104. R. Berman (ed.), "Physical Properties of Diamonds," Clarendon Press, Oxford, 1965.
105. M. Omar and M. Kenawi, The Etching of Diamonds by Low Pressure Oxygen, Phil.
Mag., 2:859-863 (1957).
106. M. S. Abrahams, Dislocation Etch Pits in GaAs, J. Appl. Phys., 35:3626-3627 (1964).
107. M. S. Abrahams and L. Ekstrom, Etch Pits Deformation and Dislocations in GaAs,
in Harry C. Gatos (ed.), "Properties of Elemental and Compound Semiconductors,"
Interscience Publishers, New York, 1960).
108. M. S. Abrahams and C. J. Buiocchi, Etching of Dislocations on the Low-Index Faces
of GaAs, J. App!. Phys., 36:2855-2863 (1965).
109. G. A. Rozgonyi and S. E. Haszko, Reflection X-Ray Topography of GaAs and GaP
Cleavage Faces, 1. Electrochem. Soc., 117: 1562-1565 (1970).
110. J. K. Howard and R. H. Cox, The Crystalline Perfection of Melt-grown GaAs Substrates
and Ga(As,P) Epitaxial Deposits, in Gavin R. Mallett, Marie Fay, and William M.
Mueller (eds.), "Advances in X-Ray Analysis," vol. 9, Plenum Press, New York, 1966.
Ill. G. H. Schwuttke and H. Rupprecht, X-Ray Analysis of Diffusion-induced Defects in
Gallium Arsenide. J. Appl. Phys., 37:167-173 (1966).
112. E. D. Jungbluth, X-Ray Diffraction Topographs of Imperfections in Gallium Arsenide
by Anomalous Transmission of X-Rays, J. Electrochem. Soc., 112:580-583 (1965).
113. G. O. Krause and E. C. Teague, Observation of Misfit Dislocations in GaAs-Ge
Heterojunctions, App!. Phys. Lett., 10:251-253 (1967).
114. Sidney G. Parker and Jack E. Pinnell, Revelation of Dislocations in (Hg, Cd)Te by
an Etch Technique, J. Electrochem. Soc., 118:1868-1869 (1971).
 Crystallographic Defects and Their Observation 59

115. M. Gershenzon and R. M. Mikulyak, Structural Defects in GaP Crystals and Their
Electrical and Optical Effects, J. Appl. Phys., 35:2132-2141 (1964).
116. J. W. Allen, On the Mechanical Properties of Indium Antimonide, Phil. Mag., 2: 1475-
1481 (1957).
117. H. C. Gatos and M. C. Lavine, "Chemical Behavior of Semiconductors: Etching
Characteristics," Lincoln Laboratory Technical Report 293, January 1962 (AD 401398).
This compendium lists etchants for many different materials.
118. Robert W. Bartlett and Malcom Barlow, Surface Polarity and Etching of Beta-Silicon
Carbide, J. Electrochem. Soc., 117:1436-1437 (1970).
119. Schlomo I. Ben-Abraham, Geometry of Etch-Pits in ZnS Crystals, J. Appl. Phys.,
36:2096-2098 (1965).
120. Marriner K. Norr, A Dislocation Etch for Lead Selenide Crystals, J. Electrochem. Soc.,
109:l113-1II4 (1962).
121. Marriner K. Norr, John V. Gilfrich, and Bland Houston, A Chemical Polish That
Reveals Compositional Variations in PbSe(1_x) Tex, J. Electrochem. Soc., 114:632-633
(1967).
122. C. M. Wolfe, C. J. Nuese, and N. Holonyak, Jr., Growth and Dislocation Structure
of Single-Crystal Ga(As1_XPX)' J. Appl. Phys., 36:3790-3801 (1965).
123. C. M. Drum and W. Van Gelder, Stacking Faults in (100) Epitaxial Silicon Caused
by HF and Thermal Oxidation and Effects on p-n Junctions, J. Appl. Phys., 43:4465-4468
(1972).
124. J. M. Charig, B. A. Joyce, D. J. Stirland, and R. W. Bicknell, Growth Mechanism and
Defect Structures in Epitaxial Silicon, Phil. Mag., 7:1847-1860 (1962).
125. G. R. Booker and R. Stickler, Crystallographic Imperfections in Epitaxially Grown
Silicon, J. Appl. Phys., 33:3281-3290 (1962).
126. H. J. Queisser, R. H. Finch, and J. Washburn, Stacking Faults in Epitaxial Silicon,
J. Appl. Phys., 33:1536-1537 (1962).
127. T. L. Chu and J. R. Gavaler, Stacking Faults in Vapor Grown Silicon, J. Electrochem.
Soc., 11 0:388-393 (1963).
128. T. L. Chu and J. R. Gavaler, Imperfections in Vapor Grown Silicon, in Geoffrey E.
Brock (ed.), "Metallurgy of Advanced Electronic Materials," Gordon and Breach,
Science Publishers, Inc., New York, 1963.
129. R. H. Dudley, Nondestructive Method for Revealing Stacking Faults in Epitaxial
Silicon, J. Appl. Phys., 35:1360-1361 (1964).
130. S. Mendelson, Stacking Fault Nucleation in Epitaxial Silicon on Variously Oriented
Silicon Substrates, J. Appl. Phys., 35:1570-1581 (1964).
131. R. H. Finch, H. J. Queisser, G. Thomas, and J. Washburn, Structure and Origin of
Stacking Faults in Epitaxial Silicon, J. Appl. Phys., 34:406-415 (1963).
132. S. Mendelson, Growth and Imperfections in Epitaxially Grown Silicon on Variously
Oriented Silicon Substrates, in Maurice H. Francombe and Hiroshi Sato (eds.), "Single
Crystal Films," pp. 251-281, The Macmillan Company, New York, 1964.
133. S. Mendelson, Twin Boundaries and Stacking Faults in Silicon, Acta Met., 13:555-558
(1965).
134. G. Dionne, Nature of Stacking-Fault Defects in Epitaxial Silicon Layers, J. Appl. Phys.,
39:2940-2941 (1968).
135. V. A. Phillips, Lattice Resolution Observations on the Structure of Twin Boundaries,
Faults, and Dislocations in Epitaxial Silicon, Acta Met., 20: 1143-1156 (1972).
136. T. Iizuka and M. Kikuchi, X-Ray Observation of Gold-induced Dislocation Loops in
Silicon Crystals, in R. R. Hasiguti (ed.), "Lattice Defects in Semiconductors," University
of Tokyo Press, Tokyo, and Pennsylvania State University Press, University Park, 1968.
137. T. Iizuka, Gold-induced Dislocation Loops in Silicon Crystals, Japan. J. Appl. Phys.,
5(11): 1018 (1966).
138. Lawrence D. Dyer and Fred W. Voltmer, Circular and Hexagonal Stacking Faults in
60 Semiconductor Measurements and Instrumentation

Bulk Silicon Crystals, J. Electrochem. Soc., 120:812-817 (1973).

139. H. J. Queisser and P. G. G. van Loon, Growth of Lattice Defects in Silicon during
Oxidation, J. Appl. Phys., 35:3066 (1964).
140. G. R. Booker and R. Stickler, Two-Dimensional Defects in Silicon after Annealing in
Oxygen, Phil. Mag., 11: 1303 (1965).
141. M. L. Joshi, Stacking Faults in Steam-oxidized Silicon, Acta Met., 14: 1157 (1966).
142. A. W. Fisher and J. A. Amick, Defect Structure on Silicon Surfaces after Thermal
Oxidation, J. Electrochem. Soc., 113: 1054-1060 (1966).
143. Yoshimitsu Sugita, Teruo Kato, and Masao Tamura, Effect of Crystal Orientation on
the Stacking Fault Formation in Thermally Oxidized Silicon, J. Appl. Phys., 42:5847-
5849 (1971).
144. J. M. Charig, B. A. Joyce, D. J. Stirland, and R. W. Bicknell, Growth Mechanism and
Defect Structures in Epitaxial Silicon, Phil. Mag., 7: 1847-1860 (1962).
145. G. Dionne, Discrepancies in the Number of Stacking Faults Revealed by Various
Methods in Epitaxial Silicon, J. Appl. Phys., 38:3417-3418 (1967).
146. W. K. Liebmann, Orientation of Stacking Faults and Dislocation Etch Pits in P-SiC,
J. Electrochem. Soc., 111 :885-886 (1964).
147. ASTM F 80, "ASTM Book of Standards," Part 8, American Society for Testing and
Materials, Philadelphia, 1968.
148. J. A. Kohn, Twinning in Diamond-Type Structures: High Order Twinning in Silicon,
Am. Mineralogist, 41 :778-784 (1956).
149. J. A. Kohn, Twinning in Diamond-Type Structure: A Proposed Boundary-Structure
Model, Am. Mineralogist, 43:263-284 (1958).
150. J. W. Faust and H. F. John, A Comparison of Etching and Fracturing Techniques
for Studying Twin Structures in Ge, Si, and I1I-V Intermetallic Compounds, J. Electro-
chem. Soc., 107:562-565 (1960).
151. P. F. Schmidt and R. Stickler, Silicon Phosphide Precipitates in Diffused Silicon,
J. Electrochem. Soc., 111 :1188-1189 (1964).
152. H. C. Gorton, Dendritic Inclusions in AlSb Grown Junction Diodes, J. Electrochem.
Soc., 107:248-249 (1965).
153. G. D. Miles, Observations ofImpurity Precipitates in Magnesium Oxide Single Crystals
by Ultra-Microscopy, J. Appl. Phys., 36:1471-1475 (1965).
154. W. Kaiser, Electrical and Optical Properties of Heat-treated Silicon, Phys. Rev.,
105:1751-1756 (1957).
155. G. H. Schwuttke, O. A. Weinreich, and P. H. Keck, A Sensitive Method for Measuring
Optical Scattering in Silicon, J. Electrochem. Soc., 105:706-709 (1958).
156. F. J. Baum and F. J. Darnell, Birefringence Studies in Electroluminescent Zinc Sulfide,
J. Electrochem. Soc., 109:165-166 (1962).
157. K. Kamiya and A. R. Lang, X-Ray Diffraction and Absorption Topography of Sym-
metric Diamonds, J. Appl. Phys., 36:579-587 (1965).
158. G. H. Schwuttke, Boron-induced Microstrains in Dislocation-free Silicon Crystals,
J. Appl. Phys., 34:1662-1664 (1963).
159. Arthur Dreeben, Precipitation of Impurities in Large Single Crystals of CdS, J. Electro-
chem. Soc., 111:174-179 (1964).
160. E. Biederman, Traveling Solvent Defects on Silicon Wafers, J. Electrochem. Soc.,
114:207-208 (1967) (note p. 676 of vol. 115).
161. C. H. L. Goodman, Melting Phenomena with Silicon, Solid State Electron., 3:72-73
(1961).
162. J. H. Westbrook, A. U. Seybolt, and A. J. Peat, A Thermal Probe for Segregation
Detection, J. Electrochem. Soc., 111 :888-891, (1964).
163. Thomas E. Seidel, Hall Measurements on Tunnel Diode Material, in Ralph O. Grubel
(ed.), "Metallurgy of Elemental and Compound Semiconductors," Interscience Pub-
lishers, Inc., New York, 1961.
 Crystallographic Defects and Their Observation 61

164. M. L. Joshi, Precipitates of Phosphorus and Arsenic in Silicon, J. Electrochem. Soc.,

113:45-48 (1966).
165. H. C. Casey, Jr., Investigation ofInhomogeneities in GaAs by Electron-Beam Excitation,
J. Electrochem. Soc., 114:153-158 (1967).
166. A. N. Knopp and R. Stickler, Transmission Electron Microscope Investigations on
Diffused Silicon Wafers with Relation to Electrical Properties of Controlled Rectifiers,
J. Electrochem. Soc., 111: 1372-1376 (1964).
167. G. R. Booker and R. Stickler, Small Particles in Silicon,J. Electrochem. Soc., 111: 1011-
1012 (1964).
168. J. F. Black and E. D. Jungbluth, Decorated Dislocations and Sub-Surface Defects
Induced in GaAs by the In-Diffusion of Zinc, J. Electrochem. Soc., 114: 188-192 (1967).
169. M. L. Joshi, Effect of Fast Cooling on Diffusion-induced Imperfections in Silicon,
J. Electrochem. Soc., 112:912-915 (1965).
170. E. D. Wolley and R. Stickler, Formation of Precipitates in Gold Diffused Silicon,
J. Electrochem. Soc., 114:1287-1292 (1967).
171. J. F. Black, The Occurrence and Identification of Precipitates in Zinc Diffused GaAs,
J. Electrochem. Soc., 114:1292-1297 (1967).
172. J. F. Butler and T. C. Harmon, Metallic Inclusions and Cellular Substructure in
Pb1_xSnxTe Single Crystals, J. Electrochem. Soc., 116:260-263 (1969).
173. Carroll F. Powell, Stresses in Deposits, in Carroll F. Powell, Joseph H. Oxley, and
John M. Blocher, Jr. (eds.), "Vapor Deposition," pp. 191-218, John Wiley & Sons, Inc.,
New York, 1966.
174. William C. Dash, Distorted Layers in Silicon Produced by Grinding and Polishing,
J. Appl. Phys., 29:228-229 (1958).
175. R. W. Vook and F. Witt, Thermally Induced Strains in Evaporated Films, J. Appl. Phys.,
36:2169-2171 (1965).
176. Ilan A. Blech and Eugene S. Meieran, Enhanced X-Ray Diffraction from Substrate
Crystals Containing Discontinuous Surface Films, J. Appl. Phys., 38:2913-2919 (1967).
177. S. M. Fairfield and G. H. Schwuttke, Strain Effects around Planar Diffused Structures,
J. Electrochem. Soc., 115:415-422 (1968); and references contained therein.
178. E. D. Jungbluth and H. C. Chiao, Intense Inteljunction Strain in Phosphorus in Diffused
Silicon, J. Electrochem. Soc., 115:429-433 (1968).
179. B. G. Cohen and M. W. Focht, X-Ray Measurement of Elastic Strain and Annealing
in Semiconductors, Solid State Electron., 13: 105-112 (1970).
180. B. D. Cullity, Sources of Error in X-Ray Measurements of Residual Stress, J. Appl.
Phys., 35:1915-1917 (1964).
181. A. K. Singh and C. Balasingh, Effect of X-Ray Diffractometer Geometrical Factors on
the Centroid Shift of a Diffraction Line for Stress Measurement, J. Appl. Phys.,
42:5254-5260 (1971).
182. Brian R. Laun, Measurement of Elastic Strains in Crystal Surfaces by X-Ray Diffraction
Topography, in John B. Newkirk, Gavin R. Mallett, and Heinz A. Pfeiffer (eds.),
"Advances in X-Ray Analysis," vol. II, Plenum Press, New York, 1968; G. A. Rozgonyi
and T. J. Ciesielka, X-ray Determination of Stress in the Thin Films and Substrates
by Automatic Bragg Angle Control, Rev. Sci. Instr., 44:1053-1057 (1973).
183. Eugene S. Meieran and Ilan Blech, X-Ray Extinction Contrast Topography of Silicon
Strained by Thin Surface Films, J. Appl. Phys., 36:3162-3167 (1965).
184. R. W. Hoffman, Physical Properties of Thin Films, in G. Haas and R. E. Thun (eds.),
"Physics of Thin Films," vol. 2, Academic Press, Inc., New York, 1966.
185. G. H. Schwuttke and J. K. Howard, X-Ray Stress Topography of Thin Films on
Germanium and Silicon, J. Appl. Phys., 39:1581-1591 (1968).
186. C. M. Drum and M. J. Rand, A Low-Stress Insulating Film on Silicon by Chemical
Vapor Deposition, J. Appl. Phys., 39:4458-4459 (1968).
187. R. GIang, R. A. Holmwood, and R. L. Rosenfield, Determination of Stress in Films
62 Semiconductor Measurements and Instrumentation

on Single Crystalline Silicon Substrates, Rev. Sci. Instr., 36:7-10 (1965).

188. J. A. Aboaft, Stresses in Si0 2 Films Obtained from the Thermal Decomposition of
Tetraethylorthosilicate-Effect of Heat-Treatment and Humidity, J. Electrochem. Soc.,
116: 1732-1736 (1969).
189. Richard Lathlaen and Donald A. Diehl, Stress in Thin Films of Silicon Vapor-deposited
Silicon Dioxide, J. Electrochem. Soc., 116:620-622 (1969).
190. E. N. Pugh and L. E. Samuels, Etching of Abraded Germanium Surfaces with CP-4
Reagent, J. Electrochem. Soc., 109:409-412 (1962).
191. R. Stickler and J. W. Faust, Jr., Comparison of Two Different Techniques to Determine
the Depth of Damage, Electrochem. Tech., 4:399-401 (1966).
192. R. Stickler and G. R. Booker, Transmission Electron Microscope Investigation of
Removal of Mechanical Polishing Damage on Si and Ge by Chemical Polishing,
J. Electrochem. Soc., 111 :485-488 (1964).
193. T. M. Buck and F. S. McKim, Depth of Surface Damage due to Abrasion on Ger-
manium, J. Electrochem. Soc., 103:593-597 (1956).
194. T. M. Buck, Damaged Surface Layers: Semiconductors, in Harry C. Gatos (ed.), "The
Surface Chemistry of Metals and Semiconductors," John Wiley & Sons, Inc., New York,
1960.
195. E. N. Pugh and L. E. Samuels, Damaged Layers in Abraded {Ill} Surfaces of InSb,
J. Appl. Phys., 35:1966-1969 (1964).
196. A. Uhlir, Electrolytic Shaping of Germanium and Silicon, Bell System Tech. J., 35:333-
347 (1956).
197. Charlie E. Jones and A. Ray Hilton, The Depth of Mechanical Damage in Gallium
Arsenide, J. Electrochem. Soc., 112:908-911 (1965).
198. G. Feher, Electron Spin Resonance Experiments on Donors in Silicon, I. Electronic
Structure of Donors by the Electron Nuclear Double Resonance Technique, Phys. Rev.,
114: 1219-1244 (1959).
199. D. Baker and H. Yemm, The Depth of Surface Damage Produced by Lapping Ger-
manium Monocrystals, Brit. J. Appl. Phys., 8:302-303 (1957).
200. T. M. Buck and R. L. Meek, Crystallographic Damage to Silicon by Typical Slicing,
Lapping, and Polishing Operations, in Charles P. Marsden (ed.), "Silicon Device
Processing," NBS Special Publication 337, 1970.
201. E. N. Pugh and L. E. Samuels, Damaged Layers in Abraded Section Surfaces, J. Elec-
trochem. Soc., 111:1429-1431 (1964).
202. E. N. Pugh and L. E. Samuels, Dislocation Cracks in Abraded Germanium Surfaces,
J. Electrochem. Soc., 109:1197-1199 (1962).
203. E. N. Pugh and L. E. Samuels, Dislocation Arrays Produced in Germanium by Room-
Temperature Deformation, Phil. Mag., 8:301-310 (1963).
204. Ronald L. Meek and M. C. Huffstutler, ID-Diamond Sawing Damage to Germanium
and Silicon, J. Electrochem. Soc., 116:893-898 (1969).
205. P. R. Camp, A Study of the Etching Rate of Single-Crystal Germanium, J. Electrochem.
Soc., 102:586-593 (1955).
206. W. R. Runyan, Earl G. Alexander, and S. E. Craig, Jr., Behavior of Large-Scale Surface
Perturbations during Epitaxial Growth, J. Electrochem. Soc., 114:1154-1158 (1967).
207. C. M. Drum and C. A. Clark, Geometric Stability of Shallow Surface Depressions during
Growth of (Ill) and (100) Epitaxial Silicon, J. Electrochem. Soc., 115:664-669 (1968).
208. J. W. Beams, Mechanical Properties of Thin Films of Gold and Silver, in C. A. Neuge-
bauer et al. (eds.), "Structure and Properties of Thin Films," John Wiley & Sons, Inc.,
New York, 1959.
209. W. R. Runyan, J. M. Willmore, and L. E. Jones, Growth Techniques and Mechanical
Properties of Optical Quality Silicon, IRIS, 4:49-58 (1958).
210. Frank Larin, "Radiation Effects in Semiconductor Devices," John Wiley & Sons, Inc.,
New York, 1968.
 Crystallographic Defects and Their Observation 63

21l. M. Bertolotti, T. Papa, D. Sette, and G. Vitali, Electron Microscope Observation of

High-Energy-Neutron-Irradiated Germanium, J. Appl. Phys., 36:3506-3512 (1965).
212. James W. Corbett, Electron Radiation Damage in Semiconductors and Metals, Solid
State Phys., Suppl. 7, 1966.
2l3. R. Gereth, R. H. Haitz, and F. M. Smits, Effects of Single Neutron-induced Displace-
ment Clusters in Special Silicon Diodes, J. Appl. Phys., 36:3884-3894 (1965).
214. W. J. Patrick and E. J. Patzner, The Detection of Surface Defects on Silicon Wafers
by Scattered Light Measurements, in Howard R. Huff and Ronald R. Burgess (eds.),
"Semiconductor Silicon 1973," pp. 482-490, Electrochemical Society, Princeton, 1973;
H. J. Ruiz, C. S. Williams, and F. A. Padovani, Silicon Slices Analyzer Using a He-Ne
Laser, J. Electrochem. Soc., 121:689-692 (1974).
215. Ch. Kiihl, H. Schlotterer, and F. Schwidefsky, Optical Investigation of Different Silicon
Films, J. Electrochem. Soc., 121 :1496-1500 (1974).
 3
Resistivity and Carrier-Concentration
Measurements

Resistivity, carrier concentration, and impurity concentration are all interrelated,

and for most impurities in most semiconductors, the interrelations are well known.
Thus a determination of any of the three will usually suffice. In many cases, special
requirements are imposed, e.g., measurement in a very small area, and while in
principle most of the methods to be discussed can be used, in practice some are
more suitable than others. Table 3.1 lists a number of these requirements and some
of the more applicable methods.

3.1 GENERAL CONSIDERATIONS

Almost all the methods to be described can be used for either polycrystalline or
single-crystal material, but a considerable amount of additional interpretation may
be required for polycrystalline samples. The grain boundaries behave differently
from the individual crystallites, and it is not always possible to tell a priori whether
the apparent resistivity will be greater or less than that of similar material without
grain boundaries (i.e., single-crystal material), particularly if there is a possibility
of precipitates along the boundaries. Interpretation difficulties also arise when phases
with widely differing resistivity are present in the sample (e.g., ,a-silicon carbide
crystallites in an amorphous silicon carbide matrix) or if there is only a single phase
but it is anisotropic. Multiple layers of alternating high-low resistivity or p-n types
Will make any material appear anisotropic, since measurements with the current
parallel to the layers will almost always be different from those with the current
flow perpendicular. Such samples can be analyzed only by some of the profiling
methods discussed in a later section.
The surface preparation can affect apparent resistivity. If an inversion layer forms
and a probe measuring system is being used, the probes may not punch through
the layer and only it will be measured. If they do punch through and contact the
bulk, the layer and the bulk will form a parallel circuit. While some conflicting
obserVations are reported for mechanically abraded surfaces l - 3 , it appears that at
least for low-resistivity silicon and germanium, an increase in the measured resistivity
occurs at room temperature (probably because of microcracks). If the surface-
damage depth (approximately proportional to the diameter of the abrasive used)
is an appreciable fraction of the total thickness of the sample, errors of from several
65
66 Semiconductor Measurements and Instrumentation

Table 3.1. Resistivity Methods for Special Requirements

non n+ layer MOS

p on p+ layer Spreading resistance
3-point probe

All of the above

non player Four-point probe sheet-resistance measurement coupled
p on n layer with thickness

Depth profiling 1. C-V measurements

2. C-V coupled with etched steps
3. Differential resistance in avalanche
4. Angle lap coupled with
a Spreading resistance
b 3-point probe
c 4-point probe
5. Sequential thin-layer removal and sheet-resistance
measurement

Lateral profiling Electroplating (qualitative only)

Electropolishing (qualitative only)
Spreading resistance
2-point probe
Close-spaced 4-point probe
Photovoltaic probe

Very high resistivity HaJl measurements

Forward-biased 4-point probe

Very small areas Spn;ading resistance

Voltage breakdown
C-V measurement

N oncontacting Eddy current, microwave, capacitative coupled probes

Small irregular-shaped sheets van der Pauw

to several hundred percent can occur. This problem is most likely when profiling
thin layers but should always be considered, since an abraded surface is often used
to make contacting easier. Conversely, exceedingly high resistivity materials may
be lowered in resistivity because of additional carriers arising from damage-induced
defects.
By their very nature, resistivity measurements are geometry-dependent and quite
sensitive to boundary conditions. Because of this sensitivity, many correction factors
have been calculated. Some are included in the following pages, and many others
are referenced. Most semiconductor materials have rather high temperature coeffi-
cients of resistivity; so if precise measurements are desired, or if the ambient varies
widely, suitable corrections should be made. Curves for silicon and germanium are
included later in the text. Since the coefficient can change appreciably with impurity
content, some caution should be exercised in extrapolations involving materials for
which few data are available.
When the material to be measured is being electrically isolated by a p-n junction,
the p-n junction may not afford complete electrical isolation, and in some cases,
the current flow used for measurement can debias the junction and allow additional
current to flow across it. 4
 Resistivity and Carrier-Concentration Measurements 67

3.2 BASIC METHODS

Direct Method. The oldest way of finding the resistivity p(ohm-centimeter) is to

use a rectangular sample of known dimensions to measure the resistance R and use
the relation R = pL/A, where L is the sample length and A its cross section. A
disadvantage is that p will also contain a contact-resistance term, which for semi-
conductors can be appreciable. The effect can be minimized by plotting measured
resistivity vs. applied voltage. 5 This resistivity will ordinarily decrease as the voltage
increases and finally become relatively constant. If injection from the contacts has
not become excessive at that point, the resistivity is probably no more than a few
percent high. Injection difficulties can arise only with long-lifetime materials such
as silicon and germanium but should seldom be a problem.
Two-Point Probe. The effect of contact resistance can be eliminated by use of
the two-point probe of Fig. 3.1 if the specimen cross section is relatively uniform.
Measurement restrictions are that the current must be kept low enough to prevent
heating of the sample, the voltmeter must have a high input impedance, and meas-
urements must be made far enough away from the contacts that any minority carriers
injected will have already recombined. The requirements for the contacts are not
very stringent and vary from plating or solder to spring-loaded crumpled-metal
mesh. However, ifthe contacting is very poor, the equipotential lines will be distorted
near the ends. To minimize this effect, ASTM F 43 recommends that the maximum
cross-sectional dimension be not more than one-third the length of the sample and
assumes the measurement will be made at the midpoint of the bar. If long bars
are used and profiling is done by moving the two voltage points along it, readings
taken at points closer than one maximum cross-sectional dimension from the ends
are suspect. As an example of the effect of poor contacts, Fig. 3.2 shows the error
introduced when the current enters and leaves at the specified corners (which should
be the worst case) and the probes displaced varying amounts from the centerline. 6,7
If there are abrupt fluctuations in either cross section or resistivity, the equipotential
surfaces may not be perpendicular to the axis of the crystal and thus lead to errors.
To simplify contacting the sample, and to minimize error due to disturbing the
equipotentiallines,6 ears protruding from the sides of the sample can be used (see
also Fig. 5.4.). These same kinds of configurations are also useful in test structures
for evaluating diffused layer resistivity.7
If more than one set of measurements is to be made on a given sample, repro-
ducibility will be improved if a positioning jig is used so that all measurements to
be compared are actually made on the same volume of semiconductor. However,
continued contacting at the same point will cause mechanical damage to the surface
and erroneous readings.
Automatic two-point-probe instruments have been developed. Some even measure

Fig. 3.1. Two-point resistivity geometry. The voltage

probes have fixed spacing and are moved in unison
along the surface.
68 Semiconductor Measurements and Instrumentation

0.81----
z

0,61-_ __

c:
o
:;::: O A I - - - - - + - - - - - t - - - - - r - / - - - - + - i - - i - - - - t - - - - - - j
.'2
>
OJ
o

0,21_----~~~--1_---~~---,~----_+-__;

OL-_ _ _ ~ ___ ~===c=_ ______ ~ ________L _______ ~ __~

o 0.2 0.4 0.6 0.8 1.0

Prabe displacement, d/b
Fig. 3.2. Graph of the deviation 8 caused by worst-case contacts vs. the probe
displacement d/b. Curve (1) is for a = 4.0, h = 4.0, I = 20.0, and s = 10.0. Curve
(2) isfor a = 6.0, h = 6.0, l = 20.0, and s = 1.0. Curve (3) is for a = 10.0, h = 10.0,
l = 20.0, and s = 1.0. (Adapted from Swartzendruber. 6 )

the crystal diameter at the point of resistivity measurement, and provide automatic
data printout of the position of measurement, crystal diameter at that point, and
resistivity. 8 Advantages of such systems are speed of evaluation and a minimization
of human errors.
Most Czochralski-grown silicon crystals have a radial-resistivity variation as well
as a longitudinal one. Because of the radial component, the two-point method and
the four-point method to be described in the next section will not give comparable
results when measurements are made the length of the crystal. That is, V/ I of Fig.
3.1 is given by
v S
(3.1 )
I 2'lTJgo[r dr/per)]
where Ro is the radius of the ingot. However the four-point-probe voltage will
depend primarily on p(Ro)' By making both readings and assuming the functional
form of the radial gradient, its magnitude can be estimated. 9 The two-point method
can be used for slice radial-resistivity measurements by cutting a test bar as recom-
mended by ASTM F 81 and shown in Fig. 3.3.
A single movable probe can be used and the voltage measured between it and
a current lead or other suitable reference. By making several readings, dV/ dx can
be plotted and the resistivity calculated from
A dV
p = -- (3.2)
I dx
where x is the distance along the surface.
 Resistivity and Carrier-Concentration Measurements 69

32mm~

Fig. 3.3 Bar and probe orientation for measuring radial-

resistivity variation by the two-point-probe method. The
maximum bar width should be less than one-tenth of the
slice diameter. (From ASTM FBi.)

Linear Four-Point Probes. In the semiconductor industry the most generally used
technique for the measurement of resistivity is the four-point probe. * The method
is normally nondestructive; however, the probe points may damage certain semicon-
ductor materials when excessive probe pressure is applied. The usual geometry is
to place the probes in a line and use equal probe spacing. Current is passed through
the outer two probes and the potential developed across the inner two probes is
measured, though any of the other five combinations of current and voltage probes
can in principle be used (see, for example, Table 3.3), and many combinations of
unequal spacings have been considered.t For probes resting on a semi-infinite
medium (Fig. 3.4) the resistivity is
27T(VII)
p =----------------~~~-------------- (3.3)
[l/Sl + I/S3 - I/(Sl + S2) - I/(S2 + S3)]
where S is the probe spacing in centimeters. When the probes are equally spaced,
Sl = S2 = S3' and Eq. (3.3) reduces to

p = 27TS..[.
I
(3.4)

The limitation of current for accurate measurements will be discussed later, but in
general it is small fractions of amperes. Further, it is often convenient to preset

*The four-point probe is by no means new. Indeed, it was used as early as 1916 to measure the
earth's resistivity and is referred to in geophysics texts as "Wenner's method" [F. Wenner, A Method
of Measuring Earth Resistivity, Bulletin of the Bureau of Standards, 12:469-478 (1916)].
tSee, for example, C. A. Heiland, "Geophysical Exploration," Prentice-Hall, Inc., Englewood Cliffs,
N.J., 1940.

I~ V

Fig. 3.4. Linear four-point resisti¥ity probe.

70 Semiconductor Measurements and Instrumentation

the current to 27TS milliamperes or microamperes so that the resistivity in ohm-

centimeters will be numerically equal to the measured voltage in milli- or microvolts,
respectively. Alternately, the probe spacing can be 0.159 cm (0.062 in), so that 27TS
equals 1, in which case p is given numerically by VI1.
More often than not, a large enough sample to be considered infinite is not
available, and in those cases Eq. (3.4) is not directly applicable. However, since
the four-point probe offers the most convenient mode of resistivity measurement,
a variety of corrections have been developed. They are summarized in Table 3.2
and mostly fall into three categories:
l. Those to be used on cylindrical samples, i.e., unsliced crystals
2. Those which are primarily applicable to slices
3. Those for rectangular parallelepipeds
In general, the solutions are such that simple multiplicative correction factors can
be applied to Eq. (3.4) to give satisfactory accuracy. The corrections are available
from the references cited in Table 3.2, sometimes as curves and sometimes in tabular
form. Figure 3.5 includes some of the more common ones. It is recommended that

Table 3.2. Linear Four-Point-Probe Formulas and Correction Index

Configuration Comments Reference

Thick sample, boundaries> lOSfrom No corrections required, p = 10

probes 2'1TS(V/I)
Thick sample, near edge For nonconducting boundaries the 10
meter may read as much as 100%
high
Circular rod Applicable to pulled crystals 11, 12
Half-cylinder 13
Rectangular bars of infinite length but If the sample becomes very thin, see 14
with cross-sectional dimensions Ref. 27
comparable with S
Thin sample, with W < O.IS, and p = 4.53 W(V/I), R8 = 4.53 (V/I) 10
boundaries >20S from probes
Intermediate-thickness slice with This and following cases are appli- 10, 15
lateral boundaries> 20S from probe cable to slice measurements
(conducting and nonconducting
bottom surface)
Circular sheet with radius <20S and 17, 20-26
probes centered on slice
Circular sheet with radius <20S and 21-25
probes displaced from center but
lying along a radius
Circular sheet with radius <20S and 21-25
probes displaced from center, lying
along a radius but perpendicular to
radius
Rectangular sheet with probes sym- 27
metrically placed
Rectangular sheet with probes dis- 27
placed from the center
Infinite sheets with holes near probes Not likely in semiconductor slices, 28
might occur in measuring metalliza-
tion R. near feedthrough
 Resistivity and Carrier-Concentration Measurements 71

1.0

Nonconducting 1.0
boundary Nonconducting
0.9 boundary
u.
u.

nJ
0.8
1.,;.,1·,1,1
1
0.7

0 1.0 5
LIS
(0)

10

1 ----------~-~-=-~------~ a = 00
0.4 '-':----!~-'----:"-:--::'::--=':__-::-!:-".....".!:-::--::l
4 2 0.4 0.2 0.1 0.04 002 0.01 4 2 04 0.2 0.1 004 0.020.01
5/0 Sia
(b)

Fig. 3.5. Correction factors for four-point probes. p = Fp meas . (a) Flat surface.
(From Valdes.1°) (b) Circular cylinder. (From Murashima et al. 12 )

those of particular interest be plotted on a scale large enough to be easily legible

and kept with the resistivity test set. *
An isolated thin slice of resistivity PI and infinite lateral expanse can be considered
as a special case of a two-layered structure in which the bottom layer is infinitely
thick and has infinite resistivity. If a metallic backing is on the slice, it can be
approximated by a zero-resistivity bottom layer. Corrections for these two limits
are given in Refs. 10 and 15. When the second layer has an intermediate resistivity
P2' the measured resistivity is given by I6

P
"" [kn
= PI (I + 4 n~
"" - ----r;====~~
kn]) (3.5)
meas v'l + (2nt/15)2 v'4 + (2nt/15)2
where the top-layer thickness is t, and

k = P2 - PI
P2 + PI
For some combinations ofthree-Iayered structures, similar expressions are available
but are seldom used. For an electrically isolated slice, P approaches 0.73 (W/S)P meas

*For methods of obtaining more accurate interpolations directly from small curves such as those in
Figs. 3.5 tlrrough 3.7, see Robert L. Wolke, An Interpolator for Reading Plots in Technical Journals,
Rev. Sci. Instr., 44:1418 (1973), and J. S. Blakemore, Comments on "An Interpolator for Reading
Plots in Technical Journals," Rev. Sci. Instr., 45:466 (1974).
72 Semiconductor Measurements and Instrumentation

(where W = slice thickness) as WIS becomes less than 1. If the back of the slice
is covered with a conducting layer, e.g., a metal layer, or a very low resistivity
substrate in the case of epitaxial layers, dependable results are possible only if WI S
is greater than about 0.5. Thus, in order to measure layers a few micrometers thick
accurately, very close probe spacing is required. In an attempt to circumvent this
difficulty, other four-point-probe geometries have been used with limited success.
These are described in later sections.
If thin slices have finite extent, two sets of corrections are required. They are
usually considered to be independent of each other and are given in terms of a
measured VI I. That is,
(3.6)
where Fl is the correction for edge effects and F; takes into account the slice thick-
ness.17,18 For thicknesses greater than the probe spacing interaction between thick-
ness and edge effects does not allow a simple set of independent corrections. Sheet
resistance Rs in ohms per square is often used in evaluating thin conducting layers.
Rs equals VI I when the contacts extend the fulllength of opposite sides of a square
of material and are independent of the size of the square. For four-point probes
Rs = F* (VII). Table 3.3 gives F* for all possible combinations of current and
voltage probes. 19 Figure 3.6 gives Fl , and Fig. 3.7 shows F2 for circular samples.
Noncollinear Probe Spacing. As mentioned earlier, the probe array need not be
linear and in principle can be of any configuration. The one most commonly used
is square (Table 3.4). However, several others which have advantages for special
applications have been investigated. These are summarized in Table 3.4.
Square Array. Table 3.5 summarizes the various corrections developed for the
square array. They are not as extensive as for the linear case but are still adequate
for most circumstances. The basic equation 17 for the square array resting on the
surface of a semi-infinite medium is
p = 2'lTS V (3.7)
2 - V2 I
van der Pauw Method. 34,35 Rather than depend on miscellaneous corrections for
finite sheets, it is possible, by placing four contacts on the periphery of the sample,
to determine Rs directly. The geometry is shown in Fig. 3.8.

Table 3.3. Four-Point-Probe Correction for Use When Measuring

Thin Slices

1 2 3 4
t t t t
Correction factor F*
Current probes Voltage probes for thin layer

1-4 2-3 (7T/ln 2) "'" 4.532

1-2 3-4 27T/(ln 4 - In 3) "'" 21.84
1-3 2-4 27T/(ln 3 - In 2) "'" 15.50
2-4 1-3 27T/(/n 3 - In 2) "'" 15.50
3-4 1-2 27T/(ln 4 - In 3) "'" 21.84
2-3 1-4 (7T/ln 2) "'" 4.532

R. = F* (V/I), p = F*W(V/J).
Adapted from Rymaszewski.1 9
 Resistivity and Carrier-Concentration Measurements 73

1.0
/"
....-
0.8
Fig. 3.6. Correction factor for a thin slice /
with nonconducting surfaces. p = Fp meas ' 0.6
"--
[Adapted from G. Knight, Measurement of 0.4
Semiconductor Parameters, in Lloyd P.
0.2
vV'
o ~--
Hunter (ed.), "Handbook of Semiconductor
Parameters," McGraw-Hill Book Company, 0.1 02 0.5 10 2.0 5.0 10.0
New York, 1956. Used by permission.] W/S

R
8
= 2/n 2 (R'
_'IT_ + R")\f'( R' )
U R"
(3.8)

where f(R'/R") is van der Pauw's function and is shown in Fig. 3.9. R'is the
potential difference between the contacts C and D per unit current through the
contacts A and B, and R" is the potential difference between the contacts A and
D per unit current through the contacts Band C.
If the contacts are placed so that they are symmetrical about a line through any
pair of nonadjacent contacts, R' / R" = I and van der Pauw's function also becomes
1. In addition to requiring contacts on the periphery, the method also must have
very small contacts, a uniform thickness sample, and no isolated holes in the interior
of the sample. When symmetrical contacts are used, any deviation in the ratio of
R' / R" is a measure of resistivity inhomogeneity and is often used for that purpose.
However, if the variation of resistivity is not too great, the value read will be very
close to the average obtained by integrating over the whole area. For large variation,
the van der Pauw average will be lower than the integrated value. 36
Delta Four-Point Probe,37 This and the following configuration have been devel-

1.0

0.9 /
~
0.8 I
tI:: 0.7
/
0.6 /
0.5
/
0.4 I I I I I I I
1 2 3 4 5 6 8 10 20 30 40 50
DIS
P = F2 WRs= F2 W (4.53 Vir) = F2Pmeasured
Fig. 3.7. Correction factor F2 for probes centered in a
circular slice of finite diameter D. (Adapted from Smits. 20)
74 Semiconductor Measurements and Instrumentation

Table 3.4. Noncollinear Four-Point-Probe Formulas and Guide

Resistivity
Description Geometry given by Advantages

Square array 2'lTS V Given probe

r-*S~I P=2-V21 spacing will fit
I v in smaller area
L., t..J = 10.7 S£.I
Square array R =~£. Given probe
8 In2 I spacing will fit
in smaller area
= 9.06£.
I

Rectangular I I 2'lTS V
ooE-nS~

. .
v
S
v
P = 2 - (2/Vf+II2) I

Random placement See van der Pauw Irregularly shaped

at periphery of samples can be
uniform-thickness
plate
0 measured without
precalculated
correction
factors

Delta See Delta Can be used to

,. ...,v
I
measure thin
high-resistivity
L-. -.....J
layers on low-
resistivity layers

Over-under See Over-under Can be used to

IE· 1
measure thin
high-resistivity
layers on low-
resistivity layers

Table 3.5. Square-Array Correction Index

Configuration Reference

Thick sample, near edge 29

Intermediate-thickness sheet 17
Thin semi-infinite sheet with probes near edge 30
Probes in center of thin circular slice of finite radius 26,24,30
Probes displaced from center of thin circular slice along radius. Voltage 24
probes parallel to radius
Probes displaced from center of thin circular slice along a radius. Voltage 24
probes perpendicular to radius
Probes symmetrical about radius perpendicular to straight side of 30
semicircular slice
Probes symmetrically placed on quarter slice 30
Square array symmetrically placed on square slice 31,32
Probes on edge of hole in infinite slice 33
 Resistivity and Carrier-Concentration Measurements 75

Fig. 3.S. A sample of arbitrary shape used

with the van der Pauw method.

oped in an effort to allow direct measurement of thin high-resistivity layers which

are in direct contact with low-resistivity substrates. The probe geometry is shown
in Table 3.4. The resistivity is a complex function of probe spacing, layer thickness,
substrate resistivity, and substrate thickness, and interpretation requires an elaborate
set of correction factors. The useful resistivity range depends on the layer thickness
and probe spacing. For lO-.um layer thickness and a spacing of 24.um, a layer
resistivity twenty times the substrate resistivity can be measured.
Over-Under Probe. 38 The placement of the probes is shown in Table 3.4. Current
flows through probes 1 and 3 and voltage is measured between probes 2 and 4.
As in the previous configuration, the solutions are complex. As an example of the
useful range, for layer resistivities of the order of 0.1 n-cm, the probe spacing must
be less than 50 .urn. Higher resistivities can tolerate wider probe spacing.

3.3 TWO- AND FOUR-POINT PROBE INSTRUMENTATION

Basic Electrical Circuitry. The electrical circuitry for a four-point probe can be
quite simple, and requires only a probe, ammeter, voltmeter, and source of current.
However, the current and voltage circuits do not have a common ground, and thus
one must float relative to the other. In addition, to minimize effects of pickup,
rectification at the probes, and Seebeck voltages, provisions are usually made for
reversing current flow. However, if the sample, probes, leads, etc., are all properly
shielded, there will be no pickup and the readings will be the same unless the current
is high enough to cause heating. This circuit suffers primarily because the current
source is not, constant so that continual adjustment is required. A somewhat better
one uses the high output impedance of a transistor as a current source. If more
sophistication is desired, constant-current sources can be used,39 and for production,
equipment with preset currents is a necessity.

Fig. 3.9. f(R'fR") vs. R'fR". To be used with

Eq. (3.8). (From van der Pauw. 34 )
l~~bl?tlbJ
1 10
R'/R"-
10 2 103
76 Semiconductor Measurements and Instrumentation

(a)

Fig. 3.10. Ratio-reading ac

meter using transformer isola-
(bl tion. (Adapted from Ref 43.)

Various ac meters have been built. 15,41,42 They have the advantage of eliminating
thermoelectric effects and of allowing tuned voltmeters to reduce system noise.
Rectification at the contacts will cause waveform distortion and should be avoided,
since it may cause appreciable error. It is possible to apply a forward dc bias to
all probes, lower contact resistance, and thus lessen errors due to the voltmeter's
loading the probes. 41,42 There are certain restrictions which must be imposed in
order that accuracy is not impaired. The bias current cannot be large enough to
flood the area between the probes with excess carriers, nor can the peak alternating
current be larger than the dc bias; otherwise rectification can occur during some
portions of the cycle.
Since the resistivity depends on VI I, rather than measuring them independently,
some equipment has been designed to determine the ratio directly. The general
scheme is as shown in Fig. 3. lOa, in which the inner-probe voltage is balanced against
the voltage generated by the current flowing through the potentiometer Pl. Practi-

Fig. 3.11. Ratio-reading ac resistivity meter. (Adapted from Logan. 21 )

 Resistivity and Carrier-Concentration Measurements 77

cally, isolation is most easily effected by using alternating current and a transformer.
Such a circuit is shown43 in Fig. 3.lOb.
An alternate approach in Fig. 3.ll uses operational amplifiers for isolation but
still is ac, so that capacitor coupling can be used where appropriate to prevent
difficulties with drift and dc levels. 21 In circuitry such as this, it is not necessary
to have a constant-current source or even to know its approximate value. From
a practical standpoint, however, it is best to monitor the current to make sure that
it is in the range recommended by the manufacturer. Otherwise, gross errors can
occur, as, for example, if the probes should not make good contact, very little current
would flow, and system noise would be balanced against the potentiometer voltage.
A different approach for comparing the probe voltage with a voltage proportional
to the current is to use a capacitor switched between points A-B and C-D of Fig.
3.12. When the voltage across Rl is equal to that of Vprobe' the capacitor will neither
charge nor discharge as it is switched. 44 In the event that it is desired to use this
method and observe the effects of current in each direction (i.e., if there is rectifica-
tion), the circuit can be suitably modified. 45
Instead of I-V measurements, the four-terminal network of either the two- or
four-point probe connected to various bridges may be used. 46,47 Also, for dc
measurements, a low-impedance potentiometer may be used between ground and
one of the voltage probes to provide a virtual ground. 46
Special Circuitry. In addition to the basic circuitry just described, circuit modi-
fications can be used to perform some of the corrections discussed earlier, and/or
to make data collection more rapid.
For W / S less than 0.5, the slice-thickness correction factor is linear in W/ S. Thus,
a simple potentiometer attenuator somewhere in the voltmeter circuit can be used
to make the calculation directly.41 Nonlinear corrections, e.g., for a finite-diameter
slice, can be approximated by a series of linear steps, and again may be done by
potentiometer. Alternatively, operational amplifiers can be used and the various
correction networks inserted in the feedback 100p.48
Many instruments use meters, but digital readout minimizes operator error and
is preferred for routine operations. Further, complete timing and sequencing con-
trols, coupled with automatic temperature compensation and punched-card (or
magnetic-tape) output, can be combined with any of the equipment described to
provide fully automatic operation and data reduction. 49-51 When profiling surfaces,
for example, along the length of a crystal, the output of the meter can be fed into
printout equipment so that distance and resistivity values can be automatically
tabulated.
If a single stylus (or an electron beam) is moved in discrete steps or is used
continuously,

p=--
A dV (3.9)
I dx

Fig. 3.12. Chopper method for comparing the inner-probe voltage

with the IR drop across resistor R I .
78 Semiconductor Measurements and Instrumentation

Thus, by differentiating the stylus voltage V, p(x) is directly determined and can
be plotted. 52 ,53 For point-by-point movement of the stylus across the surface of very
high resistivity materials, pulsed current may be used to avoid heating, and bridge
balancing of the probe can be used to minimize the effects of detector impedance
on the measured voltage. 54
Probes. Probe design centers around accurately maintaining spacing, providing
proper loading, and minimizing contact resistance. In general, a wide variety of
metals with high Young's moduli are quite satisfactory. Silicon carbide 56 has been
suggested because of its great hardness; however, its contact resistance can be very
high. Tungsten needles can be used and are easily brought to a fine point by
electrolytic shaping.
Nonjeweled phonograph needles make good probe points, since they are hard
and well pointed. "Burning in" is sometimes used to reduce contact resistance, and
consists of heating the probe tip and semiconductor surface enough with a short
current pulse (e.g., a capacitor discharge) to cause local alloying. For example,
copper-plated osmium-tipped probes 57 and tin-plated phosphorus bronze needles 58
have been used with GaAs, Duralumin for p-type silicon, and phosphorus bronze
for n-type silicon. 59 A Tesla-coil discharge also can be used with a wide variety
of points to improve the contacting. For high-temperature operation, the probe must
maintain strength and not react with the semiconductor being measured. Tungsten
carbide tips, for example, have been used on some materials at temperatures of
950°C.60
In order to minimize damage to the surface, liquid-metal probes can be built.
Mercury columns61 and globules held on the end of metallic pins62 have been used,
but the material to be measured must not amalgamate with the mercury. Liquid
gallium is also applicable, but measuring temperatures must be a little above normal
room temperature, since the gallium melting point is 29.8°C. Concern over the
possibility of probe-semiconductor chemical interaction should not be restricted to
the high-temperature range. Chance contaminates left on the surface can cause
etching, and high humidity combined with high voltages may cause an electrolytic
transfer of probe material to the semiconductor surface. 63
Numerous guides and loading mechanisms have been devised,64-70 but in general
they are either spring-loaded or at the end of pivoted arms with dead weights. The
amount of probe loading depends on the material being measured and the tip
diameter, but typically germanium will require 25 to 100 g and silicon 100 to 200 g
for tip radii of 0.2 mil. Ordinarily, guide bearings should be as near the probe ends
as possible. Most designs allow individual motion of each probe, but some have
pairs rigidly mounted. For high-temperature operation, the guides and support
(head) can be made of ceramic.
Since errors in probe spacing can cause significant errors in the resistivity readings,
considerable care must be taken in both the initial spacing and the spacing mainte-
nance. Precision boring combined with quality bearings can produce the accuracy
required, but a simple and rather unique alternate probe-head arrangement involves
the use of two sections of threaded dielectric rod as guides, with the probes being
laid in the grooves and held in place by pressure pads. The spacing is then as good
as the accuracy of the thread.71 The actual spacing can be determined by indenting
metal foil backed with paper and measuring the distance between imprints. This
procedure gives crisp imprints which are easy to observe but does not take into
account the possibility of skidding which may occur when a loose probe contacts
 Resistivity and Carrier-Concentration Measurements 79

-Contact bar
Fig. 3.13. Calibrator for four-point probes. Rl
should be many times R. Its value will depend on
specific characteristics of electronics and smiconduc-
tor. For silicon Rl should be approximately 500R.
t R1
Standard resistor, R

the hard semiconductor surface. The small impressions made in the semiconductor
itself can be measured, though they are usually somewhat indistinct. If an in-
verted-stage microscope is available, the probe may be pressed down on a microscope
slide and viewed directly.
In order to facilitate measurement-sampling plans, the equipment is sometimes
designed to step about on a slice surface to prearranged positions and to repeat
them quite accurately. Iflinear profiling is desired, table motion in only one direction
will suffice, and a variety of mechanical arrangements are possible. 63,72 As an
alternative to raising the probes each time the sample is moved, rolling-ball probes
(e.g., ball-point pens) have been used, and the resistivity read continuously.73
Calibration. It is important to be able to calibrate the equipment, and two
procedures are available. The first is to keep a sample of the material(s) to be
measured, and periodically read its value. When doing this, certain precautions
should be observed: (1) Either always measure at the same temperature, or check
the temperature and correct for it. (2) Either have a sample free of inhomogeneities
or always measure at the same spot on the sample, preferably by using permanent
jigging. (3) Resurface the sample as necessary, since after many probe applications
in the same region, considerable chipping can occur. The second procedure uses a
resistor of known value connected either between probes, or instead of probes, to
check the voltmeter and ammeter calibration circuitry. A somewhat better way uses
the resistor network of Fig. 3.13. Now, any excessive loading of the voltage probes
or failure of the constant-current source will show up as a faulty reading. In neither
case, however, will it detect any shift in probe spacing.

3.4 ERRORS IN TWO- AND FOUR-POINT MEASUREMENTS

Sample Size. One of the more obvious errors in determining resistivity arises from
failure to consider all corrections to account for limited geometry. It should be
remembered, however, that in determining slice resistivity, if the slice thickness is
less than a probe spacing (the usual case), the calculated value for p varies directly
with the assumed value for slice thickness. Thus errors in thickness measurement
translate directly into resistivity error. If no corrections are to be made, the probe
spacing can be initially chosen to minimize the errors for any expected range of
variation. 74
Substrate Leakage. If the sample being measured is isolated from a substrate
by a p-n junction, e.g., an n-on-p epitaxial layer, substrate leakage current can
introduce errors.4 The current may arise either from defective junctions or from
debiasing. The latter is more likely to occur as the sheet value of the layer increases.
For silicon, reasonable measurements can be made if the sheet resistance is less than
1,000 Q/square and the measuring current is low enough. If there is doubt about
the current range, Rs should be measured as a function of probe current and
operation restricted to the region of Rs independent of current.
Probe Spacing. Probe spacing enters directly into four-point bulk-resistivity
80 Semiconductor Measurements and Instrumentation

calculations, so that if the spacings are equal, any error in determining that spacing
translates into the same error in resistivity. If the spacing between each probe of
a linear array is slightly different from the nominal S,
dp 1
-P = -(3~Xl
4S
- 5~X2 + 5~X3 - 3~X4) (3.10)

where probes 2 and 3 are the voltage probes and ~Xi is the linear displacement
of the ith probe from its nominal position. 75 If the ~i are measured for each
resistivity determination, Eq. (3.10) can be used to make corrections as required.
As an example, if one of the voltage probes of a lO-mil spaced set is displaced 1 mil
toward the other one, the measured resistivity value will be approximately 12 percent
low.
When the probe wander is random, independent, and has a standard deviation
of 8x, the standard deviation of the resistivity is
8p = 2.068x (3.11)
S
For two-point measurements, the standard deviation is

8p = 1.418x (3.12)
S
so that for comparable probe design, a two-point probe is more accurate.
For very thin slices, if the calculations are based on VI I measurements and not
on a previously bulk-calibrated machine, S does not affect the readings as long as
all spacings are equal. When the spacing is not equal, but known, an additional
correction factor F. can be introduced such that 76
p = F,.Pmeas
where (3.13)

For small variations,

(3.14)

where Sis the mean value of separation. When other multiplicative corrections must
be applied, F,. can be added to the list. If the probe displacements are random and
independent, each with a standard deviation 8x, the relative standard deviation of
F,., if all probe spacings are nominally equal, is given by
8F,. = ('-IS 8S)(Sln 4) (3.15)
For square arrays, first-order probe-displacement error can be eliminated by
averaging the value obtained from two separate measurements using different pairs
of current probes but with one current probe common between the two measure-
ments.77
Light. Light shining on the surface may introduce spurious photovoltages which
will cause instrumentation problems.
Temperature Effects. Since semiconductors have a relatively large temperature
 Resistivity and Carrier-Concentration Measurements 81

coefficient of resistivity, a few percent error can be introduced either by failure to

compensate for varying ambient or by unknowingly heating the sample during the
measurement itself. The latter is most likely to occur in low-resistivity samples where
large currents are required in order to obtain readily measurable voltages. The
National Bureau of Standards recommended procedure suggests placing the sample
on a large copper block* which has a thermometer placed in it. Figure 3.14 gives
CT for Si and Ge. 78 Note that for 10 Q-cm and greater, a 5° temperature difference
will produce a 4 percent difference in the resistivity reading.
Thermoelectric Effects. Temperature gradients in the sample, whether caused by
the ambient or by excessive probe current, will generate a thermoelectric voltage.
The use of alternating or low current will minimize the effect.
Probe Injection. For long-lifetime material, the contacts may inject enough carriers
to cause conductivity modulation and seriously affect resistivity readings.
AC Pickup. DC sets are likely to have errors introduced through contact rectifica-
tion of miscellaneous induced stray currents. Operation in a shielded room is
sometimes required or, better still, the probe assembly is enclosed in a carefully
shielded box. Readings should be taken with current flow in each direction and
the corresponding resistivity values averaged. If the two values differ by more than
a few percent, more shielding should be used.
Instrument Current. From a pure instrumentation standpoint, higher currents
make the voltage measurement easier and less susceptible to noise. However, the
high currents cause local heating and, sometimes, conductivity modulation. Because
these effects are difficult to evaluate analytically, it is helpful to plot measured

* A thin mica spacer can be used to electrically insulate the slice from the copper and still maintain
good thermal contact.

1.0 1.0,---------------.
l.--rr-r-- :t~.,,-p.
0.8
,/ 08
0.6 /

/r"II-II- I
I
0.6
0.4 I
l N-type silicon
I
I This work OA

!~.J +
C>
Q) 0.2 Chopman,et 01
"0
(Ref.2) ~ 0.2 / N - type germanium
"-
<f!. 'i~{I I This work
0 ~ Lattice scattering (/2. 0 - Lattice scatter i ng
>- >-
~ -0.2 10-310-2 10-' 1 10 10 2 103 ~ -0.2 '----1-"-0""-3;--10L-72-10-"---:-'-'----.--l10--,L
02,,--J
'Vi Resistivity (.a-cm) w
~ ~ Resistivity ( .a-cm)
't 't
1:::
Q)
1:::
'u .~ 1 . 0 , - - - - - - - - - - - - - - - ,
~ 1.0,---------------".--,
~ D~ ~
'l-

8 0.8 g._~ _ _ " I S 0.8

4-

/~- II
ill ~
~ ,/"t/ ~ 0.6 /I
""§ 0.6 il,lp-type silicon +-
o
Q)
(L OA I 11
, /
I this ork[Boron doped ~ 0.4
/ lI p:type germanium
~ /" / w lAlu~in~~doDed E
I- I ---- I this work
~ 0.2 ..II
0.2.,-+

o
"*.t
•
{

~
0
+ Chapman,etal (Ref2)
Long and Myers(Ref.3)
Lattice scattering
o
- Lattice scattering

- O. 2 '----1..1
0 --;3;--10
.L--;:-2-1..10,"",-,,--.1.--10'----1..1.
0"'"2---.J
-02 10-3 10-2 10-1 10 102 103
Resistivity (.a-cm) Resistivity (.a -cm)

Fig. 3.14. Temperature coefficient of resistivity of silicon and germanium in the

extrinsic region. peT) = P23o[l - CreT - 23)], where T is the temperature of
measurement. (From Bullis et aU B)
82 Semiconductor Measurements and Instrumentation

resistivity vs. current for each range to be covered. Usually there will be a broad
region where the resistivity is independent of current. From the boundary of this
region, safe operating currents can be drawn. 79.8o
Applied Voltage. If the electric field becomes too high, a mobility decrease occurs
which will make the resistivity reading too high.

3.5 SPREADING RESISTANCE

In order to minimize the corrections that must be used with probe arrays and
limited volumes of material, spreading resistance of a point-contact probe is some-
times used.58.81-87 For a flat circular contact of radius a uniformly affixed to the
surfaCe of a semi-infinite medium of resistivity p, the spreading resistance Rsp is 88
(3.16)

If the contact is a hemisphere of radius r embedded in the solid, as could happen

if a needle were pressed down into the material,
R =-p- (3.17)
sp 27Tr
For values of other geometries see Refs. 88 to 91. For a brittle semiconductor
material, the probe would normally be expected to flatten, and the geometry is
probably a flat circular contacting area with radius 90.91

a=1.1 [-Fr ( -I +-I )J1/3 (3.18)

2 E1 E2
where F is the force on the probe tip, r the tip radius, E1 Young's modulus for the
probe material, and E2 Young's modulus for the material being measured.
Rather than attempting to calculate Rsp from Eqs. (3.16) and (3.18), the usual
procedure is carefully to construct a tip, plot the measured Rsp for se leral known
resistivities of homogeneous material, and prepare a calibration curve. Experience
has shown that reproducibility of a given tip increases with use up to perhaps 1,000
measurements, after which it remains constant until damaged. In order to shorten
the "burn-in" cycle, various probe treatments such as a short abrasion with a
sandblaster have been used with some success.
The calibr~tion curve varies with the probe pressure and the rate of pressure
loading but ordinarily is more reproducible with increasing pressure. However,
loading should be low enough to prevent fracture and minimize plastic flow of either
the semiconductor or probe tip. The mean pressure P over the contact area described
by Eq. (3.18) is given by

P = 0.42F1I3 [r (~1 + L) T/3 (3.19)

and plastic flow can be expected when P is about 0.4 of the indentation hardness. 81
Even though resistivity itself is independent of orientation in cubic materials,
spreading-resistance calibration curves are observed to vary with orientation. 86 The
surface finish can also affect the calibration curve; so care should be taken to ensure
that the same kind of surface is used for all measurements which use a given
calibration curve. It has also been tacitly assumed that the resistance of the probe
is negligible and that the metal-semiconductor barrier resistance is very small. The
latter may not necessarily be true, but if the barrier is reproducible, the calibration
curve will accommodate it.
 Resistivity and Carrier-Concentration Measurements 83

( 0)

(b)

Fig. 3.15. Various spreading-resistance probe arrangements. (c)

The actual contacting configuration may take several forms. It can be a single
movable probe for one contact, and a broad area contact for the current-return path.
It can be two closely spaced points so that the measured resistance is actually the
sum of two spreading resistances and hence has twice the problem of reprod ucibility
of a single probe, but has the advantage of being compact and self-contained. As
a compromise, current in and current out can each be by point-contact probe, but
an additional voltage probe can be added so that only the voltage drop across one
is measured. These are all illustrated in Fig. 3.15.
Most of the potential drop of a point contact occurs within a distance 3a from
the point. 86 Thus, resistance readings will be nearly independent of what lies at
depths greater than 3a, and conversely, if the sample changes concentration within
that distance, or if the whole sample is thinner than 3a, readings must be treated
accordingly. It is possible to make corrections for arbitrary concentration profiles
below the surface, but the mathematics are quite tedious. 92 However, if reasonably
accurate results are to be obtained when profiling near p-n junctions or abrupt steps
such as at an epitaxial film-substrate interface, such corrections are a necessity. In
addition to mathematical corrections, some experimental caution must also be
exercised when examining thin layers because with heavy probe loading, the top
layer may be so physically damaged and deformed that the next layer down is the
one which contributes to the spreading resistance. For silicon, layers of less than
2 pm usually begin to require less probe pressure than would normally be used for
good reproducibility. .
84 Semiconductor Measurements and Instrumentation

3.6 NONCONTACTING RESISTIVITY METHODS

Noncontacting resistivity methods* can be broken into several categories: (1) those
in which the sample is capacitance-coupled to a resistance-measuring apparatus,93-100
(2) those which measure the additional losses of an inductance when it is coupled
to the sample, 101-108 (3) those which measure the decay of eddy currents induced
in the sample (most applicable in the 10-5 to 10- 10 Q-cm range and hence not
ordinarily used for semiconductors),109 (4) those which measure the amount of
shielding the sample affords,llo (5) microwave measurements in which the sample
perturbs the transmission or reflection characteristics ofa wave guide or cavity,111-128
and (6) those which depend on a force interaction between the sample and its
environment. l29,l30 These measurements can be made without inducing probe
damage and, if properly done, will have no chance of adding contamination even
at high temperatures where contacting probes could react with the semiconductor.
In addition, the effect of high-resistivity grain boundaries can be minimized. Con-
tact-resistance effects are removed, though variations in sample size can change the
coupling between sample and measuring circuit. However, despite these potential
advantages and the considerable investigation in the early 1960s none of them have
gained acceptance.
The resistance measurements required for the first two methods are usually done
at megahertz frequencies. Bridges, Q meters, and amplitude of oscillation have all
been reported, but the wide variety of rf configurations available has by no means
been exhausted. The choice appears to be primarily one of availability and personal
preference, though for a given resistivity and frequency range some will perform
better than others.
Bridges can be direct-reading in series or parallel equivalent resistance, but
Q-meter readings must be converted into the equivalent resistance. With Q meters,
very low impedance samples should be put in series with the inductance, and high
ones in parallel. However, with commercial equipment, the exposed terminals may
allow only parallel connections. In that case, in order to keep the Q high enough
for oscillation, a small capacitance may be added in series with low-resistivity samples
(for example, by increasing the plate-to-sample gap), though sensitivity may suffer.
Regardless of whether a bridge or a Q meter is used, the problem finally is one
of relating resistance change to sample resistivity. For the specific case of cylindrical
and spherical samples centered within a cylindrical solenoid, exact expresssions have
been derived,101 but for other geometries, experimentally determined calibration
curves must largely be used, though some corrections for slice thickness have been
calculated. 13l
Instead of using either a bridge or a Q meter, the sample can be coupled to an
oscillator-resonant circuit which, if appropriately designed, will oscillate with an
amplitude which depends on the resistivity. Depending on the frequency and the
conductivity of the sample, the energy will penetrate different depths into the sample,
so that a sample which is infinitely thick for one resistivity range may not be at
another. 132, 133
There are several methods by which microwaves can be used for resistivity me as-
urement.ll1-l28 However, before any extensive program to use microwave resistivity
measurements is embarked upon, carrier behavior in that frequency range should
*There are also noncontacting optical methods for directly determining carrier concentration. They
are described a little later in this chapter.
 Resistivity and Carrier-Concentration Measurements 85

be investigated, since resistivity may not be frequency-independent. 134 Silicon and

germanium can be dependably measured up to at least a few gigahertz. The percent
power transmitted through a tight-fitting sample inserted in a waveguide can be
calculated as a function of resistivity. Measurements will then give the resistivity
without any calibration requirements, but the precision shaping of the sample is
a major disadvantage. Fitted samples with a high-conductivity backplating can also
be used. In this arrangement the frequency is adjusted until the waveguide section
with the sample is a quarter wavelength, and then the standing-wave ratio is mea-
sured. The change in Q of a resonant cavity can be measured with the sample
mounted inside as a post. To remove the necessity of accurate cutting, slices, large
slabs, or whole crystals (if they have one smooth surface) can be placed against the
open end of a waveguide or a hole in the resonant cavity and the standing-wave
ratio or change in Q measured. If both the phase and the amplitude of the reflected
wave are determined, the resistivity of thin layers (e.g., epitaxial films) can be
measured if the substrate resistivity is known. 128

3.7 CARRIER CONCENTRATION

There are several methods that measure either carrier concentration or ionized-
impurity concentration rather than resistivity. Most of them can, if desired, be
calibrated in terms of resistivity, but in any event, for well-known materials conver-
sion from one to the other is a simple matter.
Hall Coefficient. The Hall coefficient may be used to determine the carrier
concentration. For details, see Chap. 5.
Thermoelectric Probe.1 35 ,136 The voltage developed between a hot probe contact-
ing the surface to be measured and large-area cold contact can be used as an
indication of carrier concentration, but the sensitivity is very poor.
Thermal Rebalance. 137 In general, the temperature vs. resistivity curve exhibits
a peak in resistivity, and the sharpness of the peak is a function of impurity concen-
tration. * For those materials such as silicon and germanium which have a maximum
resistivity not far above room temperature, it is possible to measure the resistance
of a sample at room temperature, increase the temperature to the point where the
resistance has gone through its peak and decreased to its original value, and deter-
mine the carrier concentration from the observed 6.T. Thus, the resistivity is deter-
mined without any knowledge of the geometry of the sample.t It is necessary,
however, for the contacts to be ohmic and have a much smaller temperature coeffi-
cient than the semiconductor. The major limitations of this method are the require-
ment for an ohmic contact and the fact that it is a destructive test.
Three-Point Probe.138-145 Diode breakdown voltage has been used to evaluate
material "quality" since the work on germanium and silicon in the early 1940s. If
good diodes can be constructed, breakdown voltage can be related to carrier concen-
tration through suitable curves.t However, even a poor diode formed by a point

* If there is appreciable compensation, interpretation is difficult because the width depends in a complex
manner on total impurity concentration.
tIn a similar vein, the slope of the R-T curve near room temperature has been used as a measure
of carrier concentration in tellurium. (See H. H. Hall, "Task A-I, Development of a Low Impedance
Pressure Gage," Physics Department, University of New Hampshire, NOrd 10358 Rep. 33, 1951.)
tS. M. Sze and J. C. Irvin, Impurity Levels in GaAs, Ge, and Silicon at 300 o K, Solid State Electron.,
11 :599-602 (1968).
86 Semiconductor Measurements and Instrumentation

contact on a polished surface, combined with an empirical curve, can give reasonable
reproducibility. As long as the point is slightly farther away from a conducting or
high-recombination surface boundary than the width of the depletion layer at
breakdown, the reading is independent of boundary effects. Because of this it is
suited for measuring thin high-resistivity layers on low-resistivity substrates. If the
space charge reaches a boundary before avalanche begins, large currents will flow
and the unit will appear in breakdown. Thus, instead of a single-line calibration
curve, multivalues occur, as shown in Fig. 3.16a. In the simplest form, a curve tracer
or oscilloscope can be used to observe the break in the I-V curve as voltage across
the sample is increased (Fig. 3.16). The forward drop across the broad area contact
can affect reproducibility and is eliminated by using an additional voltage probe
shown in Fig. 3.16b ("three-point probe").
To prevent local heating and possible damage to the semiconductor when break-
down occurs, some form of current limiting and pulsing should be used. Either a
series of short pulses of increasing amplitude 139 or a single sawtooth pulse can be
used with circuitry which detects the point of maximum voltage and automatically
stops current flow and reads the maximum voltage. When using calibration curves,
the fact that the "breakdown voltage" will depend on the probe material, probe
radius, probe loading, probe spacing, pulse length, and surface preparation should
be kept in mind, and care should be taken not to change any of those parameters
without a corresponding change in calibration.
Optical Methods. Both the optical-absorption coefficient and index of refraction
of semiconductors are dependent on the free-electron or hole concentration. It is
therefore possible in principle to determine the carrier concentration optically.
Such a method has the potential advantage of being nondestructive as well as
being able to respond to the properties near the surface, independent of what might
be below it (and thus it is useful for evaluating epitaxial layers). Its disadvantage
is that the range of concentrations that can be examined is usually very limited and
the equipment rather complex.

500.-----------------------~

10~-W~~~~~~~~~~~
2 5 810 15 2 5 810 16 2 5 810 17
Impurity concentrotion,atoms/cm3
(0 )

Fig. 3.16. Three-point calibration curve

and circuit. (From Allen, Clevenger, and
( bl Gupta. 139 )
 Resistivity and Carrier-Concentration Measurements 87

For wavelengths corresponding to energies less than the bandgap of the semicon-
ductor, the absorption coefficient a is reasonably sensitive to resistivity (carrier con-
centration).146.147 For shorter wavelengths, the total absorption coefficient is ordi-
narily orders of magnitude greater than the absorption due to carriers. In the
long-wavelength region, as the carrier concentration decreases, a drops to the point
where, unless the sample is very thick, reflective losses predominate. At that point,
small variations in surface finish will completely overshadow any effect of concen-
tration change. The wavelength used is not critical, but the free-carrier losses increase
as the wavelength; so a longer wavelength may be of some advantage. Care should
of course be taken to ensure that the wavelength chosen does not coincide with an
absorption line due to some other phenomenon. An example would be the 9-ftm
oxygen band in silicon. The total absorption is a measure of the total number of
carriers in the path, and can be used as an alternate to conventional sheet resistance
measurements for evaluating diffused layers in slices provided both surfaces are
optically finished. 202
From a convenience standpoint, reflectivity measurements are much more desir-
able, since they require just one polished surface and the only thickness limitation
is that it be greater than a few (l/a)s. In the same wavelength range, the reflectivity
R is related to impurity concentration only through changes in the absorption
coefficient and is relatively insensitive. Typically, R will be approximately 0.1 percent
higher for an absorption coefficient of 1,000 per centimeter than for an a of zero.
Very small changes in reflectivity may be detected by using the method of attenuated
total reflection. 156 When the light wave travels from a medium of higher to one
oflower refractive index, it will be reflected unless the angle of incidence cf> is greater
than the critical angle cf>c, in which case it will be totally reflected. When cf> is very
close to cf>c' the amplitude of the reflected wave is quite sensitive to the index of
refraction of the second medium. Thus, otherwise indiscernible changes in the index
can produce readily measured changes in reflectivity. Rather than fixing the angle
very close to critical and measuring changes in reflectivity, the reflectivity can be
measured as a function of angle. In that case the critical angle changes as the
absorption coefficient of the sample changes. 157
Plasma resonance 148-155 produces a minimum in the reflectivity vs. wavelength
curve that shifts appreciably with free-carrier concentration in the higher concen-
tration ranges (typically 5 X 10 18 to 5 X 1020 atoms/cm3 for silicon) and is readily
measurable. It should be possible to calculate the minimum for any given concen-
tration; however, the minimum is usually experimentally measured and calibration
curves constructed. 154 When applied to circumstances where there are large concen-
tration gradients perpendicular to the surface, additional interpretation difficulties
arise, since the radiation will penetrate to depths of about l/a and in a diffused layer,
for example, the concentration could change orders of magnitude in that depth.
It is possible, however, by measuring the sheet resistance and assuming a known
profile (e.g., gaussian or complementary error function), to predict the surface con-
centration of diffused layers. 155 When the layers are very thin, or when a uniform
sample of low carrier concentration is examined, the reflectivity minimum is found
to be very broad. Without some additional signal processing the accuracy oflocating
the exact minimum is therefore greatly reduced. Multiple scans combined with
multichannel digital integration have been used to reduce trace noise, and electronic
differentiation of the trace can help pinpoint the minimum more closely.155 In some
cases, the depth of the minimum can be used to estimate compensation. 203 Also,
the envelope of the IR interference pattern often used for measuring epitaxial layer
88 Semiconductor Measurements and Instrumentation

thickness (see Chap. 6) will exhibit a minimum due to the plasma resonance of the
substrate and can thus be used to check its concentration. 204
Instead of trying to measure the effect of carrier absorption on reflectivity, it is
also possible to measure the optical constants nand k directly by use of an ellipso-
meter. The wavelength of light used must be in the range where carrier effects will
be observable, and this usually implies infrared. For example, silicon measurements
have been in the neighborhood of 50 /-tm. Unfortunately, instrumentation problems
associated with long-wavelength ellipsometers are fairly severe, and accuracy is not
exceptional. 158
Capacitance-Voltage Measurements. The differential capacitance of a depletion
layer, whether formed by Schottky barrier, p-n junction, or MIS structure, can be
used to determine the majority carrier-concentration profile as the space-charge-
region width is changed by a reverse bias voltage. The general expression is

(3.20)

where Nl and N2 are the net majority carrier concentrations on each side of the
junction at positions Xl and X 2, which are the respective distances that the space-
charge region has moved out from the junction owing to the applied voltage V.
C is the capacitance measured by a small-signal high-frequency capacitance bridge,
A is the junction area, q the electronic charge, and ee o the dielectric constant. All
the terms in the expression can be measured except Nl and N 2 • For N2 ~ Nl (i.e.,
an abrupt junction), the 1/N2 term can be neglected and Nl determined. Such C-V
measurements are widely used and have many variations for special circumstances.
They are, however, more device-oriented and as such are not described in detail.
References 159 to 163 and those contained therein are suggested for background
reading before these measurements are pursued.
Deep Level Impurities. The methods described have been most applicable to
shallow fully ionized impurities which contribute to conductivity. However, there
are also electrical measuring techniques which can be used to determine the concen-
tration of some deep and intermediate level impurities. They all involve measuring
either the capacitance or current of a p-n junction as a function of temperature.
The procedure requires packaged diodes and the capability of detecting capacitance
changes of a few tenths of a picofarad. Again, such methods are more device oriented
and will not be discussed.205-208

3.8 RESISTIVITY PROFILING

It is often desirable to determine the impurity profile normal to the surface of

a slice after some operation (e.g., epitaxial deposition, diffusion, or ion implantation)
or to measure resistivity fluctuations laterally across the surface. Each of these
requirements usually necessitates a finer resolution than is normally used and thus
requires special procedures and/or equipment. Various direct methods are sum-
marized in Tables 3.6 and 3.7 as well as some chemical and electrochemical tech-
niques. The latter depend on differences of etching or plating speed with impurity
concentration and are most useful in looking at variations across a large surface
area. It is difficult to determine the actual magnitude or resistivity in this manner,
 Resistivity and Carrier-Concentration Measurements 89

Table 3.6. Methods of Profiling Normal to Surface

Value
Method Description measured Limitations

I. Use of variable- p(z) Sensitivity poor,

width four-
point probe
(ill-=l interpretation diffi-
cult

2. Four-point p(z) Destructive, as-

~
probe combined sumes uniform re-
with beveling sistivity in x di-
rection

3. Four-point p(z) Destructive, re-

probe combined quires careful
with successive measurement of
layer removal
F9
------ material removal;
resistivity must re-
main constant or
increase with
depth

4. Differential re- p(z) Must be sure

sistance of breakdown oc-
diode in break- curs when profile
down desired. Requires
pulsed current.

5. Same as 2 and 3 p(z)

except using
-
spreading re-
sistance

6. Capacitance- N(z) Requires diode,

voltage depth limited un-

~
less multiple di-
odes are combined
with steps or bev-
els

7. Depth of junc- N(z) Destructive, re-

tion combined
with different
r1F1R
p, P, p,
quires generating
same profile in
resistivities several samples

8. Double bevel- N(z) Destructive, re-

ing
@ quires a diffusion,
which may
change distribution

9. Neutron activa- N(z) Impurity must be

tion combined amenable to neu-
with successive
layer removal
n ----
tron activation;
destructive, re-
quires careful
measurement of
material removal

10. Radio tracer N(z) Impurity must be

combined with radioactive; de-

~
successive layer structive, requires
removal careful measure-
ment of material
removal

II. Ion microprobe

12. Selective stain-

m N(z)

N(z)
Difficult to deter-
mine depth of
hole and hence z

Magnitude of vari-
ing, plating,
and etching ~ ation unknown
90 Semiconductor Measurements and Instrumentation

Table 3.7. Methods of Profiling Laterally

Value

-
Method Description measured Limitations

Four-point probe HH p(x) Resolution limited

-\ I
I ! by probe spacing

Spreading p(x) Probably the best

resistance method listed

Two-point probe p(x) Requires end

contacts and
known sample
4H - ~ geometry.
Resolution
limited by probe
spacing

Moving voltage p(x) Requires end

~
probe contacts and
~ known sample
geometry

Moving electron Interpretation

beam
6- difficult,
requires E-beam
source

Moving-spot
photovoltage
rClll~ N(x) Interpretation
difficult

X-ray microprobe III N(x) Sensitivity poor

I I
Selective N(x) Magnitude of

~
staining, variation unknown
plating, and
etching

Multiple MIS Resolution limited

~o~o~
N(x)
capacitors by photolithography

but spatial variations become clearly visible. Sirt!, copper, or anodic etching have
all been used for delineation.
Normal to the Surface. When the samples are very thick relative to normal probe
spacing and the resistivity variations are slowly varying, changes in spacing, either
by increasing the S of the equal-spaced system or by using some configuration with
one probe movable, can be used to estimate resistivity vs. depth. Interpretation is
difficult, resolution is poor, and the method is seldom used, though it does find
application in geophysical prospecting. 164,165
More commonly, the four-point probe is combined with material removal, by
either angle section or successive layer removal. The method of interpretation is
basically the same in either case, but each has certain practical advantages. Histori-
cally, parallel sections were removed by mechanical polishing, using a carefully
 Resistivity and Carrier-Concentration Measurements 91

constructed jig. These may have varying degrees of complexity 166-171 but if the
thickness is determined independently, e.g., by weighing, simple equipment similar
to that described in Chap. 7 may be used. A lapping block with three diamond
stops on compound screws used with conventional lapping equipment gives good
control, but initial alignment of the plane of the stops with the semiconductor surface
is difficult. With such arrangements, it is difficult to maintain parallelism, but by
deliberately allowing polishing to produce a wedge-shaped section and making
measurements along the incline, the necessity for parallelism is eliminated. 172 The
angle does not need to be ground to some preset value, because it can be measured
afterward. However, in order to obtain good resolution, very small angles, e.g., 0.1
to 0.2 are required. If the total thickness to be examined is greater than the sample
0 ,

length L, a sequential process of incremental angle lapping and probing may be

employed. The incremental steps should be chosen so that some overlap of sheet
resistance from step to step is possible.
When parallel layers are desired, it is more reproducible to oxidize the surface
and then remove the oxide. Where applicable, e.g., silicon, anodic oxidation is
preferred 173 so that possible high-temperature redistribution of impurities does not
occur.
If the impurity profile is one of rapidly increasing surface concentration away from
the surface, the removal of a layer will affect the average resistivity of the remaining
material very little and sensitivity will be very poor. For this reason it is better to
profile from high to low concentration even if it means measuring from the back
of a slice.
Interpretation of data for either angle or parallel sectioning is as follows: The
probe spacing to total layer thickness ratio is assumed large enough that sheet-
resistance values are measured, in which case the sheet resistance R. of the ith layer
removed is given by

(3.21 )

where Ri is the sheet value before removal of the ith layer and Ri+l is the value
after removal of the layer. If L1x is the thickness of the ith layer, 174

p(x) = Ri R i+l ilx (3.22)

Ri+l - Ri
The computed p is very sensitive to small instrumentation errors in Ri and Ri+l and
on Xi and Xi+1' To minimize these effects, instead of using Eq. (3.22), make use
of the relation
dG (3.23)
a(x) = dx

where G is the sheet conductance of the layerP5 The logarithm of the sheet con-
ductance will have some functional dependence of depth such that
F(x) = InG(x) (3.24)
Differentiation with respect to X gives
dF (l/G)dG (3.25)
dx dx
so that
92 Semiconductor Measurements and Instrumentation

1 dx
- - = p(x) = -dG
a (x)
= --:-:-=-:-::-
GdF/dx
(3.26)

Thus log G vs. x can first be plotted and smoothed as desired (either by machine
or manually),17Z,176 the slope taken at any desired value of x, and p determined
all without resorting to the use of small differences in either R. or x. As an alternate
experimental procedure, contacts can be made on opposite ends of a rectangular
sample by using a "wrap-around" diffusion and the sheet resistance determined by
conventional I-V measurements.1 77
Either bevel or parallel sectioning can be combined with spreading-resistance
measurements, but different interpretation is required. The main contribution to
spreading resistance will be in a layer less than one-fifth the diameter of the contact
area and virtually all from a depth less than 1.5 diameters. Thus, until the tip gets
within 1.5 diameters of an abrupt discontinuity, it will be measuring an average
value for a thin layer of fixed width, independent of the total sample thickness.
For close spacing, corrections have been computed. 86,87,209
Voltage-capacitance measurements are ideal for making profile measurements, but
the depth is limited by the width of the space charge at avalanche. In order to extend
the range, steps may be etched into the surface and diodes made on each step,z
or a bevel much like that used for four-point profiling will serve the same purpose. 178
Instead of determining N directly from the C- V measurements, it is also possible
to measure the resistance of the bulk semiconductor remaining between the space-
charge boundary and the back contact. 179,180 As the voltage across the junction is
increased, the space charge moves closer to the back and has the same electrical
effect as physically removing part of the layer. Two ways of measuring the resistance
have been used. One is to employ extra contacts and a lateral current flow; the
other is to determine the series resistance from Q measurements of the capacitor.
The differential resistance of the device after avalanche breakdown can also be used
for extending the profile depth, provided avalanche really occurs where the profile
is desired. 210,211
Probably the most sensitive and widest-range method of all, but one that is
applicable only if the impurity profile to be measured can be simultaneously intro-
duced into several separate samples, is the measurement of the p-n-junction depth
in materials of differing resistivity.174 The depth of the junction may be determined
by staining or other techniques (Chap. 7), and the concentration at that depth is
equal to the background concentration of that particular sample. For silicon it is
not unreasonable to measure a profile which ranges from 10 1Z to 1019 atoms/cm 3 .
Double beveling, combined with diffusion of a known profile and an appropriate
stain, can be used to give a pictorial view of the concentration variation. 181 Consider
Fig. 3.17, in which it is desired to know the profile normal to surface A. First make
a diffusion into the B face (which has been produced by beveling at a low angle
( 1 ) such that its concentration vs. depth is known and its type is opposite that already
in the sample. Next, bevel the sample again as shown by face C and stain to delineate
the junction. For any given depth Zj below the original surface given by Zj = x sin 0z,
the concentration is approximately equal to that of the diffusion at a depth of x sin Oz.
If the impurity is amenable to neutron-activation analysis, the sample can be·
irradiated and successive parallel layers removed from surface. Counting can then
be done on either the layers removed or the remaining material. If the impurity
itself is radioactive, similar removal and counting techniques can be used. In either
 Resistivity and Carrier-Concentration Measurements 93

Fig. 3.17. Double-bevel method

of displaying impurity concentra-
tion. (Adapted from Sits et al. 181 )

case, of course, handling, sectioning, etc., must be done in a work area which provides
protection for the operator. Because of this restriction, plus the requirements for
irradiation and counting, these two methods are seldom used for routine analysis,
but they are exceedingly useful for laboratory investigations. X-ray microprobe
fluorescence can be used if combined with a bevel but is not particularly sensitive
and is most applicable for high concentrations of impurities.
Lateral Profiling. The simplest method of lateral profiling is just to step four-point
probes across the surface. Resolution is limited by probe spacing, and edge correc-
tions should be used as required. If finer resolution is desired, spreading resistance
can be used. It has proved very successful in finding inhomogeneities in silicon,82,182
and in fact when combined with beveling, can be used to construct three-dimensional
impurity profiles. 212 Iffine resolution is not required and there is concern over probe
damage, very small metal contacts with expanded pads for probing can be used. 213
When samples of uniform cross section are available, either a two-point or a mov-
ing-voltage probe can be moved across the surface. Similarly, electron-beam scans
are applicable. 53 ,183-189 (Also see Sec. 3.3.) The photovoltage or photoconductivity
change generated by a moving spot of light can also be used,190-201 and while
difficult, interpretation of the signals for circular slices as well as for filaments is
possible and gives reasonable correlation with probe measurements. 201 It is interest-
ing to note that the resolution limit is given not necessarily by the light-spot size
but, depending on which is larger, by either it or the carrier-diffusion length.

REFERENCES

1. H. Frank, Influence of Damaged Surface Layer on Resistivity and Mobility of Thin

Semiconductor Sheets, Solid State Electron., 9:609-614 (1966).
2. Earl Alexander, S. Watelski, Ken Bean, W. R. Runyan, and Murray Bullis, "Develop-
ment of Epitaxial Structures for Radiation Resistant Silicon Solar Cells," NASA Report
CR46l, Clearing House for Federal Scientific and Technical Information, May 1966.
3. Edward N. Clark and Robert L. Hopkins, Electrical Conductivity of Mechanically
Disturbed Germanium Surfaces, Phys. Rev., 91: 1566 (1953).
4. W. J. Patrick, Measurement of Resistivity and Mobility in Silicon Epitaxial Layers on
a Control Wafer, Solid State Electron., 9:203-211(1966).
5. George G. Harmon and Theodore Higier, Some Properties of Dirty Contacts on
94 Semiconductor Measurements and Instrumentation

Semiconductors and Resistivity Measurements by a Two-Terminal Method, J. Appl.

Phys., 33:2198-2206 (1962).
6. Lydon J. Swartzendruber, "Calculations for Comparing Two-Point and Four-Point
Probe Resistivity Measurements on Rectangular Bar-shaped Semiconductor Samples,"
National Bureau of Standards, Tech. Note 241, 1964; J. Marshall Reber, Potential
Distribution in a Rectangular Semiconductor Bar for Use with Four-Point Probe
Measurements, Solid State Electron., 7:525-529 (1964); Serg Jandl, K. D. Usade1, and
Gaston Fischer, Resistivity Measurements with Samples in the Form of a Double Cross,
Rev. Sci. Instr., 45:1479-1480 (1974).
7. M. G. Buehler, J. M. David, R. L. Mattis, W. E. Phillips, and W. R. Thurber, Planar
Test Structures for Characterizing Impurities in Silicon, Ab. No. 171, Spring Meeting,
E.C.S. Extended Abstracts, 75-1 (1975).
8. E. Eadeywine, L. P. Hilton, and D. Townley, Measuring the Properties of Semiconductor
Grade Materials, SCP and Solid State Tech., 8:17-28 (October 1965).
9. F. Padovani and G. Valant, Resistivity Characterization of Semiconductor Crystal Ingots,
J. Electrochem. Soc., 120:585-587 (1973).
10. L. B. Valdes, Resistivity Measurements on Germanium for Transistors, Proc. IRE,
42:420-427 (1954).
11. Helen H. Gegenwarth, Correction Factors for the Four-Point Probe Resistivity Meas-
urements on Cylindrical Semiconductors, Solid State Electron., 11 :787-789 (1968).
12. Sadayuki Murashima, Hitoshi Kanamori, and Fumio Ishibashi, Correction Devisors for
the Four-Point Probe Resistivity Measurement of Cylindrical Semiconductors, Japan.
J. Appl. Phys., 9:58-67 (1970); Sadayuki Murashima and Fumio Ishibashi, Correction
Devisors for the Four-Point Probe Resistivity Measurements on Cylindrical Semicon-
ductors, II, Japan. J. Appl. Phys., 9: 1340-1346 (1970).
13. Erik B. Hansen, On the Influence of Shape and Variations of the Sample on Four-Point
Measurements, Appl. Sci. Res., 88:93-104 (1960).
14. A. Marcus and J. J. Oberly, Four-Probe Resistivity Measurements on Rectangular
Semiconductor Filaments, IRE Trans. Electron Devices, ED-3: 161-162 (1956).
15. G. Knight, Measurement of Semiconductor Parameters in Lloyd P. Hunter (ed.),
"Handbook of Semiconductor Electronics," McGraw-Hill Book Company, New York,
1956.
16. J. N. Hummel, A Theoretical Study of Apparent Resistivity in Surface Potential
Methods, AIME, Tech. Pub. 418, 1931.
17. A. Uhlir, Jr., The Potentials of Infinite Systems of Sources and Numerical Solutions
of Problems in Semiconductor Engineering, Bell System Tech. J., 34:105 (1955).
18. Method of Test for Resistivity of Silicon Using Four-Point Probes, Standard Test Method
F 43, American Society for Testing and Materials, Philadelphia, 1968.
19. R. Rymaszewski, Relationship between the Correction Factor of the Four-Point Probe
Value and the Selection of Potential and Current Electrodes, J. Sci. Instr., (2) 2:170-174
(1969); P. J. Severin, Four-Point-Probe Resistivity Measurements on Silicon Heterotype
Epitaxial Layers with Altered Probe Order, Philips Res. Rept. 26:279-297 (1971).
20. F. M. Smits, Measurement of Sheet Resistivities with the Four-Point Probe, Bell System
Tech. J., 37:711-718 (1958).
21. M. A. Logan, An AC Bridge for Semiconductor Resistivity Measurement Using a
Four-Point Probe, Bell System Tech. J., 40:885 (1961).
22. J. F. Combs and M. P. Albert, Diameter Correction Factors for the Resistivity Meas-
urement of Semiconductor Slices, Semicond. Prod., 6:26-27 (Feb., 1963).
23. M. P. Albert and J. F. Combs, Correction Factors for Radial Resistivity Gradient
Evaluations of Semiconductor Slices, IEEE Trans. Electron Devices, ED-11:l48-151
(1964).
24. Lydon J. Swartzendruber, "Correction Factor Tables for Four-Point Probe Resistivity
Measurements on Thin, Circular Semiconductor Samples," National Bureau of Stand-
ards, Tech. Note 199, 1964.
 Resistivity and Carrier-Concentration Measurements 9S

25. Lydon J. Swartzendruber, Four-Point Probe Measurement of Non-Uniformities in

Semiconductor Sheet Resistivity, Solid State Electron., 7:413-422 (1964).
26. D. E. Vaughan, Four-Point Probe Resistivity Measurements on Small Circular Speci-
mens, Brit. J. Appl. Phys., 12:414-416 (1961).
27. M. A. Logan, Sheet Resistivity Measurements on Rectangular Surfaces-General
Solutions for Four-Point Probe Conversion Factors, Bell System Tech. J., 46:2277-2322
(1967).
28. P. M. Hall and J. T. Koo, Sheet Resistance Measurements, J. Appl. Phys., 38:3112-3116
(1967).
29. S. B. Catalano, Correction Factors for Square-Array and Rectangular-Array Four-Point
Probe near Conducting or Non-Conducting Boundaries, IEEE Trans. Electron Devices,
ED-I 0: 185-188 (1963).
30. M. G. Buehler, A Hall Four-Point Probe on Thin Plates, Solid State Electron., 10:801-
812 (1967).
31. Frank Keywell and George Dorosheski, Measurements of the Sheet Resistivity of a
Square Wafer with a Four-Point Probe, Rev. Sci. Instr., 31 :833-837 (1960).
32. A. Mircea, Semiconductor Sheet Resistivity Measurements on Square Samples, J. Sci.
Instr., 41:679-681 (1964).
33. M. G. Buehler and G. L. Pearson, Magnetoconductive Correction Factors for an
Isotropic Hall Plate with Point Sources, Solid State Electron., 9:395-407 (1966).
~L. J. van der Pauw, A Method of Measuring Specific Resistivity and Hall Effect of
Discs of Arbitrary Shape, Philips Res. Repts., 13:1-9 (1958).
,,35. L. J. van der Pauw, A Method of Measuring the Resistivity and Hall Coefficient on
.;-" .-~ Lamellae of Arbitrary Shape, Philips Tech. Rev., 20:220-224 (1959); Ronald Chwang,
B. S. Smith and C. R. Crowell, Contact Size Effects on the van der Pauw Method for
Resistivity and Hall Coefficient Measurements, Solid State Electron., 17: 1217-1227
(1974); Patrick M. Hemenger, Measurement of High"Resistivity Semiconductors Using
the van der Pauw Method, Rev. Sci. Insfr., 44:698-700 (1973).
36. S. Amer, van der Pauw's Method of Measuring Resistivities on Lamellae of Non-
--"- Uniform Resistivity, Solid State Electron., 6:141-145 (1963); W. L. V. Price, Electric
Potential and Current Distribution in a Rectangular Sample of Anisotropic Material
With Applications to the Measurement of the Principal Resistivities by an Extension
of van der Pauw's Method, Solid State Electron., 16:753-762 (1973).
37. P. A. Schumann, Jr., and E. E. Gardner, Four-Point Probe Evaluation of Silicon n/n+
and p/p+ Structures, Trans. Met. Soc. AIME, 233:602 (1965).
38. P. A. Schumann, Jr., and J. F. Hallenbeck, Jr., A Novel Four-Point Probe for Epitaxial
and Bulk Semiconductor Resistivity Measurements, J. Electrochem. Soc., 110:538 (1963).
39. P. J. Olshefski, Constant Current Generator Measures Semiconductor Resistance,
Electronics, 34:63 (Nov. 24, 1961).
40. A. L. Barry and W. D. Edwards, Circuit to Facilitate the Measurement by the Four
Point Probe Method of the Resistivity of Silicon in the Range 0.002 to 1O,OOOOhm-Cm,
J. Sci. Instr., 39:119-121 (1962).
41. H. G. Rudenberg, Resistivity Measuring Techniques in Semiconductors, Semicond.
Prod., 2:28-34 (September 1959).
42. C. C. Allen and W. R. Runyan, An AC Silicon Resistivity Meter, Rev. Sci. Instr.,
32:824-828 (1961).
43. Data Sheet, J. A. Radley Research Institute, Reading, England.
44. T. M. Dauphinee and E. Mooser, Apparatus for Measuring Resistivity and Hall Co-
efficient of Semiconductors, Rev. Sci. Instr., 26:660-664 (1955).
45. W. D. Edwards, Resistivity Measuring Circuit Using Chopped Direct Current, J. Sci.
Instr., 42:432-434 (1965).
46. G. Fischer, D. Greig, and E. Mooser, Apparatus for the Measurement of Galvano-
magnetic Effects in High Resistance Semiconductors, Rev. Sci. Instr., 32:842-846
(1961).
96 Semiconductor Measurements and Instrumentation

47. J. H. Fermor and A. Kjekshus, Servocontrolled Measuring Bridge for Semiconductors

of High Resistivity, Rev. Sci. Instr., 36:763-766 (1965).
48. L. S. Swartzendruber, F. H. Ulmer, and J. A. Coleman, Direct Reading Instrument for
Silicon and Germanium Four-Probe Resistivity Measurements, Rev. Sci. Instr.,
39:1855-1863 (1968).
49. John F. Hallenback, Jr., and Daniel Piscitally, Precision Four-Point Probe Resistivity
Instrumentation in Rolf R. Haberecht and Edward L. Kern (eds.), "Semiconductor
Silicon," The Electrochemical Society, New York, 1969.
50. E. H. Putley, "The Hall Effect and Semiconductor Physics," Dover Publications, Inc.,
New York, 1968.
51. L. G. Sapugin and V. M. Ivko, Circuit for Measuring and Recording the Resistance
of Semiconductors in Coordinates Log R = f(lIT), Soviet Phys. Solid State,
2:1346-1351 (1961).
52. Luther Davis, Jr., Lawrence G. Rubin, and W. D. Straub, Rapid Determination of Some
Electrical Properties of Semiconductors, IRE Prof Group Electron Devices, ED1 :34-40
(1954).
53. Chusuke Manakata and Hiroshi Watanabe, Measurement of Resistance by Means of
Electron Beam-III, Japan. J. Appl. Phys., 8:1307-1309 (1969).
54. H. H. Lehner, Probing Techniques for Measuring the Potential Distribution in Semi-
conductors, Rev. Sci. Instr., 38:699-700 (1967).
55. Pierre Wagrez and Albert Soffa, A New Technique for Measuring the Resistivity of
Individual Semiconductor Dice, Semicond. Prod., 6:23-25 (February 1963).
56. V. A. Dorin and M. M. Kazlov, Probe of Silicon Carbide for Testing Semiconductor
Materials, Zavodsk. Lab., 30:206. (1964).
57. C. L. Paulnack, Technique for Two and Four Point Resistivity Measurements in GaAs,
Rev. Sci. Instr., 35:1715-1717 (1964).
58. H. Frank and Samy Abdel Azim, Measurement of Diffusion Profile of Zn in n-type
GaAs by a Spreading Resistance Technique, Solid State Electron., 10:727-728 (1967).
59. R. H. Creamer, The Measurement of the Electrical Resistivity of Silicon, Brit. 1. Appl.
Phys., 7: 149 (1956).
60. Alex Cybriwsky, Wide Temperature Range Four Point Probe Device for Measuring
Electrical Resistivity, Rev. Sci. Instr., 37:961-962 (1966).
61. R. A. Cooper and E. Lerner, Four-Point Mercury Contact Probe for Electrical Resistivity
Measurement of Thin Films, Rev. Sci. Instr., 39:1207-1208 (1968); P. J. Severin and
H. Bulle, Four-Point Probe Measurements on N-Type Silicon with Mercury Probes,
J. Electrochem. Soc., 22:133-137 (1975); P. J. Severin and H. Bulle, Spreading Resistance
Measurements on N-type Silicon Using Mercury Probes, J. Electrochem. Soc.,
22:137-142 (1975); P. J. Severin and G. Poodt, Capacitance-Voltage Measurements with
a Mercury-Silicon Diode, J. Electrochem. Soc., 119: 1384-1389 (1972).
62. Gerald Abowitz and Emil Arnold, Simple Mercury Drop Electrode for MaS Measure-
ments, Rev. Sci. Instr., 38:564-565 (1967).
63. D. W. F. James and R. G. Jones, On the Four-Probe Method of Resistivity Measurement,
J. Sci. Instr., 42:283 (1965).
64. D. B. Gasson, A Four-Point Probe Apparatus for Measuring Resistivity, J. Sci. Instr.,
33:85 (1956).
65. C. L. Paulnack and N. J. Chaplin, Minimal Maintenance Probe for Precise Resistivity
Measurement of Semiconductors, Rev. Sci. Instr., 33:873-874 (1962).
66. John K. Kennedy, Four-Point Probe for Measuring the Resistivity of Small Samples,
Rev. Sci. Instr., 33:773-774 (1962).
67. Alexander L. MacDonald, Julius Soled, and Carl A. Stearns, Four-Probe Instrument
for Resistivity Measurement of Germanium and Silicon, Rev. Sci. Instr., 24:884-885
(1953).
68. A & M Fell, Ltd., "Resistivity Measurement Literature."
 Resistivity and Carrier-Concentration Measurements 97

69. P. P. Clerx, Mechanical Aspects of Testing Resistivity of Semiconductor Materials and

Diffused Layers, Solid State Tech., 12:16 (June 1969).
70. R. W. Germann and D. B. Rogers, Four-Probe Device for Accurate Measurement of
Temperature Dependence of Electrical Resistivity on Small Irregular Shaped Single
Crystals with Parallel Sides, Rev. Sci. Instr., 37:273-274 (1966).
71. Dr. C. Goodman, Standard Telephone Laboratory, private communication, 1963.
72. D. Dew-Hughes, A. H. Jones, and G. E. Brock, Improved Automatic Four-Point Probe,
Rev. Sci. Instr., 30:920-922 (1959).
73. J. C. Brice and A. A. Stride, A Continuous Reading Four-Point Resistivity Probe, Solid
State Electron., 1:245 (1960).
14. R. Hall, Minimizing Errors of Four-Point Probe Measurements on Circular Wafers,
J. Sci. Instr., 44:53-54 (1967).
75. J. K. Hargreaves, and D. Millard, The Accuracy of Four-Probe Resistivity Measurements
on Silicon, Brit. J. Appl. Phys., 13:231-234 (1962).
76. W. Murray Bullis, "Standard Measurements of the Resistivity of Silicon by the Four-
Probe Method," National Bureau of Standards, Rept. 9666, December 1967.
77. Donald R. Zrudsky, Harry D. Bush, and John R. Fassett, Four-Point Sheet Resistivity
Techniques, Rev. Sci. Instr., 37:885-890 (1966).
78. W. M. Bullis, F. H. Brewer, C. D. Kolstad, and L. J. Swartzendruber, Temperature
Coefficient of Resistivity of Silicon and Germanium near Room Temperature, Solid
State Electron., 11 :639-646 (1968).
79. L. H. Garrison, Proper Current Input for True Resistivity Measurements of Single
Crystal Silicon of Both n- and p-Type and Single Crystal Slices, Solid State Tech., 9:47-50
(1966).
80. DavidD. Valley, Probe Shows Silicon Resistivity Accurately, Electronics, 34:70-73 (Mar.
31, 1961).
81. R. G. Mazur and D. H. Dickey, A Spreading Resistance Technique for Resistivity
Measurements on Silicon, J. Electrochem. Soc., 113:255-259 (1966).
82. R. G. Mazur, Resistivity Inhomogeneities in Silicon Crystals, J. Electrochem. Soc.,
114:255-259 (1967).
83. J. M. Adley, M. R. Poponiak, C. P. Schneider, P. A. Schumann, Jr., and A. H. Tong,
The Design of a Probe for the Measurement of the Spreading Resistance of Semi-
conductors, in Rolf R. Haberecht and Edward L. Kern (eds.), "Semiconductor Silicon,"
The Electrochemical Society, New York, 1969.
84. D. C. Gupta and J. Y. Chan, A Semiautomatic Spreading Resistance Probe, Rev. Sci.
Instr., 41:176-179 (1970).
85. W. A. Keenan, P. A. Schumann, Jr., A. H. Tong, and R. P. Phillips, A Model for the
Metal-Semiconductor Contact in the Spreading Resistance Probe, in Bertram Schwartz
(ed.), "Ohmic Contacts to Semiconductors," The Electrochemical Society, New York,
1969.
86. E. E. Gardner, P. A. Schumann, and E. F. Gorey, Resistivity Profiles and Thickness
Measurements on Multilayered Semiconductor Structures by the Spreading Resistance
Technique, in B. Schwartz and N. Schwartz (eds.), "Measurement Techniques for Thin
Films," The Electrochemical Society, New York, 1967; P. J. Severin, Measurement of
Resistivity of Silicon by the Spreading Resistance Method, Solid State Electron.,
14:247-255 (1971); P. J. Severin, Measurement of the Resistivity and Thickness of a
Heterotype Epitaxially Grown Silicon. Layer with the Spreading-Resistance Method,
Philips Res. Rept., 26:359-372 (1971).
87. Dinesh C. Gupta, Determination of Mobility and Its Profile in n/n+ Silicon Epitaxial
Layers, J. Electrochem. Soc., 116:670-671 (1969).
88. R. Holm, "Electric Contacts Handbook," 3d ed., Springer-Verlag OHG, Berlin, 1958.
89. Henry C. Torrey and Charles A. Whitmer, "Crystal Rectifiers," McGraw-Hill Book
Company, New York, 1948.
98 Semiconductor Measurements and Instrumentation

90. F. P. Bowden and D. Tabor, "The Friction and Lubrication of Solids," Clarendon Press,
Oxford, 1950.
91. F. L. Jones, "Physics of Electrical Contacts," Oxford University Press, London, 1957.
92. P. A. Schumann, Jr., and E. E. Gardner, Spreading Resistance Correction Factors, Solid
State Electron., 12:371-375 (1969).
93. Von Wolfgang Keller, Measurement of Resistivity of Semiconductors with High Fre-
quencies, Z. Angew. Phys., 11 :346-350 (1959).
94. V. G. Sidyakin and E. T. Skorik, Measuring the Resistance of Semiconductors at High
Frequencies, Instr. Exptl. Tech., 326-329 (1960).
95. Paul J. Olshefski, A Contactless Method for Measuring Resistivity of Silicon, Semicond.
Prod., 4:34-36 (1961).
96. I. R. Weingarten and M. Rothberg, Radio Frequency Carrier and Capacitative Coupling
Procedures for Resistivity and Lifetime Measurements on Silicon, J. Electrochem. Soc.,
108:167-171 (1961).
97. S. T. Kynev, M. K. Sheinkman, I. B. Shul'ga, and V. D. Fursenko, Contactless Method
for Measuring the Parameters of Certain Semiconductors, Instr. Exptl. Tech.,
376-381 (1962).
98. Jun-Ichi Nishizawa, Yuzo Yamoguchi, Naotoshi Shoji, and Yoshio Tominga, Application
of Siemens Method to Measure the Resistivity and Lifetime of Small Slices of Silicon,
in Marvin S. Brooks and John K. Kennedy (eds.), "Ultrapurification of Semiconductor
Materials," The Macmillan Company, New York, 1962.
99. C. A. Bryant and J. B. Gunn, Noncontact Technique for the Local Measurement of
Semiconductor Resistivity, Rev. Sci. Instr., 36:1614-1617 (1965).
100. Nobuo Miyamoto and Jun-Ichi Nishizawa, Contactless Measurements of Resistivity of
Slices of Semiconductor Materials, Rev. Sci. Instr., 38:360-367 (1967).
101. H. K. Henisch and J. Zucker, Contactless Method for the Estimation of Resistivity and
Lifetime of Semiconductors, Rev. Sci. Instr., 27:409-410 (1956).
102. R. C. Powell and A. L. Rasmussen, A Radio Frequency Permittimeter, IRE Trans. Instr.,
1-9:179-184 (1960).
103. J. C. Brice and P. Moore, Contactless Resistivity Meter for Semiconductors, J. Sci. Instr.,
38:307 (1961).
104. J. E. Zimmerman, Measurement of Electrical Resistivity of Bulk Metals, Rev. Sci. Instr.,
32:402-405 (1961).
105. S. J. Yosim, L. F. Grantham, E. B. Luchsinger, and R. Wike, Electrodeless Determi-
nation of Electrical Conductivities of Melts at Elevated Temperatures, Rev. Sci. Instr.,
34:994-996 (1963).
106. T. O. Poehler and W. Liben, Induction Measurement of Semiconductor and Thin Film
Resistivity, Proc. IEEE, 52:731-732 (1964).
107. R. W. Haisty, Electrodeless Measurements of Resistivities over a Very Wide Range,
Rev. Sci. Instr., 38:262-265 (1967).
108. R. W. Haisty, Measurement of High Resistivities by the Electrodeless Falling Sample
Method, Rev. Sci. Instr., 39:778 (1968).
109. J. Le Page, A. Bernalte, and D. A. Linholm, Analysis of Resistivity Measurements by
the Eddy Current Decay Method, Rev. Sci. Instr., 39:1019-1026 (1968).
110. A. C. Brown, A Non-contacting Resistivity Meter, J. Sci. Instr., 41 :472-473 (1964).
111. T. S. Benedict and W. Shockley, Microwave Observations of the Collision Frequency
of Electrons in Germanium, Phys. Rev., 89:1152-1153 (1953).
112. H. Hsieh, S. M. Goldey, and S. C. Brown, A Resonant Cavity Study of Semiconductors,
J. Appl. Phys., 25:302-307 (1954).
113. J. G. Linhart, I. M. Templeton, and R. Dunsmuir, A Microwave Resonant Cavity
Method for Measuring the Resistivity of Semiconducting Materials, Brit. J. Appl. Phys.,
7:36-38 (1956).
114. T. Kohane and M. H. Siruetz, Measurement of Microwave Resistivity by Eddy Current
Loss in Spheres, Rev. Sci. Instr., 30:1059-1060 (1959).
 Resistivity and Carrier-Concentration Measurements 99

115. G. L. Allerton and J. R. Seifert, Resistivity Measurements of Semiconductors at

9000 MC, IRE Trans. Instr., 1-9:175-179 (1960).
116. T. Kohane, The Measurement of Microwave Resistivity by Eddy Current Loss in Small
Spheres, IRE Trans. Instr., 1-9:184-186 (1960).
117. K. S. Champlin and R. R. Krongard, The Measurement of Conductivity and Permittivity
of Semiconductor Spheres by an Extension of the Cavity Perturbation Method, IRE
Trans. Microwave Theory Tech., MTT-9:545-551 (1961).
118. H. Jacobs, F. A. Brand, J. D. Meindl, M. Benanti, and R. Benjamin, Electrodeless
Measurement of Semiconductor Resistivity at Microwave Frequencies, Proc. IRE,
49:928-932 (1961).
119. K. S. Champlin and D. B. Armstrong, Explicit Forms for the Conductivity and Per-
mittivity of Bulk Semiconductors in Wave Guides, Proc. IRE, 50:232 (1962).
120. B. R. Nag and S. K. Roy, Microwave Measurements of Conductivity and Dielectric
Constant of Semiconductors, Proc. IRE, 50:2515-2516 (1962).
121. J. N. Bhar, Microwave Techniques in the Study of Semiconductors, Proc. IEEE,
51: 1623-1631 (1963).
122. J. Lindmayer and M. Kutsko, Reflection of Microwaves from Semiconductors, Solid
State Electron., 6:377-382 (1963).
123. B. R. Nag, S. K. Roy, and C. K. Chatterjee, Microwave Measurement of Conductivity
and Dielectric Constant of Semiconductors, Proc. IEEE, 51 :962 (1963).
124. M. W. Gunn, The Microwave Measurement of the Complex Permittivity of Semicon-
ductors, Proc. IEEE, 52:185 (1964).
125. D. A. Holmes, D. L. Feucht, and H. Jacobs, Microwave Interaction with a Semiconduc-
tor Post, Solid State Electron., 7:267-273 (1964).
126. J. A. Naber and D. P. Snowden, Application of Microwave Reflection Technique to
the Measurement of Transient and Quiescent Electrical Conduction of Silicon, Rev.
Sci. Instr., 40:1137-1141 (1969).
127. Keith S. Champlin, Gary H. Glover, and John D. Holm, Bulk Microwave Conductivity
of Semiconductors Determined from TE81 Reflectivity of Boule Surface, IEEE Trans.
Instr. Meas., IM-18:105-110 (1969).
128. M. R. E. Bichara and S. P. R. Poitevin, Resistivity Measurement of Semiconducting
Epitaxial Layers by the Reflection of a Hyperfrequency Electromagnetic Wave, IEEE
Trans. Instr. Meas., IM-13:323-328 (1964).
129. T. Ogawa, Measurement of the Electrical Conductivity and Dielectric Constant without
Contacting Electrodes, J. Appl. Phys., 32:583-592 (1961).
130. M. W. Ozelton and J. R. Wilson, A Rotating Field Apparatus for Determining Re-
sistivities of Reactive Liquid Metals and Alloys at High Temperatures, J. Sci. Instr.,
43:359-363 (1966).
131. A. C. Brown, Thickness Corrections to Resistivity Measurement by Q-Meter, J. Sci.
Instr., 41 :335-336 (1964).
132. Edward C. Jordan and Keith G. Balmain, "Electromagnetic Waves and Radiating
Systems," Prentice-Hall, Inc., Englewood Cliffs, N.J., 1968.
133. A. H. Frei and M. J. D. Strutt, Skin Effect in Semiconductors, Proc. IRE, 48:1272-1277
(1960).
134. O. Sandus, Comments on Electrodeless Measurements of Semiconductor Resistivity at
Microwave Frequencies, Proc. IRE, 50:473-474 (1962).
135. C. C. Allen and E. G. Bylander, Evaluation Techniques for, and Electrical Properties
of Silicon Epitaxial Films, in John B. Schroeder (ed.), "Metallurgy of Semiconductor
Materials," Interscience Publishers, a division of John Wiley & Sons, Inc., New York,
1963.
136. E. Batifol and G. Duraffourg, J. Phys. Radium, 24(Suppl. to No. 11):207A (1960).
137. J. R. Biard and Stacy B. Watelski, Evaluation of Germanium Epitaxial Films, J. Elec-
trochem. Soc., 109:705-709 (1962).
138. John Brownson, A Three-Point Probe Method for Electrical Characterization of Epi-
100 Semiconductor Measurements and Instrumentation

taxial Films, Electrochemical Society Meeting, May 1962; J. Electrochem. Soc.,

111 :919-924 (1964).
l39. C. C. Allen, L. H. Clevenger, and D. C. Gupta, A Point Contact Method of Evaluating
Epitaxial Layer Resistivity, J. Electrochem. Soc., 113:508-5lO (1966).
140. E. E. Gardner, J. F. Hallenback, Jr., and P. A. Schumann, Jr., Comparison of Resistivity
Measurement Techniques on Epitaxial Silicon, Solid State Electron., 6:311-313 (1963).
141. E. E. Gardner and P. A. Schumann, Jr., Measurement of Resistivity of Silicon Epitaxial
Layers by the Three-Point Probe Technique, Solid State Electron., 8:165-174 (1965).
142. P. A. Schumann, Jr., M. R. Poponiak, J. F. Hallenback, Jr., and C. P. Schneider,
Measurement Electronics for the Three-Point Probe, Solid State Tech., 11 :32-36 (No-
vember 1968).
143. P. A. Schumann, Jr., A Theoretical Model of the Three-Point Probe Breakdown Tech-
nique, J. Electrochem. Soc., 115:1197-1203 (1968).
144. M. H. Norwood, Three-Point Probe Calibration for GaAs, J. Electrochem. Soc., 112:875
(1965).
145. H. Frank, Contribution to the Measurement of Resistivity of nn+ and pp+ Epitaxial
Layers by the Punch through Method (in German), Phys. Stat. Solidi, 18:401-414 (1966).
146. W. G. Spitzer and H. Y. Fan, Infrared Absorption in n-Type Silicon, Phys. Rev.,
108:268-271 (1957).
147. N. J. Harrick, Semiconductor Type and Local Doping Determination through the Use
of Infrared Radiation, Solid State Electron., 1:234-244 (1960).
148. W. G. Spitzer and H. Y. Fan, Determination of Optical Constants and Carrier Effective
Mass of Semiconductors, Phys. Rev., 106:882-890 (1957).
149. David F. Edwards and Paul D. Maker, Quantitative Measurement of Semiconductor
Homogeneity from Plasma Edge, J. Appl. Phys., 33:2466-2468 (1962).
150. I. Kudman, ANon-destructive Measurement of Carrier Concentration in Heavily Doped
Semiconductor Materials and Its Application to Thin Surface Layers, J. Appl. Phys.,
34:1826-1827 (1963).
151. L. A. Murray, J. J. Rivera and P. A. Hoss, Infrared Reflectivity of Heavily Doped
Low-Mobility Semiconductors, J. Appl. Phys., 37:4743-4745 (1966).
152. E. E. Gardner, W. Kappallo, and C. R. Gorden, Measurement of Diffused Semiconduc-
tor Surface Concentrations by Infrared Plasma Reflection, Appl. Phys. Lett., 9:432-434
(1966).
153. P. A. Schumann and R. P. Phillips, Comparison of Classical Approximations to Free
Carrier Absorption in Semiconductors, Solid State Electron., 10:943-948 (1967).
154. P. A. Schumann, Jr., Plasma Resonance Calibration Curves for Silicon, Germanium
and Gallium Arsenide, Solid State Tech., 13:50-52 (1970).
155. Toshio Abe and Yoshio Nishi, Non-destructive Measurement of Surface Concentrations
and Junction Depths of Diffused Layers, Japan. J. Appl. Phys., 7:397-403 (1968).
156. T. G. R. Rawlins, Measurement of the Resistivity of Epitaxial Vapor Grown Films of
Silicon by an Infrared Technique, J. Electrochem. Soc., III :8lO-814 (1964).
157. Dinesh C. Gupta, Non-destructive Determination of Carrier Concentration in Epitaxial
Silicon Using a Total Internal Reflection Technique, Solid State Electron., 13:543-552
(1970).
158. Charlie E. Jones and A. Ray Hilton, Optical Properties by Far Infrared Ellipsometry,
J. Electrochem. Soc., 115: lO6-lO7 (1968).
159. J. Hi1ibrand and R. D. Gold, Determination of the Impurity Distribution in Junction
Diodes from Capacitance-Voltage Measurements, RCA Rev., 21 :245-252 (1960).
160. C. Jund and R. Poirer, Carrier Concentration and Minority Carrier Lifetime Measure-
ment in Semiconductor Epitaxial Layers by the MOS Capacitance Method, Solid State
Electron., 9:315-319 (1966).
161. M. G. Buehler, Peripheral and Diffused Layer Effects on Doping Profiles, IEEE Trans.
Electron Devices, ED-19:1171-1178 (1972).
 Resistivity and Carrier-Concentration Measurements 101

162. K. H. Zaininger and F. P. Heiman, The C-V Technique as an Analytical Tool-Part

I, Solid State Tech., 13:49-55 (May 1970).
163. K. H. Zaininger and F. P. Heiman, the C-V Technique as an Analytical Tool-Part
II, Solid State Tech., 13:46-55 (June 1970).
164. J. J. Jakosky, Exploration Geophysics, Times-Mirror Press, Los Angeles, 1940.
165. E. W. Carpenter and G. M. Habberzam, A Tri-potential Method of Resistivity Pros-
pecting, Geophysics, 21 :455-469 (1956).
166. Harry Letaw, Jr., Lawrence M. Slifkin, and William M. Portnoy, A Precision Grinding
Machine for Diffusion Studies, Rev. Sci. Instr., 25:865-868 (1954).
167. L. M. L. J. Leblans and M. L. Verheijke, A Precision Grinding Machine for Tracer
Diffusion Studies, Philips Tech. Rev., 25:191-194 (1963-1964).
168. B. Goldstein, Precision Lapping Device, Rev. Sci. Instr., 28:289-290 (1957).
169. H. W. Schamp, D. A. Oakes, and N. M. Reed, Grinder for Sectioning Solid Diffusion
Specimens, Rev. Sci. Instr., 30:1028-1031 (1959).
170. H. J. de Bruin, and Ralph L. Clark, Precision Lapping Device for the Determination
of Diffusion Coefficients in Ceramic Materials, Rev. Sci. Instr., 35:227-228 (1964).
171. W. C. Dunlap, Jr., Diffusion of Impurities in Germanium, Phys. Rev., 94:1531-1540
(1954).
172. Stacy B. Watelski, W. R. Runyan, and R. C. Wackwitz, A Concentration Gradient
Profiling Method, J. Electrochem. Soc., 112: 1051-1053 (1965).
173. B. McDonald and F. C. Collins, Anodic Sectioning of Diffused Silicon p-n Junctions,
Bull. Am. Phys. Soc., 6:106 (March 1961).
174. Howard Reiss and C. S. Fuller, Diffusion Processes in Germanium and Silicon, in N. B.
Hannay (ed.), "Semiconductors," Chap. 6, Reinhold Publishing Corporation, New York,
1960.
175. Don L. Kendall, Texas Instruments Inc., unpublished work. See also Refs. 172 and 176.
176. R. A. Evans and R. P. Donovan, Alternative Relationship for Converting Incremental
Sheet Resistivity Measurements into Profiles of Impurity Concentration, Solid State
Electron., 10:155-157 (1967).
177. M. F. Lamorte, Calculation of Concentration Profiles and Surface Concentration from
Sheet-Conductance Measurements of Diffused Layers, Solid State Electron., 1: 164-171
(1960).
178. T. E. McGahon and W. H. Hackett, Jr., A Technique for Determining p-n Junction
Doping Profiles and Its Application to GaP, Rev. Sci. I nstr., 41: 1182-1183 (1970).
179. H. Kressel and M. A. Klein, Determination of Epitaxial-Layer Impurity Profiles by
Means of Microwave Diode Measurements, Solid State Electron., 6:309-310 (1963).
180. D. Pomerantz, Measuring Mobility and Density of Charge Carriers near a p-n Junction,
J. Electrochem. Soc., 112:196-200 (1965).
181. V. Sils, R. W. Berkstrosser, P. Wang, and T. A. Longo, Doping Profile Determination
in Epitaxial Silicon Films, Electrochem. Tech., 2:138-143 (1964).
182. D. C. Gupta, J. Y. Chan, and P. Wang, Observations on Imperfections in Silicon Material
Using the Spreading Resistance Probe, J. Electrochem. Soc., 117:1611-1612 (1970).
183. Chusuke Munakata, Detection of Resistivity Striations in a Ge Crystal with an Electron
Beam, Japan. J. Appl. Phys., 5:336 (1966).
184. Hiroshi Watanabe and Chusuke Munakata, Measurement of Resistance by Means of
Electron Beam-I, Japan. J. Appt. Phys., 4:250-258 (1965).
185. Chusuke Munakata, Bulk Electron Voltaic Effect, Japan. J. Appt. Phys., 4:697' (1965).
186. Chusuke Munakata and Hiroshi Watanabe, Measurement of Resistance by Means of
Electron Beam-II, Japan. J. Appt. Phys., 5:1157-1160 (1966).
187. Chusuke Munakata, An Electron Beam Method of Measuring Resistivity Distribution
in Semiconductors, Japan. J. Appl. Phys., 6:963-971 (1967).
188. Chusuke Munakata, An Application of Beta Conductivity to Measurement of Resistivity
Distribution, J. Sci. Instr., (2) 1 :639-642 (1968).
102 Semiconductor Measurements and Instrumentation

189. J. Tauc, Generation of an EMF in Semiconductors with Nonequi1ibrium Current Carrier

Concentrations, Revs. Mod. Phys., 29:308-324 (1957).
190. J. Oroshnik, and A. Many, Evaluation of the Homogeneity of Germanium Single
Crystals by Photovoltaic Scanning, J. Electrochem. Soc., 106:360-362 (1959).
191. C. D. Cox, Bulk Photoeffects in Inhomogeneous Semiconductors, Can. J. Phys.,
38: l328-l342 (1960).
192. J. Oroshnik and A. Many, Quantitative Photovoltaic Evaluation of the Resistivity
Homogeneity of Germanium Single Crystals, Solid State Electron., 1:46-53 (1960).
193. E. I. Rashba and V. A. Romanov, A Photoelectric Method of Observing Inhomogeneity
with Depth in Semiconductors, Soviet Phys. Solid State, 2:2393-2396 (1961).
194. D. T. Kokorev and N. F. Kovtonyuk, Analysis of the Homogeneity of Semiconductor
Materials by Using the Method of the Volume Photo-EMF, Instr. Exptl. Tech.,
28:382-387 (1962).
195. K. Thiessen and H. Hornung, Measurement of Inhomogeneous Distribution of Recom-
bination Centers in Germanium by Means of Photoconductive and Photomagnetoelec-
tric Effects (in German), Phys. Stat. Solidi, 2: 1158-1164 (1962).
196. I. A. Baev and E. G. Valyashko, Study of the Homogeneity of Semiconductor Crystals
with the Use of a Moving Light Probe, Soviet Phys. Solid State, 6:l357-l361 (1964).
197. M. I. Iglitsyn, D. I. Levinson, and V. U. Chernopisskii, Checking the Uniformity of
Monocrystalline Germanium by the Single Probe Method, Ind. Lab., 30:251-254 (1964).
198. M. I. Iglitsyn, A. A. Meier, o. V. Karagioz, D. I. Levinzon, and A. V. Ivanov, A
Single-Probe Method of Measuring the Resistivity of Semiconductors with Alternating
Current, Ind. Lab., 31 :1355-l357 (1965).
199. M. G. Mil'vidshii, S. P. Grishina, and A. V. Berkova, Detecting Inhomogeneities in
Silicon Single Crystals with Infrared Transillumination, Ind. Lab., 31 :586-588 (1965).
200. I. A. Baev and E. G. Valyashko, An Investigation of the Distribution of Inhomogeneous
Regions in Semiconductors, Soviet Phys. Solid State, 7:2093-2099 (1966).
201. W. Murray Bullis (ed.), "Methods of Measurement for Semiconductor Materials, Process
Control, and Devices," National Bureau of Standards, Tech. Note 488, July 1969.
202. A. H. Tong, Nondestructive and Contactless Sheet Resistance and Junction Depth
Measurements by Infrared Transmission through the Diffusion, in Howard R. Huff and
Ronald R. Burgess (eds.), "Semiconductor Silicon 1973," pp. 596-605, Electrochemical
Society, Princeton, 1973.
203. J. K. Kung and W. G. Spitzer, Infrared Reflectivity and Free Carrier Absorption of
Si-doped, N-type GaAs, J. Electrochem. Soc., 121 :1482-1487 (1974).
204. Alvin H. Tong, Paul A. Schumann, Jr., and William A. Keenan, Epitaxial Substrate
Carrier Concentration Measurement by the Infrared Interference Envelope (IRIE)
Technique, 1. Electrochem. Soc., 119:l381-l384 (1972).
205. M. G. Buehler, Impurity Centers in PN Junctions Determined from Shifts in the
Thermally Stimulated Current and Capacitance Response with Heating Rate, Solid State
Electron., 13:69-79 (1972).
206. Martin G. Buehler, Thermally Stimulated Measurements: The Characterization of
Defects in Silicon p-n Junctions, in Howard R. Huff and Ronald R. Burgess (eds.),
"Semiconductor Silicon 1973," pp. 549-560, Electrochemical Society, Princeton, 1973.
207. D. V. Lang, Fast Capacitance Transient Apparatus: Application to ZnO and 0 Centers
in GaP p-n Junctions, J. Appl. Phys., 45:3014 (1974).
208. D. V. Lang, Deep-Level Transient Spectroscopy: A New Method to Characterize Traps
in Semiconductors, J. Appl. Phys., 45:3023-3032 (1974).
209. Bernard L. Morris, Some Device Applications of Spreading Resistance Measurements
on Epitaxial Silicon, J. Electrochem. Soc., 121 :422--426 (1974).
210. G. H. Glover and W. Tantraporn, Doping Profile Measurements from Avalanche
Space-Charge Resistance: A New Technique, 1. Appl. Phys., 46:867-874 (1975).
 Resistivity and Carrier-Concentration Measurements 103

211. G. H. Glover and W. Tantraporn, R-I Profiling: A New Technique for Measuring
Semiconductor Doping Profiles, Appl. Phys. Lett., 25:348-349 (1974).
212. P. A. Schumann, Jr., C. P. Schneider, and L. A. Pietrogallo, Three-Dimensional Impurity
Profile of an Epitaxial Layer, Solid State Tech., 16:54-55 (Sept., 1973).
213. J. Burtscher, H. W. Dorendorf, and J. Krausse, Electrical Measurement of Resistivity
Fluctuations Associated with Striations in Silicon Crystals, IEEE Trans. Electron.
Devices, ED-20:702-708 (1973).
 4
Lifetime

4.1 INTRODUCTION

When the equilibrium number of holes and electrons is disturbed by introducing

additional carriers, the lifetime is a measure of the time required for the excess
carriers to recombine. Their behavior in an infinite block of material with no
complications* is described by
ap !::.p
(4.1)
at 'T

an !::.n
at 'T

where n, p = number of carriers present at time t

!::.n, !::.p = excess number of carriers
'T = lifetime

or !::.n = Ae- t / T
(~.2)
!::.p = Be-t/T
where A and B are constants.
Should the block not be infinite, the carriers which diffuse to the surface will
generally combine at a rate quite different from the one in the bulk. The most
common way of characterizing such surface recombination is to define a surface-
recombination velocity s through the equations
In = qs!::.n (4.3)
Jp = qs!::.p

or (4.4)
Dp ap = s!::'p
ax
where J is the perpendicular component of the current density flowing to or from
the surface. When the appropriate equations are solved for some specific geometry

*No trapping and negligible diffusion.

105
 106 Semiconductor Measurements and Instrumentation

rather than the infinite block described by Eq. (4.1), Eq. (4.4) can be used as one
of the boundary conditions and will give an effective lifetime lower than that which
would be observed in the bulk unless s = O. Some specific cases are discussed in
a later section.
Excess holes can directly recombine with conduction-band electrons, and excess
electrons can directly recombine with valence-band holes, in which case the lifetimes
for holes and electrons will be equal. If traps are present, there are two limiting
cases. Should the captured carrier reside in the trap only for a time short compared
with the lifetime before combining with an opposite type of carrier, both hole and
electron lifetime will still be equal, and the trap is ordinarily referred to as a
recombination center. However, if upon trapping, the carrier resides there for a longer
time, the process is referred to as trapping, and lifetime will usually vary with type
and the method of measurement. The details of the various trapping models that
give rise to the differing lifetimes will not be considered in any detail. Occasionally,
the method used will measure the generation rate of carriers rather than their
recombination rate. Further, depending on the approach and sample geometry, the
measured value may be determined by either bulk or surface-recombination proc-
esses, and depending on the injection level, the value of 'T can theoretically vary
by a factor of 2. Therefore, before lifetimes measured by various methods are
compared, some care should be taken to ensure that there is in fact some justification
for the comparison.
Literally dozens of approaches have been reported, although they can in general
be grouped in two categories. One uses a single conductivity-test sample wmch may
be as simple as a rectangular specimen of millimeter dimensions to observe the decay
lof carriers directly. The other uses p-n junctions or metal-oxide-semiconductor
I (MOS) capacitors, usually in the form of finished devices, and attempts to correlate
I some device parameter with lifetime. Normally the material manufacturers strive
for long lifetime, whereas many finished devices require either the lowest possible
lifetime or at least some controlled intermediate value. When lifetime measurements
are to be used for initial material characterization and/or process control, those
methods which require the fewest additional fabrication steps are the most desirable
since any additional steps not only slow down the evaluation process but may also
materially change the lifetime. However, since the lifetime in finished devices is
very process-sensitive and is generally so important to device performance, consid-
erable effort has been expended in methods to interpret device performance in terms
of lifetime.
As the technology of a given material matures and the lifetime of the average
material produced becomes more than adequate for its intended use, fewer lifetime
measurements are required of the starting material. Indeed the majority of silicon
-\) crystals grown are never checked for lifetime. Similarly, as the device processing
becomes more fixed, there is less inclination to determine actual lifetime in the
devices. What is usually done is to monitor the device parameter of interest and
relate it directly to some process variation which affects lifetime. For example, in
making fast diodes, instead of measuring recovery times, calculating lifetime, relating
that lifetime value to a specific concentration of recombination centers, and then
further considering the relation between the number of centers and the mode of
introduction of that recombination center, curves of diode recovery time are plotted
directly against gold-diffusion temperature and used for process control and opti-
mization.
 Lifetime 107

Table 4.1 summarizes some forty variations of lifetime-measurement techniques

that will be discussed. The final choice of a particular method or variation depends
primarily on the magnitude of the lifetime, the sample size, and whether the sample
can only be a piece of bulk material or a completed device is available. The usual
working range for several of these methods is shown in Table 4.2. It should be
remembered, however, that with special emphasis and attention to a particular case,
nearly any method can be extended in either direction. But the photoconductive
decay (PC) method is so simple it is used whenever possible, so there has been little
inclination to extend other methods into the longer-lifetime region. The one excep-
tion has been that as longer and longer lifetimes have been achieved after various
processing stages, the PC method sometimes becomes size-limited (for example, with
slices). In such circumstances surface photovoltage, which allows approximately a
4 to I reduction in thickness for a given lifetime measurement, becomes very at-
tractive even though it is quite tedious. For cases where an oxide at least a few
hundred angstroms thick is present (e.g., after the first step in bipolar and MaS
processing) the MaS capacitor will allow measurements over a rather broad range
of lifetimes and is not necessarily destructive. At the other end of the scale, diode
recovery measurements are favored whenever possible, again because of simplicity.
However, in keeping with the theme of this volume, which is devoted to bulk
measurements, device-related methods are not discussed, although references are
given in Table 4.1.

4.2 PHOTOCONDUCTIVE DECAY

In this method the excess carriers are generated by irradiating the sample with
light of short enough wavelength to produce hole-electron pairs. The conductivity
(J ofthe sample is directly proportional to the number of carriers, and the conductivity

change is proportional to the number of excess carriers, or

(4.5)
Thus monitoring the conductivity after the light is removed allows the lifetime to
be determined.
Detection of Decay. The simplest method of observing the carrier decay is by
use of the circuit of Fig. 4.1. If current is supplied by a constant-current source,
then it can be shown96 that the time constant for the voltage decay is quite close
to the effective carrier time constant and is given by

'reff = 'rvott (l _11;) (4.6)

°
if IlVis small compared with the dark IR drop Va developed by the constant current
across the portion of the sample illuminated by the chopped light. Actual measure-
ment of the time constant is by means of an oscilloscopic display. Then the variable
sweep can be used to match a curve drawn on the face. Other methods include
using a fixed sweep and measuring the time for an amplitude reduction to lie of
the value at the start of the time measurement, by generating a second curve from
a photocell and a variable but known RC time constant and matching it to the
photodecay curve by using a dual-trace oscilloscope, or by putting one signal on
the x plates and the other on the y plates.1°,19,33,37 The latter has the added advan-
tage of visually displaying difficulties arising when conditions such as excessive light
108 Semiconductor Measurements and Instrumentation

Table 4.1. Literature Guide to Methods of Measuring Carrier Lifetime

Method Reference

Diffusion-length methods:
Traveling spot 1, 11, 12, 13, 28, 71, 103, 125, 140, 153, 154
Flying spot 7, 30, 125
Dark spot 81
Drift field 2, 12, 14, 16, 20, 32
Emitter-point efficiency 12
Conductivity-decay methods:
Photoconductive decay
Direct observation of resistivity 4, 12, 21, 33, 37, 53, 55, 57 80, 94, 96,
107, 116, 134, 171
Q changes 107, 114, 139, 167
Microwave absorption 66, 69, 75, 76, 88, 97, 111, 118, 121
Spreading resistance 20
Eddy-current losses 165
Infrared-absorption coefficient 26, 47, 62, 133
Pulse decay
Direct observation of resistivity 3, 10,40,41
Microwave absorption 66, 69, 88
High-energy-radiation-generated carrier decay 31, 117, 135, 137
Conductivity-modulation methods:
Photoconductivity
Steady state 18, 25, 46, 82, 136, 146
Modulated source 19, 45, 49, 52, 89, 102, 156, 160, 180
Infrared detection, steady state 26
Infrared detection, modulated source 62
Q changes 27
Microwave absorption 75
Eddy-current losses 116
Pulse injection-spreading resistance 20, 40, 41
Device methods:
Diode open-circuit voltage decay 15, 17, 23, 98, 112, 145, 169, 181
Diode reverse-current behavior 6, 8, 9, 35, 39, 73, 101, 113, 120, 127, 128,
132, 141, 145, 150, 155, 166, 172, 173, 174,
177, 185, 189
Diffusion capacitance 108, 123
Junction photocurrent or photovoltage 50,68, 83, 84, 91, 99, 115, 131, 142, 159,
187, 193
I-V 130, 190
Stored charge 127, 129, 144, 148
Current-distortion effects 113, 161, 183, 188
Base transport 24, 51, 60, 95, 126, 145, 151
Collector response 145, 158
Offset voltage
MOS capacitance method: 152, 163, 164, 175, 176, 180, 182, 184
Photomagnetoelectric effect 34, 58, 64, 72, 74, 77, 100, 104, 105, 109,
122, 124, 162, 179, 192
Surface photovoltage:
Steady state 92, 179, 192
Decay 42
Miscellaneous methods:
Photoluminescence 147
Cathodoluminescence 168
Suhl and related effects 5,44
Electroluminescence 93
Charge-collection efficiency 61, 149
Noise 78, 116
Lifetime definitions and interpretation 22, 29, 36, 48, 54, 56, 59, 70, 85, 86, 90,
138, 157

Adapted in part from W. Murray Bullis, "Measurement of Carrier Lifetime in Semiconductors-An

Annotated Bibliography Covering the Period 1949-1967," National Bureau of Standards, Tech. Rep!.
AFML-TR-68-108, 1968.
 Lifetime 109

Table 4.2. Range and Limitations of Lifetime Measuring Methods

Lower Lifetime, s Upper Misc.
Method limitation lf9 10- 6 10- 3 limitation limitation

Device
Diode
recovery
Pulsing @W//?/j geometry
instrumentation

PME-PC Inodequote signol

to noise
0Vfi7Al Complex equipment
very sensitive to
surface effects

Surface
photovoltage
Inodequote signal ~...M Somple
size
Time-consuming
measurement
to noise

Inadequate signal
Photodecay to nOise, lack of
rapid cutoff light
I ... 1Z0'fl0%1 Sample
size
source.

MOS Doping level to n; Surface

capacitance ratio I I recombination

Adapted from Joseph Horak, "Minority Carrier Lifetime Measurements on Silicon Material for Use
in Electron Irradiation Studies," AF Contract F19628-67-0043, SCientific Report, May 1968.
*May be extended into this range by using high-energy electron excitation.

intensity preclude an exponential decay. If the semiconductor signal is exponential

and both amplifiers are matched in phase, a straight line will appear. If a complex
Lissajous figure appears, the data should be suspected. 37 An excessive electric field
may cause some of the carriers to be transported to the contacts before normal
recombination can occur. This will give rise to a reduced value of measured lifetime,
and usually a nonexponential decay as well. 80
The use of microwave absorption for detecting the excess carriers and their
subsequent decay is quite appealing because there is then no necessity for making
ohmic contacts to the specimen. To that end considerable effort has been expended,
but in general the added complexity of the microwave equipment overshadows
contacting difficulties. It is first necessary to establish that the microwave detector
signal is indeed proportional to the number of excess carriers. For a simple post
inserted into a waveguide, theory would indicate that only under very limited con-
ditions is it true,69,88,97 although good agreement between microwave and contact
measurements has been reported. 66,75,76 By completely filling the cavity with the
sample, the limitations are considerably reduced and the calculations simplified, but
with the added complexity of requiring a carefully sized sample. 121 To keep from
shaping the sample at all, coupling to odd-shaped pieces via an open waveguide
or horn has been used. Again, there are complications of interpretation, as well
as more susceptibility to errors caused by reflections and a reduced signal-to-noise
ratio. ll1 ,118

Steody bios light

Interrupted
light
source

Fig. 4.1. Photodecay equipment.

110 Semiconductor Measurements and Instrumentation

The same advantage of no direct electrical contact can be realized by using lower
frequencies and capacitance coupling. The actual circuitry can vary considerably
and may range from rf bridges 107 to Q meters. 27 Coupling to rods, e.g., crystals
in plastic bags, can be conveniently accomplished by having wide metal bands which
clamp around the rod. 107 Slices, however, can best be laid over two adjacent flat-
plate electrodes covered by a thin plastic or mica spacer.114,167 Eddy currents can
also be used by inserting the sample into an rf coil and observing the change of
oscillator loading after a light pulse. A "cage" to short out the axial component
of the field will make the power absorbed vs. conductivity linear over a much broader
range of a/wE than would otherwise be possible165 (a = conductivity, I' = dielectric
constant).
An increase in the number offree carriers will increase the long-wavelength optical
absorption. Thus by monitoring the absorption coefficient, the decay of carriers can
be followed, again without direct contact. 26 The straightforward approach requires
an infrared detector with a response time shorter than that of the lifetime being
measured. However, because of the nonlinear relationship between the transmitted
intensity and the number of excess carriers, if the light generating the carriers is
chopped, the average value of transmitted intensity will depend on the chopping
frequency. Thus very slow detectors can be used,62,133 but sensitivity is not very
good.
Light Source. The simplest sort of light source is the combination of an incandes-
cent bulb and a rotating-blade mechanical chopper. It does, however, have the
disadvantage of producing a rather slow light-pulse fall time for any reasonable disk
rotational speed. Despite this handicap, it has been widely used for measuring the
lifetime of germanium. Fall times can be decreased by using a combination of
rotating mirror and a slit so that a larger angular velocity of the beam relative to
the limiting aperture can be obtained without either excessive speed or large wheel
diameter,21 as shown in Fig. 4.2a. This approach has been carried to the extreme
by using a mirror-sample separation of several feet and a many-faceted mirror
rotated tens of thousands of revolutions per minute. 79,87 The mirror velocity can
be reduced (or the pulse made more rapid) by using multiple reflections,38,94 as
shown in Fig. 4.2b and c, but eventually the limit is reached, not by the inability
to increase relative velocity further but by the decrease in light intensity available
at the sample. One distinct advantage that mechanically modulated systems have
over others is that the spectral distribution of the source can be chosen inde-
pendently. Such an independent choice is very important when studying narrow-
bandgap materials where the wavelength might be several micrometers. Modulation
may also be effected by the use of a Kerr cell, but electrical noise associated with
the high-voltage pulses required to operate the cell is difficult to shield against. The
natural decay of arcs in air,63,65 hydrogen,43 or xenon 21 has also been used to produce
short light pulses. Xenon flash tubes are particularly convenient, and an ordinary
commercial strobe light can be used. Air arcs were the light source in most of the
early silicon lifetime-test sets. Neither of them can be used to measure lifetimes
ofless than 2 or 3 MS, however, since that is the order of the decay time of the ionized
gas. Filters are sometimes used to remove short wavelengths and thereby reduce
surface effects. For silicon a thin slice of silicon or GaAs may be used as the filter.
Laser pulses can be obtained with very fast fall times and thus can be used for
light sources. 198 Modulation of the defocused beam of a high-intensity short-persist-
ence cathode-ray tube is useful for moderate lifetimes,19 and for certain selected
wavelengths, light-emitting diodes can be used. 156
 Lifetime 111

~_--I-_Rotating
mirror

Sample

(a)

In

(c)

Rotating mi rrar

(b)

Fig. 4.2. Mechanical methods of modulating light. (a) Single rotat-

ing mirror. (Adaptedfrom Williams. 87 ) (b) Multiple reflections from
a rotating mirror combined with a fixed mirror. (Adapted from
Holeman and Hilsum. 94 ) (c) Multiple reflections from a rotating mir-
ror combined with a fixed mirror. (Adapted from Garbuny, VagI, and
Hansen. 38 )

If the absorption coefficient is very high, the light may be predominantly absorbed
near the surface and give rise to excess carrier densities comparable with the doping
carrier density. If this happens, the initial decay will not be a simple exponential
and will be slower than expected. However, after enough time has elapsed for some
of the carriers either to diffuse into the bulk or to recombine, satisfactory measure-
ments can be made. 32
Boundary Effects. Because surface recombination can seriously affect inter-
pretation of photodecay curves, it is recommended practice either to calculate the
surface contribution or else to use very large samples. 21 In any event, light with
wavelengths near the band edge (and thus with relatively low absorption coefficients)
should be used to ensure that the carriers are generated in the body of the semi-
conductor and not all at the surface. For those materials which have a pronounced
dependence of T on the ratio of excess carriers to equilibrium number of majority
carriers, high concentrations near the surface will give a longer measured lifetime
and may partially counteract the effect of the excess surface recombination. Never-
theless, both circumstances should be avoided if possible.
The use of large samples and sandblasted surfaces is the procedure recommended
by the IRE standards. 96 The exact size of sample required is somewhat subjective,
and varies with the diffusion coefficient of the minority carriers. Figure 4.3 gives
a suggested minimum sample dimension as a function of lifetime to be measured
for various diffusion coefficients. For convenience, typical high-resistivity D values
are also tabulated.
If the dimensions are not as large as indicated in Fig. 4.3, the bulk lifetime can
be obtained by applying a suitable correction factor to the measured value. If the
112 Semiconductor Measurements and Instrumentation

Mat Dn Dp

Ge 100 50

Si 35 13

GoAs 275 11

0.001 ' - _ . . . L - _ - ' - _ - - ' -_ _' - - - - '

0.1 1.0 10 100 1,000 10,000
T bulk,fLs

Fig. 4.3. Minimum sample thickness required for photodecay

lifetime measurement. (Adapted in part from Stevenson and
Keyes. 21 )

sample is rectangular and is sandblasted so that the surface-recombination term is

very large,21
~ = _1__ 'lT 2D (_1_ + _1_ + _1_) (4.7)
'T 'Tefl A2 B2 C2
where D is an ambipolar diffusion coefficient given by

D = n +p (4.8)
(n/Dp) + (p/D n)
and A, B, and C are the rectangular dimensions. For reasonably heavily doped
material, D reduces to Dn for p-type and Dp for n-type. In the event the surface
recombination is not extremely large, the correction equations are much more
complex, and the reader is referred to Refs. 21, 53, 55, and 57. Corrections have
also been calculated for circular cross sections uniformly illuminated over the whole
surface by either penetrating or nonpenetrating light. 53 For radius a and length
I, limiting values are 53

(4.9)

~
'T -
1 _ D [( 2.4s
__
'Teff D + as
)2 +::C.]
f2
(4.10)

For s = 0 over the surface the only effect is that of the end contacts, which are still
assumed to have s = 00. When I is very large, 'T = 'T eff• When s ~ 00, Eq. (4.10)
reduces to 21

-;1= I
'T eff - 'IT
2 (9
D 16a2
1)
+ [2
and is the right-circular-cylinder counterpart of Eq. (4.7).
The complete solution for the decay is actually a series of exponentials with
different time constants. Their sum is not a simple exponential, but the higher-order
terms decay rapidly and leave the single exponential as described by Eqs. (4.7), (4.9),
and (4.10). Figure 4.4 shows the effect to be expected, and in principle it should
be possible to determine both. sand 'T from a measurement of 'Teff' 53 To prevent
misinterpretation when using Eqs. (4.7), (4.9), or (4.10), IRE standards recommend
 Lifetime 113
10

o
C
0>
'iIi 1.0
~\. ---
l;-..~ ~ -S=400
5=1,600

"0
\ --=:: ::::0- ~
-~
Fig. 4.4. Calculated effect of surface recom- o -\~S=80 ~~
~
binations on photoconductive decay of a cy-
E
o S=O r=500 ~ =::::::::::,.
z
lindrical ingot. The radius was assumed to
be 0.5 cm, the length infinite, and 0.1
o 100 200 300 400 500 600 700 800
D = 40 cm 2 /s. (Adapted from McKelvey. 53) t, f.Ls

that no measurement of the decay slope be made until the signal has decayed to
less than 60 percent of its peak value if half or less of the width of the sample is
exposed to illumination. If more than half of the width is illuminated, no measure-
ment should be made until the signal is less than 25 percent of the peak value.
A rather complex alternate approach has been proposed which is based on the fact
that a forward-biased p-n junction should present a low recombination surface. Then
thin samples, e.g., slices with a skin of opposite type, could be contacted so that
the inner region behaves as a standard photodecay sample and the junctions formed
by the skin are forward-biased so that surface recombination is virtually eliminated.
For such an arrangement the light must be penetrating enough to generate carriers
in the central core. 171 As another alternative, light can enter radially from the edge
of a relatively thick slice and the photo current collected by a contact completely
covering one side and a centered contact of reduced diameter on the other. The
contacts will then only collect carriers which have recombined well into the slice. 199
If trapping is present, a long tail on the decay curve will be observed. Shining
a continuous background light on the sample 12 •16 or heating it to about 70°C should
remove the effect and allow useful measurements to be made. Germanium usually
can be measured with a minimum of trapping difficulties, whereas with silicon, ~"\~
lifetimes an order of magnitude too long may be obtained because of trapping.

4.3 ALTERNATE INJECTION METHODS

Contact Injection. Instead of generating carriers by light as just described, it is

possible, particularly with long-lifetime samples, to inject sufficient carriers from
the end contacts to change the sample conductance measurably. Injection can then
be abruptly stopped and the conductance decay observed exactly as before. 3 If the
injection pulse is not long compared with the lifetime, the voltage Ll V will not be
exponential, but that can be corrected by plotting time vs. 10gf(LlV), wheref(LlV)
is given in Ref. 3. By injecting from a point contact and then sampling the spreading
resistance as a function of time, the lifetime in very localized areas can be studied. 20
High-Energy Particles. A pulsed high-energy electron source may be used to
generate the carriers. Van de Graaff accelerators can be pulsed with fall times of
the order of 5 X 10-9 s and thus can be used to measure lifetimes of the order of
10-8 S.31
Flash X-Ray. Very short x-ray pulses can be generated and used instead of light.
They have the advantage of supplying more carriers than can normally be produced
114 Semiconductor Measurements and Instrumentation

by a high-speed light flash, but the high-voltage pulses required to produce the x-rays
(up to 150 kV) make shielding more difficult.

4.4 PHOTOCONDUCTIVITY MODULATION

Sinusoidal light excitation can be used instead of pulses and the phase angle 8
between the photoconductivity of the sample and the impinging light interpreted
in terms of T eff• Teff is found through the expression
tan 8 = WT eff
As before Teff will depend on the geometry and the relative value of T, s, and
surface-barrier capacitance. 19 Experimentally, the modulated light falls on both the
sample and a detector known to introduce negligible phase shift between the incident
light and the electrical signal. For relatively low frequencies the signal from the
photocell can be processed through a parallel RC network and compared with the
signal from the sample. If amplitudes and the RC product are adjusted, a null will
occur for RC = T eff• When the process can be characterized by a single time constant,
i.e., sL/ D is small, the RC time constant will be independent of frequency. Alterna-
tive arrangements have included the use of the signal driving the x and y plates
of an oscilloscope to match the RC network phase shift against that of the sample,52
and the use of a vector voltmeter. 186 Kerr cells have been used to provide modulation
frequencies of up to 4 MHz for measuring InSb lifetimes in the 10-8 s range. 108
For even higher frequencies, a Michelson interferometer with one mirror oscillat-
ing 156 or a modulated laser186 can be used.
An estimate of T should be made and the modulation frequency W chosen so that
WT ~ 0.3. For maximum sensitivity the voltage across the sample should be as high
as possible without overheating the sample or sweeping out too many carriers. The
latter can be checked by gradually increasing the field until T eff begins to decrease,
and then reducing it slightly. Correction curves are available if it is desirable to
operate with somewhat higher fields. 49 With no trapping, white light, a thickness
w greater than ten times the diffusion length, and a lapped surface,
(4.11 )
The actual numerical relation will vary somewhat depending on the absorption
coefficient lX, and the choice of 1.2 is a compromise that covers both Si and Ge.
Should the thickness be such that it is not large compared with L, the use of
correction curves will still allow T to be found. 89
One interesting variation of this method allows measurement of radiative recom-
bination lifetime independently of other processes by using a monochrometer tuned
to the recombination radiation wavelength between a photo detector and the sample.
The phase of the modulation of this signal rather than that from the photocon-
ductivity is then compared with that of the incident light. 186

4.5 PHOTOCONDUCTIVITY

Instead of following the transient behavior of carriers after they are generated,
the increase in steady-state conductivity can be examined. In general, the change
in resistance !lR is given by46
 Lifetime 11 5

where p is the dark resistivity of the sample, I the length of sample irradiated, and
A the sample cross section. When using a constant-current source, the voltage
change ~ V will be proportional to ~R. The number of excess carriers ~p and ~n
will depend on lifetime, light intensity and absorption coefficient, surface-recombin-
ation velocity, and sample dimensions. The exact expression is somewhat intractable,
but provided the sample is thick enough to absorb all the light, it can be expressed
as
Ap = cpf3(l - R )f(a, L, s, D, and sample dimensions) (4.13)
where cp is the incident-light intensity, f3 is the efficiency of converting photons to
hole-electron pairs (usually considered 1), R is the reflection coefficient, and L is
the carrier diffusion length, given by L = ~. By making various assumptions
regarding the relative magnitude of the various parameters, considerable simplifica-
tion can be achieved. The problem is to pick simplifications that are physically
realizable and also amenable to experimental interpretation.
Spatial variations in lifetime can in principle be measured by using a relatively
small spot oflight136 or an electron beam 153 and scanning it over the surface. Since
only a small region is illuminated, the sensitivity is reduced; so careful signal
processing is required.
Experimentally none of the ~ V readings actually have to be taken with steady
illumination. As long as the frequency is relatively low, the light may be chopped
and ac signal processing used. To simplify instrumentation, bridges have been
constructed using a photoresistor in one of the balancing arms so that light intensity
and current variations are both, compensated. 102

4.6 SURFACE PHOTOVOLTAGE

When light shines on the surface of a semiconductor without an intentional

junction, a surface photovoltage will occur which is similar to the voltage developed
at a p-njunction. By capacitively coupling to the surface, the voltage can be detected
without direct contact and can be used to measure the carrier diffusion length. 42 ,92
It is a rather unique method in that surface recombination does not influence the
measured value of lifetime, and it can be used even if there is extensive majority-
carrier and moderate minority-carrier trapping. 181 There are restrictions in the ratio
of ~p, ~n to nand p that dm be tolerated, but in general, they are less severe than
in some of the other methods. The sample thickness must be greater than -4L.
(If used, for example, on epitaxial layers, if the layer is greater than 4L there are
no problems; if it is less192 than -O.5L, the substrate diffusion length is measured.)
The expression for the equilibrium numbers of carriers is similar to that used for
photoconductivity, except that now only those carriers generated within approxi-
mately one diffusion length of the surface will contribute to the photovoltage and
~ _ f3cp(l - R) aL
.p - D / L + s 1 + aL
In deriving this expression, the value of a was not allowed to go to an extreme,
since the surface voltage V. is measured as a function of a. V. will be some function
of ~p which actually need not be known in order to determine L. That is, V. = f(~p),
116 Semiconductor Measurements and Instrumentation

or conversely, !:J.p = F(17.). From this, the light intensity cp can be expressed in terms
of 17.. Thus

cp = F (17.)M (I + ex~) (4.15)

where M= s + D/L
- fi(1 - R)

For a given sample, M should be a constant as long as the wavelength is not changed
enough to affect either fi or R appreciably. Experimentally, if ex is changed by
varying the wavelength and cp is always adjusted to give the same value of 17., F(V.)
should also remain constant. Under those conditions a plot of cp vs. 1/ex extrapolated
to cp = 0 gives L. That is,

cp=O=I+ex~ (4.16)

The experimental arrangement is shown in Fig. 4.5a, and a typical plot in Fig.
4.5b. The wave analyzer is used only as a narrow-band detector. Other instru-
mentation such as a lock-in amplifier can be used instead. Either a monochrometer

Sample
Tungsten
lightsouree

Wave
1.....------1-0 Ampl ifier analyzer

(a)

1/a ,em
( b)

Fig. 4.5. Use of surface photovoltage to determine the

diffusion length L from 10 and lX. (From Joseph Horak,
"Minority Carrier Lifetime Measurements on Silicon Material
for Use in Electron Irradiation Studies," AF Contract
F19628-67-0043, Scientific Report, May 1968.)
 Lifetime 11 7

or a series of interference filters can be used for changing the wavelength. Filters
have the advantage of providing large-area illumination inexpensively. The
(sample-screen) combination must be free of vibration so that no capacitor modula-
tion at the chopping frequency occurs. The pickup-capacitor plate must allow light
through it and can be either a fine wire mesh or a semitransparent evaporated-metal
film. Some care must be given to the value of a used in the calculations, since for
the case of silicon at least, it appears to depend on surface treatment and may vary
enough to alter the shape of the cp, l/a curve substantially.192

4.7 PEM EFFECT

The photoelectromagnetic (PEM) effect is the Hall effect of a photoinduced

diffusion current. That is, the light-generated hole-electron pairs will, under the
influence of the magnetic field as shown in Fig. 4.6, separate and cause either a
short-circuit current to flow or an open-circuit voltage to develop. Both the short-
circuit current and the open-circuit voltage are proportional to YL and so can be
used to measure L and hence T. 64 The photoconductance and photovoltage depend
on L rather than the square root, and hence as T decreases, those effects will become
immeasurably small more rapidly than the PEM effect. For that reason it was used
very early to study short-lifetime semiconductors. As with the other methods dis-
cussed, the geometry can be chosen so that the surface recombination is dominant.
If it is desired to study high values of s, the PEM effect is very useful. 58
The simplest theory gives
Isc(per unit width) = cp{3qLB(!l-n + !l-p) (4.17)
where B is the magnetic induction. When the thickness is not many times L, the
surface recombination not zero, and the light absorbed at varying depths, the
expressions become increasingly complicated. However, if both the zero-magnetic-
field photoconductance (j,G and the PEM short-circuit current are measured with
the same light intensity, the ratio of (j,G to Isc removes the need to know either cp,
{3, or s. Under these conditions, and assuming L ~ thickness,
B2D«(j,G)2
T - ----::-- (4.18)
- (Isc)2

Incident light

Magnetic field

v----t-+---+-~/

-7'--- PME current

r------..fJ(:'-i(G<;~==h{-- Carriers separate

in magnetic field

Fig. 4.6. The photoelectro-

magnetic (also referred to as
Voltage probes to
PME) method for measuring be used when measuring
lifetime. photoconductivity
 118 Semiconductor Measurements and Instrumentation

4.8 DIFFUSION-LENGTH MEASUREMENTS

In several of the preceding methods, L was deduced by measuring current or

voltage as some parameter such as the depth of light absorption was changed. It
is also possible to use geometries such that the separation of the light source and
the detector of carriers can be varied at will. For example, carriers can be generated
by shining light on the surface and collected some distance away by a suitable biased
point-contact electrode! or built-in p-n junction if one is available. * The carrier
motion is described by the continuity equation, and for the particular geometry used,
the equation must be solved for current collected as a function of distance between
the collector and point of generation. 4 For a line oflight falling on a large expanse
(Fig. 4.7), the solution is in terms of a zero-order Hankel function, provided that
< <
the geometrical restrictions 5do r %z are followed. 4 (See Fig. 4.7 for a definition
of terms.) For large r/ L the solution reduces to an exponential, as it does for most
other geometries. That is, there will usually be a region that can be approximated
by 1 = 10 exp( -r/ L). Therefore, if response vs. distance is plotted on semilog paper,
the diffusion length is given by the slope of the line.
These measurements are quite insensitive to trapping, but surface recombination
can cause errors much as it does for photodecay. If the surface-recombination
velocity s is small compared with the diffusion velocity yD/r, negligible error will
occur. Thus, for materials like Ge, which tend to have long lifetimes and low-
recombination-velocity surfaces, there is little trouble. Si, however, usually has a
:J lower lifetime and much higher surface recombination. One approach is to calculate
, curves for various L, s combinations and choose the best fit. l ,103 Other details may
be found in Ref. 22. A better way perhaps is to treat the surface to produce either
a low or at least a reproducible value of s. Etching is often used for low s, and
lapping or sandblasting for very high s. Surface treatments to give heavy surface
accumulation should reduce surface recombination and have been suggested for
silicon. 28 Inversion layers can cause serious error, since they may give rise to rather
large signals far from the collector. These measurements normally give only the
diffusion length L, so that to find T, a determination of the diffusion coefficient is
necessary. However, by moving the spot at a uniform velocity great enough to be
an appreciable fraction of yD/r, both D and T can be estimated from the asym-
metry of the response. 7 An alternate approach is to use chopped light and measure
both the variation of signal intensity with distance from the source and the phase
difference between the light source and the signaU3

'The general method does not depend on the mode of detection, and indeed the infrared absorption
of the free carriers has been used to make diffusion-length measurements in Ge. 47

To amplifier
Illuminated
area

Movable
collector
point

Fig. 4.7. Geometry for diffusion-length measurements.

 Lifetime 119

For materials such as Si, Ge, and GaAs, an ordinary incandescent bulb and
conventional optics are satisfactory, but for materials like InSb much longer wave-
length and special optics (e.g., reflective) may be necessary. An additional advantage
of reflective optics is that the spot size can be determined using visible light and
will not change as the wavelength is increased. In order to simplify instrumentation,
chopped light and ac amplifiers are ordinarily used. However, unless the chopping
frequency w is such that W 2 'T2 ~ 1, the measurement value will not be the lifetime
but something between it and a limiting value of 21w. 13 For lifetimes of 100 p,s,
chopping frequencies of 100 Hz are appropriate.
An electron beam can also be used to generate the carriers. It has the advantage
of providing a very small spot size and allows the measurement of very short diffusion
lengths. If done in conjunction with a scanning electron microscope, the area near
the junction can first be viewed in the normal way and the exact area of interest
chosen.140
Microwave detection of the carriers can be used for materials with long diffusion
lengths. 75, 118 The procedure is complicated and offers no advantage unless there
is no way to establish electrical contact to the sample.
By using a p-n junction as the detector and a bevel across it as shown in Fig.
4.8, the distance from source to detector can be varied by moving a light spot (or
> >
electron beam191) down the incline. For Xj 2L, aL 3, and aD ~ s, the short-
circuit current is given by
I =Aexp(-x/L)
(4.19)
se 1 + sLID
where A is a constant involving the various optical parameters. By keeping the light
intensity and s constant and plotting Ise vs. Xi' L can be determined from 131,142

(4.20)

Movable
spot of light

Junction _____ t - - -_ _ _ _ _.:=.._ Xj

T-

(0)

Fig.4.8. Details of bevel probing.

(Adapted from Ashley and Biard. 194 ) (0 )
 120 Semiconductor Measurements and Instrumentation

In terms of the distance x along the incline which makes an angle 0 with the plane
of the junction
lS == sin O(tix)
(4.21)
ti(/nIsc)
If there are two discrete layers of the same type but of different Vs (e.g., n+, n) above
the junction, the response curve will show a break when the light spot crosses the
boundary.142 The equipment necessary is as shown in Fig. 4.8b. A metallurgical
microscope can be used to provide small spot size* for wavelengths out to about 1 !-Lm
and is usually the basis for such equipment. Additionally, a light chopper and
phase-sensitive detector or other narrow-band amplifier are necessary in order to
provide the required signal-to-noise ratio over the two to three decades of Isc that
should be plotted.
The wavelength can be chosen to ensure that ex is sufficiently large for Eq. (19)
to be valid. In some cases, e.g., GaP, this may require ultraviolet. 197

4.9 DRIFT

Historically, this is the oldest of the methods discussed. 2 A pulse of minority

carriers is injected into a thin rod of material and swept along the rod by an applied
field. Some distance down the rod the carriers are collected. From the decrease
in amplitude during the time of travel, the lifetime may be calculated. A rectangular
pulse originally injected will gradually take a bell distribution and spread more and
more as time increases. Thus, pulse amplitude is no longer a measure of the number
of surviving carriers. For a very short pulse that area will be proportional to
Pulse height VI (4.22)

or Pulse height _r 1/2 exp -t (4.23)

'T

However, for long pulses and the short times used, the t 1/2 dependence is small and
usually neglected in comparison with the exponential.
, If there are no traps, the envelope of the detected carrier should be symmetrical.
-U However, trapping causes a tail to occur (Fig. 4.9), much like that observed in
photodecay.16 The collector may also be nonlinear in that the collector current is
not always proportional to the minority-carrier concentration over the range of
concentrations likely to be encountered. In particular, efficiency is usually degraded
at very low levels. Thus, either pulse amplitudes must be rather large, or as has
been suggested for silicon, the collector may be continually flooded with light.12
Rather than moving the collector point or changing the sweep field in order to
*When L is very short, the size and light distribution in the spot may affect the calculations. For
a discussion, see Ref. 200.

Fig. 4.9. Collector signal shape as a function of

time. Dotted line without trapping. Solid line
with trapping. (Adapted from Hornbeck and
Haynes. 16)
 Lifetime 121

vary the time between injection of the carriers and their collection, a collector voltage
pulse can be used. That is, the carriers can be allowed to diffuse for a time, and
then the drift field applied to sweep them to the collector for detection. A plot of
collector response vs. delay time will then vary as exp(_t/r).14,20

4.10 MISCELLANEOUS METHODS

Charge-Collection Efficiency. For very high resistivity materials, if carrier pulses

are generated by high-energy particles such as alpha particles and the sample is
used as a counter, the pulse amplitude is given by

A = Ao !L~E [1 - exp !L~;J (4.24)

where E is the electric field, d the counter (sample) thickness, which must be large
compared with the particle range, !L the carrier mobility, and 7" the lifetime. A plot
of A vs. E will enable the !L7" product to be determined so that if JL is independently
known, 7" is available. 61 ,149
Noise. Noise in semiconductors can sometimes be related to the lifetime when
the generation-recombination process is the predominant noise generator. In that
case
Vn 2(R + RL)4 n(AL)
7" =~~~~~~~-- (4.25)
4V2R2RL2!::.f
where v,. is the noise voltage, R the sample resistance, RL the series load resistance,
n the carrier density, AL the sample volume, V the applied voltage, and !if the
bandwidth used to measure the noise (the center frequency assumed to be ~ 1/7").78,106
Electroluminescence. For wide-bandgap semiconductors the excitation frequency
at which the electroluminescence intensity is reduced by one-third is approximately
equal to 1/7".93

REFERENCES

1. F. S. Goucher, Measurement of Hole Diffusion in n-Type Germanium, Phys. Rev.,

81 :475 (1951).
2. J. R. Haynes and W. Shockley, The Mobility and Life of Injected Holes and Electrons
in Germanium, Phys. Rev., 81:835-843 (1951).
3. D. Navon, R. Bray, and H. Y. Fan, Lifetime of Injected Carriers in Germanium, Proc.
IRE, 40:1343-1347 (1952).
4. L. B. Valdes, Measurement of Minority Carrier Lifetime in Germanium, Proc. IRE,
40:1420-1423 (1952).
5. L. P. Hunter, E. J. Huibregtse, and R. L. Anderson, Current Carrier Lifetimes Deduced
from Hall Coefficient and Resistivity Measurements, Phys. Rev., 91:1315-1320 (1953).
6. E. M. Pell, Recombination Rate in Germanium by Observation of Pulsed Reverse
Characteristic, Phys. Rev., 90:278-279 (1953).
7. G. Adam, A Flying Light Spot Method for Simultaneous Determination of Lifetime
and Mobility of Injected Current Carriers, Physica, 20:1037-1041 (1954).
8. R. H. Kingston, Switching Time in Junction Diodes and Junction Transistors, Proc. IRE,
42:829-834 (1954).
9. B. Lax and S. F. Neustadter, Transient Response of a p-n Junction, J. Appl. Phys.,
25: 1148-1154 (1954).
122 Semiconductor Measurements and Instrumentation

10. A. Many, Measurement of Minority Carrier Lifetime and Contact Injection Ratio on
Transistor Materials, Proc. Phys. Soc., 867:9-17 (1954).
11. D. G. Avery and D. P. Jenkins, Measurements of Diffusion Length in Indium Anti-
monide, J. Electron., 1:145-151 (1955).
12. J. B. Arthur, W. Bardsley, A. F. Gibson, and C. A. Hogarth, On the Measurement
of Minority Carrier Lifetime in n-Type Silicon, Proc. Phys. Soc., 868:121-129 (1955).
13. D. G. Avery and J. B. Gunn, The Use of a Modulated Light Spot in Semiconductor
Measurements, Proc. Phys. Soc., 868:918-921 (1955).
14. N. F. Durrant, Measurement of Minority Carrier Lifetimes in Semiconductors, Proc.
Phys. Soc., 868:562-563 (1955).
15. B. R. Gossick, On the Transient Behavior of Semiconductor Rectifiers, J. Appl. Phys.,
26:1356-1365 (1955).
16. J. A. Hornbeck and J. R. Haynes, Trapping of Minority Carriers in Silicon. I. p-Type
Silicon, Phys. Rev., 97:311-321 (1955).
17. S. R. Lederhandler and L. J. Giacoletto, Measurement of Minority Carrier Lifetime
and Surface Effects in Junction Devices, Proc. IRE, 43:477-483 (1955).
18. Sumner Mayburg, dc Photoconductivity Technique for the Determination of Lifetime
of Minority Carriers in Silicon Filaments, Rev. Sci. Instr., 26:616-617 (1955).
19. B. H. Schultz, Analysis of the Decay of Photoconductance in Germanium, Philips Res.
Rept., 10:337-348 (1955).
20. W. G. Spitzer, T. E. Firle, M. Cutler, R. G. Schulman, and M. Becker, Measurement
of the Lifetime on Minority Carriers in Germanium, J. Appl. Phys., 26:414-417 (1955).
2l. D. T. Stevenson and R. J. Keyes, Measurement of Carrier Lifetimes in Germanium
and Silicon, J. Appl. Phys., 26:190-195 (1955).
22. W. van Roosebroeck, Injected Current Carrier Transport in a Semi-infinite Semi-
conductor and the Determination of Lifetimes and Surface Recombination Velocities,
J. Appl. Phys., 26:380-391 (1955).
23. H. L. Armstrong, On Open Circuit Transient Effects in Point Contact Rectifier, J. Appl.
Phys., 27:420-421 (1956).
24. D. M. Evans, Measurements on Alloy-Type Germanium Transistors and Their Relation
to Theory, J. Electron., 1:461-476 (1955).
25. K. D. Glinchuk, E. G. Mise1iuk, and E. I. Rashba: Measurement of Rate of Recombina-
tion of Carriers by Conductivity Modulation, Soviet Phys. Tech. Phys., 1:2521-2528
(1956).
26. N. J. Harrick, Lifetime Measurements of Excess Carriers in Semiconductors, J. Appl.
Phys., 27:1439-1442 (1956).
27. H. K. Henisch and J. Zucker, Contactless Method for the Estimation of Resistivity and
Lifetime of Semiconductors, Rev. Sci. Instr., 27:409-410 (1956).
28. C. A. Hogarth, On the Measurement of Minority Carrier Lifetimes in Silicon, Proc.
Phys. Soc., 869:791-795 (1956).
29. S. G. Kalashnikov, Recombination of Electrons and Holes when Various Types of Traps
Are Present, Soviet Phys. Tech. Phys., 1:237-247 (1956).
30. O. V. Sorokin, Measurement of the Lifetime, Diffusion Coefficient, and Rate of Surface
Recombination for Non-equilibrium Current Carriers in a Thin Semiconductor Speci-
men, Soviet Phys. Tech. Phys., 1:2390-2396 (1956).
3l. G. K. Wertheim and W. M. Augustyniak, Measurement of Short Carrier Lifetimes, Rev.
Sci. Instr., 27:1062-1064 (1956).
32. R. L. Watters and G. W. Ludwig, Measurement of Minority Carrier Lifetime in Silicon,
J. Appl. Phys., 27:489-497 (1956).
33. H. L. Armstrong, Comparator Method for Optical Lifetime Measurements on Semi-
conductors, Rev. Sci. Instr., 28:202 (1957).
34. T. M. Buck and F. S. McKim, Measurements on the PME Effect in Germanium, Phys.
Rev., 106:904-909 (1957).
 Lifetime 123

35. M. Byczkowski and J. R. Madigan, Minority Carrier Lifetime in p-n Junction Devices,
J. Appl. Phys., 28:878-881 (1957).
36. D. H. Clarke, Semiconductor Lifetime as a Function of Recombination State Density,
J. Electron. Control, 3:375-386 (1957).
37. A. R. Engler and C. J. Kevane, Direct Reading Minority Carrier Lifetime Measuring
Apparatus, Rev. Sci. Instr., 28:548-551 (1957).
38. M. Garbuny, T. P. Vogl, and J. R. Hansen, Method for the Generation of Very Fast
Light Pulses, Rev. Sci. Instr., 28:826-827 (1957).
39. J. C. Henderson and J. R. Tillman, Minority Carrier Storage in Semi-conductor Diodes,
Proc. lEE, 1048:318-332 (1957).
40. M. I. Iglitsyn, Iu. A. Kontsevoi, Measuring the Lifetime of Charge Carriers in Semi-
conductors, Soviet Phys. Tech. Phys., 2:1306-1315 (1957).
41. M. I. Iglitsyn, Iu. A. Kontsevoi, and V. D. Kudin, Measurement of Lifetime in Mono-
crystalline Silicon, Soviet Phys. Tech. Phys., 2:1316-1321 (1957).
42. E. O. Johnson, Measurement of Minority Carrier Lifetimes with the Surface Photo-
voltage, J. Appl. Phys., 28:1349-1353 (1957).
43. J. H. Malmberg, MillimicroSecond Duration Light Source, Rev. Sci. Instr., 28:1027-lO29
(1957).
44. O. V. Sorokin, A Method for Measuring the Volume Lifetime and the Diffusion
Coefficient of Current Carriers by Measuring the Resistance of a Semiconductor in a
Magnetic Field, Soviet Phys. Tech. Phys., 2:2572-2574 (1957).
45. L. J. van der Pauw, Analysis of the Photoconductance in Silicon, Philips Res. Rept.,
12:364-376 (1957).
46. H. M. Bath and M. Cutler, Measurement of Surface Recombination Velocity in Silicon
by Steady-State Photoconductance, J. Phys. Chern. Solids, 5:171-179 (1958).
47. Lermart Huldt and Torsten Stafiin, Infrared Absorption of Photogenerated Free Carriers
in Germanium, Phys. Rev. Lett., 1:236-237 (1958).
48. G. Bemski, Recombination in Semiconductors, Proc. IRE, 46:990-lO04 (1958).
49. N. B. Grover and E. Harnik, Sweep-out Effects in the Phase Shift Method of Carrier
Lifetime Measurements, Proc. Phys, Soc. London, 72:267-269 (1958).
50. R. Gremmelmaier, Irradiation on p-n Junctions with Gamma Rays: A Method for
Measuring Diffusion Length, Proc. IRE, 46:1045-lO49 (1958).
51. F. J. Hyde, Some Measurements on Commercial Transistors and Their Relation to
Theory, Proc. lEE, 1058:45-52 (1958).
52. E. Harnik, A. Many, and N. B. Grover, Phase Shift Method of Carrier Lifetime
Measurements in Semiconductors, Rev. Sci. Instr., 29:889-891 (1958).
53. J. P. McKelvey, Volume and Surface Recombination ofInjected Carriers in Cylindrical
Semiconductor Ingots, IRE Trans. Electron Devices; ED-5:260-264 (1958).
54. A. Many and R. Bray, Lifetime of Excess Carriers in Semiconductors, in "Progress in
Semiconductors," vol. 3, pp. 117-151, John Wiley & Sons, Inc., New York, 1958.
55. B. K. Ridley, Measurement of Lifetime by the Photoconductive Decay Method, J. Elec-
tron. Control, 5:549-558 (1958).
56. D. J. Sandiford, Temperature Dependence of Carrier Lifetime in Silicon, Proc. Phys.
Soc., 71 :1002-lO06 (1958).
57. A. C. Sim, A Note on Surface Recombination Velocity and Photoconductive Decays,
J. Electron. Control, 5:251-255 (1958).
58. W. Van Roosbroeck and T. M. Buck, Methods for Determining Volume Lifetimes and
Surface Recombination Velocities, in F. J. Biondi (ed.), "Transistor Technology," vol. 3,
pp. 309-324, D. Van Nostrand Company, Inc., Princeton, N.J. 1958.
59. R. N. Zitter, Role of Traps in the Photoe1ectromagnetic and Photoconductive Effects,
Phys. Rev., 112:852-855 (1958).
60. M. B. Das and A. R. Boothroyd, On the Determination of the Minority Carrier Lifetime
in the Base Region of Transistors, J. Electron. Control, 7:534-539 (1959).
124 Semiconductor Measurements and Instrumentation

61. W. D. Davis, Lifetimes and Capture Cross Sections in Gold-doped Silicon, Phys. Rev.,
114:1006-1008 (1959).
62. L. Huldt, Optical Method for Determining Carrier Lifetimes in Semiconductors, Phys.
Rev. Lett., 2:3-5 (1959).
63. Quentin A. Kerns, Frederick A. Kirsten, and Gerald C. Cox, Generator of Nanosecond
Light Pulses for Phototube Testing, Rev. Sci. Instr., 30:31-36 (1959).
64. T. S. Moss, "Optical Properties of Semiconductors," Academic Press, Inc., New York,
1959.
65. G. Porter and E. R. Wooding, Simple Light Source of about 10 mILS Duration, J. Sci.
Instr., 36:147 (1959).
66. A. P. Ramsa, H. Jacobs, and F. A. Brand, Microwave Techniques in Measurement of
Lifetime in Germanium, J. Appl. Phys., 30:1054-1060 (1959).
67. A. C. Sim, A Note on the Use of Filters in Photoconductivity Decay Measurements,
Proc. lEE, 1068(Suppl. 15):308-310 (1959).
68. M. Waldner, Measurement of Minority Carrier Diffusion Length and Lifetime by Means
of the Photovoltaic Effect, Proc. IRE, 47:1004-1005 (1959).
69. H. A. Atwater, Microwave Measurement of Semiconductor Carrier Lifetimes, J. Appl.
Phys., 31 :938-939 (1960).
70. J. S. Blakemore and K. C. Nomura, Influence of Transverse Modes on Photoconductive
Decay in Filaments, J. Appl. Phys., 31:753-761 (1960).
71. Z. Bodo', Determination of Minority Carrier Lifetime in Semiconductors, in "Solid-State
Physics Electronics Telecommunications," pp. 194-198, Academic Press, Inc., New York,
1960.
72. B. Ya Moizhes, Elimination of Edge Effect during the Measurement of the Photo-
magnetic EMF in Semiconductor, Soviet Phys. Solid State, 1:1135-1138 (1960).
73. A. E. Bakanowski and J. H. Forster, Electrical Properties of Gold-doped Diffused Silicon
Computer Diodes, Bell System Tech. J., 39:87-104 (1960).
74. C. Hilsum and B. Holeman, "Carrier Lifetime in GaAs," Proceedings of the International
Conference on Semiconductor Physics, Prague, 1960.
75. H. Jacobs, A. P. Ramsa, and F. A. Brand, Further Considerations of Bulk Lifetime
Measurement with a Microwave Electrodeless Technique, Proc. IRE, 48:229-233
(1960).
76. R. D. Larrabee, Measurement of Semiconductor Properties through Microwave Ab-
sorption, RCA Rev., 21:124-129 (1960).
77. E. G. Landsberg, The Influence of Geometrical Dimensions of Samples in Measure-
ments of Diffusion Length Using the Photomagnetic Method, Soviet Phys. Solid State,
2:777-781 (1960).
78. S. Okazaki and H. Oki, Measurement of Lifetime in Germanium from Noise, Phys.
Rev., 118:1023-1024 (1960).
79. C. G. Peattie, W. J. Odom, and E. D. Jackson, An Ultra-short Lifetime Apparatus, Proc.
lEE, 1068(Suppl. 15):303-307 (1960).
80. B. K. Ridley, The Effect of an Electric Field on the Decay of Excess Carriers in
Semiconductors, Proc. Phys. Soc., 75:157-161 (1960).
81. A. C. Sim, The Dark-Spot Method for Measuring Diffusion Constant and Length of
Excess Charge Carriers in Semiconductors, Proc. lEE, 1068(Suppl. 15):311-328
(1960).
82. V. K. Subashiev, V. A. Petrusevich, and G. B. Dubrovskii, Determination of Recom-
bination Constants from the Spectral Response of Photoconductivity, Soviet Phys.'Solid
State, 2:925-926 (1960).
83. V. K. Subashiev, Determination of Recombination Parameters from Spectral Response
of a Photocell with a p-n Junction, Soviet Phys. Solid State, 2:187-193 (1960).
84. V. K. Subashiev, G. B. Dubrovskii, and V. A. Petrusevich, Determination of the Recom-
bination Constant and the Depth of a p-n Junction from the Spectral Characteristics
of a Photocell, Soviet Phys. Solid State, 2:1781-1782 (1961).
 Lifetime 125

85. W. van Roosbroeck, Current Carrier Transport and Photoconductivity in Semiconductors

with Trapping, Phys. Rev., 119:636-652 (1960).
86. W. van Roosbroeck, Theory of Current Carrier Transport and Photoconductivity in
Semiconductors with Trapping, Bell System Tech. J., 39:515-614 (1960).
87. R. L. Williams, High Frequency Light Modulation, J. Sci. Instr., 37:205-208 (1960).
88. H. A. Atwater, Microwave Determination of Semiconductor Carrier Lifetimes, Proc.
IRE, 49:1440-1441 (1961).
89. S. V. Bogdanov and V. D. Kopylovskii, Concerning the Utilization of the Phase Method
for Measuring Lifetime of Nonequilibrium Charge Carriers in Semiconductors, Soviet
Phys. Solid State, 3:674-679 (1961).
90. F. M. Berkovskii, S. M. Ryvkin, and N. B. Strokan, Effect of Trapping Levels on the
Decay of Current through p-n Junctions, Soviet Phys. Solid State, 3:169-172 (1961).
91. G. B. Dubrovskii, Determination of the Basic Parameters of Photovoltaic Cells with
p-n Junctions with Respect to Their Spectral Characteristics, Ind. Lab., 27:1236-1239
(1962).
92. A. M. Goodman, A Method for the Measurement of Short Minority Carrier Diffusion
Lengths in Semiconductors, J. Appl. Phys., 32:2550-2552 (1961).
93. G. G. Harman and R. L. Raybold, Measurement of Minority Carrier Lifetime in SiC
by a Novel Electroluminescent Method, J. Appl. Phys., 32:1168-1169 (1961).
94. B. Holeman and C. Hilsum, Photoconductivity in Semi-insulating Gallium Arsenide,
J. Phys. Chem. Solids, 22:19-24 (1961).
95. F. J. Hyde and H. J. Roberts, Minority Carrier Lifetime in the Base Regions of Transis-
tors, J. Electron. Control, 11:35-46 (1961).
96. Institute of Radio Engineers, Measurement of Minority-Carrier Lifetime in Germanium
and Silicon by the Method of Photoconductive Decay, Proc. IRE, 49:1292-1299 (1961).
97. H. Jacobs, Microwave Determination of Semiconductor Carrier Lifetimes-Author's
Reply, Proc. IRE, 49:1441-1442 (1961).
98. W. H. Ko, The Reverse Transient Behavior of Semiconductor Junction Diodes, IRE
Trans. Electron Devices, ED-8: 123-131 (1961).
99. J. J. Loferski and J. J. Wysocki, Spectral Response of Photovoltaic Cells, RCA Rev.,
22:38-56 (1961).
100. E. G. Landsberg, Photomagnetic Method of Measuring the Lifetime Electrons and
Holes, Ind. Lab., 27:1226-1230 (1962).
101. M. A. Melehy and W. Shockley, Response of a p-n Junction to a Linearly Decreasing
Current, IRE Trans. Electron Devices, ED-8:135-139 (1961).
102. A. A. Meier, E. A. Soldatov, and V. P. Sushkov, Some Methods of Measuring Lifetime
of Non equilibrium Charge Carriers Based on the Modulation of Photoconductivity, Ind.
Lab., 27:1223-1226 (1962).
103. A. A. Meier, Measurement of the Local Diffusion Length and the Surface Recombina-
tion Rate with Respect to Two Points on Semiconductor Bars, Ind. Lab., 27:1230-1235
(1962).
104. V. A. Petrusevich, Photoelectric Methods of Studying Semiconductors, Ind. Lab.,
27:1217-1223 (1962).
105. Yu. I. Ravich, Determining the Characteristic Parameters of Minority Carriers, in
Semiconductors from Measurements of Photoconductivity and the Photomagnetic Effect,
Soviet Phys. Solid State, 3:1162-1168 (1961).
106. T. P. Vogl, J. R. Hansen, and M. Garbuny, Photoconductive Time Constants and Related
Characteristics ofp-Type Gold Doped Germanium, J. Opt. Soc. Am., 51:70-75 (1961).
107. I. R. Weingarten and M. Rothberg, Radio-Frequency Carrier and Capacitive Coupling
Procedures for Resistivity and Lifetime Measurements on Silicon, J. Electrochem. Soc.,
108:167-171 (1961).
108. E. I. Aderovich, A. N. Gubkin, and B. D. Kopylovskii, Measurement of Short Lifetimes
from Phase Characteristics of the Voltage Transmission Coefficient in a Circuit Con-
taining a p-n Junction, Soviet Phys. Solid State, 4: 1359-1365 (1963).
126 Semiconductor Measurements and Instrumentation

109. A. R. Beattie, and R. W. Cunningham, Large-Signal Photomagnetoe1ectric Effect, Phys.

Rev., 125:533-540 (1962).
110. S. C. Choo and E. L. Heasell, Technique for the Measurement of Short Carrier Life-
times, Rev. Sci. Instr., 33:1331-1334 (1962).
111. S. Deb and B. R. Nag, Measurement of Lifetime of Carriers in Semiconductors through
Microwave Reflection, J. Appl. Phys., 33:1604 (1962).
112. N. R. Howard, A Simple Pulse Generator for Semiconductor Diode Lifetime Measure-
ments, J. Sci. Instr., 39:647-648 (1962).
113. S. M. Krakauer, Harmonic Generation, Rectification, and Lifetime Evaluation with the
Step Recovery Diode, Proc. IRE, 50:1665-1676 (1962).
114. J. Nishizawa, Y. Yamoguchi, N. Shoji, and Y. Tominaga, Application of Siemens
Method to Measure the Resistivity and the Lifetime of Small Slices of Silicon, in
"Ultrapurification of Semiconductor Materials," pp. 636-644, The Macmillan Company,
New York, 1962.
115. W. Rosenzweig, Diffusion Length Measurement by Means of Ionizing Radiation, Bell
System Tech. J., 41 :1573-1588 (1962).
116. G. Suryan and G. Susila, Lifetime of Minority Carriers in Semiconductors: Experi-
mental Methods, J. Sci. Ind. Res., 21A:235-246 (1962).
117. J. A. W. van der Does de Bye, Transient Recombination in Silicon Carbide, Philips
Res. Rept., 17:419-430 (1962).
118. J. N. Bhar, Microwave Techniques in the Study of Semiconductors, Proc. IEEE,
51:1623-1631 (1963).
119. L. W. Davies, The Use ofP-L-N Structures in Investigation of Transient Recombination
from High Injection Levels in Semiconductors, Proc. IEEE, 51:1637-1642 (1963).
120. J. J. Dlubac, S. C. Lee, and M. A. Melehy, On the Measurement of Minority Carrier
Lifetime in p-n Junctions, Proc. IEEE, 51 :501-502 (1963).
121. H. Jacobs, F. A. Brand, J. D. Meindl, S. Weitz, R. Benjamin, and D. A. Holmes, New
Microwave Techniques in Surface Recombination and Lifetime Studies, Proc. IEEE,
51 :581-592 (1963).
122. V. K. Subashiev, Determination of Semiconductor Parameters from the Photomagnetic
Effect and Photoconductivity, Soviet Phys. Solid State, 5:405-406 (1963).
123. E. I. Adirovich, S. P. Lunezhev, and Z. P. Mironenkova, Measurement of 10-10 Sec
Relaxation Times in p-n Junctions by the Phase Compensation Method, Soviet Phys.
Doklady, 9:999-1002 (1965).
124. A. R. Beattie and R. W. Cunningham, Large-Signal Photoconductive Effect, J. Appl.
Phys., 35:353-359 (1964). '
125. I. A. Baev, Measurements of the Minority Carrier Lifetime and Diffusion Coefficient
in InSb by the Moving-Light-Spot Method, Soviet Phys. Solid State, 6:217-221 (1964).
126. A. N. Daw and N. K. D. Chowdhury, On the Variation of the Lifetime of Minority
Carriers in a Junction with the Level oflnjection, Solid State Electron., 7:799-809 (1964).
127. H. J. Fink, Reverse Recovery Time Measurements of Epitaxial Silicon p-n Junctions
at Low Temperatures, Solid State Electron., 7:823-831 (1964).
128. A. S. Grove and C. T. Sah, Simple Analytical Approximations to the Switching Times
in Narrow-Base Diodes, Solid State Electron., 7:107-110 (1964).
129. A. Hoffman and K. Schuster, An Experimental Determination of the Carrier Lifetime
in P-I-N Diodes from the Stored Carrier Charge, Solid State Electron., 7:717-724 (1964).
130. E. A. Ivanova, D. N. Nasledov, and B. V. Tsarenkov, Carrier Lifetime in the Space-
Charge Layer of GaAs p-n Junctions, Soviet Phys. Solid State, 6:604-606 (1964).
131. G. Jungk and H. Menniger, On the Measurement of the Diffusion Length of Minority
Carriers in Semiconductors, Phys. Stat. Solidi, 5:169-174 (1964).
132. H. J. Kuno, Analysis and Characterization of p-n Junction Diode Switching, IEEE
Trans. Electron Devices, ED-11 :8-14 (1964).
133. N. G. Nilsson, Determination of Carrier Lifetime, Diffusion Length, and Surface
 Lifetime 127

Recombination Velocity in Semiconductors from Photo-excited Infrared Absorption,

Solid State Electron., 7:455-463 (1964).
134. G. Susila, A Method for the Determination of Short Lifetime of Carriers in a Photo-
conductor from the Transient Photoresponse, Indian J. Pure Appl. Phys., 2:44-47 (1964).
135. V. A. J. van Lint, and J. W. Harrity, Carrier Lifetime Studies in High-Energy Irradiated
Silicon, in "Radiation Damage in Semiconductors," pp. 417-423, Academic Press, Inc.,
New York, 1964.
136. I. A. Baev and E. G. Valyashko, An Investigation of the Distribution ofInhomogeneous
Regions in Semiconductors, Soviet Phys. Solid State, 7:2093-2099 (1966).
137. O. L. Curtis, Jr., and R. C. Wickenhiser, An Efficient Flash X-Ray for Minority Carrier
Lifetime Measurements and Other Research Purposes, Proc. IEEE, 53: 1224-1225 (1965).
138. D. A. Evans and P. T. Landsberg, Theory of the Decay of Excess Carrier Concentrations
in Semiconductors, J. Phys. Chern. Solids, 26:315-327 (1965).
139. E. Earlywine, L. P. Hilton, and D. Townley, Measuring the Properties of Semiconductor
Grade Materials, Sernicond. Prod. Solid State Tech., 8:17-30 (1965).
140. H. Higuchi and H. Tamura, Measurement of the Lifetime of Minority Carriers in
Semiconductors with a Scanning Electron Microscope, Japan. J. Appl. Phys., 4:316-317
(1965).
141. I. M. Muratov, On the Problem of Determining the Lifetime of Unbalanced Current
Carriers, Radio Eng. Electron. Phys., 10:132-135 (1965).
142. M. H. Norwood and W. G. Hutchinson, Diffusion Lengths in Epitaxial Gallium Arsenide
by Angle Lapped Junction Method, Solid State Electron., 8:807-811 (1965).
143. G. I. Suleiman, N. F. Kovtonyuk, and D. T. Kokorev, Automatic Apparatus for Record-
ing the Lifetime Distribution of Non-Equilibrium Charge Carriers in Semicon'luctors,
Instr. Exptl. Tech., 8:203-205 (1965).
144. K. Schuster, Determination of the Lifetime from the Stored Carrier Charge in Diffused
p-s-n Rectifiers, Solid State Electron., 8:427-430 (1965).
145. K. Santha Kumari, and B. A. P. Tantry, Measurement of Lifetime of Minority Carriers
in Junction Transistors, Indian J. Pure Appl. Phys., 3:380-384 (1965).
146. A. A. Vol'fson, S. M. Gorodetskii, and V. K. Subashiev, A Study of Photoconductivity
in Heavily Doped p-Silicon, Soviet Phys. Solid State, 7:53-57 (1965).
147. J. Vilms and W. E. Spicer, Quantum Efficiency and Radiative Lifetimes in p-Type
Gallium Arsenide, J. Appl. Phys., 36:2815-2821 (1965).
148. P. W. C. Chilvers and K. Foster, Measurement of Lifetime and Transition Time in
Charge Storage Diodes, Electron. Lett., 2: 108-110 (1966).
149. J. A. Coleman and L. J. Swartzendruber, Effective Charge Carrier Lifetime in Silicon
P-I-N Junction Detectors, IEEE Trans. Nuclear Sci., NS-13:240-244 (1966).
150. L. A. Davidson, Simple Expression for Storage Time for Arbitrary Base Diode, Solid
State Electron., 9: 1145-1147 (1966).
151. M. Fournier and C. Lemyre, Measurement of the Effective Minority Carrier Lifetime
in the Floating Region of a P-N-P-N Device, IEEE Trans. Electron Devices, ED-13:511-
512 (1966).
152. C. Jund and R. Poirier, Carrier Concentration and Minority Carrier Lifetime Measure-
ment in Semiconductor Epitaxial Layers by the MOS Capacitance Method, Solid State
Electron., 9:315-319 (1966).
153. C. Munakata and H. Todokoro, A Method of Measuring Lifetime for Minority Carriers
Induced by an Electron Beam in Germanium, Japan. J. Appl. Phys., 5:249 (1966).
154. C. Munakata, Measurement of Minority Carrier Lifetime with a Non-ohmic Contact
and an Electron Beam, Microelectron. Reliability, 5:267-270 (1966).
155. D. B. B. Owen and E. L. G. Wilkinson, Junction Recovery and Trapping in Silicon
p+n Junctions, Intern. J. Electron., 20:21-29 (1966).
156. C. M. Penchina and H. Levinstein, Measurement of Lifetimes in Photoconductors by
Means of Optical Beating, Infrared Phys., 6:173-182 (1966)it,;*
128 Semiconductor Measurements and Instrumentation

157. B. G. Streetman, Carrier Recombination and Trapping Effects in Transient Photocon-

ductive Decay Measurements, J. Appl. Phys., 37:3137-3144 (1966).
158. K. Santha Kumari, and B. A. P. Tantry, Rise and Fall Times of Transistors in Switching
Operation with Finite Impedance, Solid State Electron., 9:730-733 (1966).
159. H. Y. Tada, Theoretical Analysis of Transient Solar Cell Response and Minority Carrier
Lifetime, J. Appl. Phys., 37:4595-4596 (1966).
160. G. V. Zakhvatikin, O. V. Karagioz, V. N. Solomatin, and E. N. Gerasimov, Device for
Measuring the Lifetime of Carriers in High-Resistance Silicon by Means of the Phase
Method, Instr. Exptl. Tech., 10:444-448 (1966).
161. A. Bilotti, Measurement of the Effective Carrier Lifetime by a Distortion Technique,
Solid State Electron., 10:445-448 (1967).
162. A. V. Dudenkova and V. V. Nikitin, Utilization of a Laser to Measure the Lifetime
of Excess Carriers in Gallium Arsenide Single Crystals, Soviet Phys. Solid State,
9:664-665 (1967).
163. F. P. Heiman, On the Determination of Minority Carrier Lifetime from the Transient
Response of an MOS Capacitor, IEEE Trans. Electron Devices, ED-14:781-784 (1967).
164. S. R. Hofstein, Minority Carrier Lifetime Determination from Inversion Layer Transient
Response, IEEE Trans. Electron Devices, ED-14:785-786 (1967).
165. R. M. Lichtenstein and H. J. Willard, Jr., Simple Contactless Method for Measuring
Decay Time of Photoconductivity in Silicon, Rev. Sci. Instr., 38:133-134 (1967).
166. D. J. McNeill, Measurement of Minority Carrier Lifetime in Semiconductor Junction
Diodes, Am. J. Phys., 35:282-283 (1967).
167. N. Miyamoto and J. Nishizawa, Contactless Measurement of Resistivity of Slices of
Semiconductor Materials, Rev. Sci. Instr., 38:360-367 (1967).
168. D. B. Wittry and D. F. Kyser, Measurement of Diffusion Lengths in Direct-Gap
Semiconductors by Electron-Beam Excitation, J. Appl. Phys., 38:375-382 (1967).
169. P. G. Wilson, Recombination in Silicon p-'IT-n Diodes, Solid State Electron., 10:145-154
(1967).
170. David K. Lynn, Charles S. Meyer, and Douglas J. Hamilton (eds.), "Analysis of
Integrated Circuits," McGraw-Hill Book Company, New York, 1967.
171. R. J. Bassett and C. A. Hogarth, A Novel Method for the Direct Determination of
the Small Signal Bulk Minority Carrier Lifetime in the Middle Region of a Semi-
conductor Sandwich, Intern. J. Electron., 24:301-316 (1968).
172. David P. Kennedy, Reverse Transient Characteristics of a p-n Junction Diode due to
Minority Carrier Storage, IRE Trans. Electron Devices, ED-9:174-182 (1962).
173. J. L. Moll, S. Krakaver, and R. Shen, p-n Junction Charge-Storage Diodes, Proc. IRE,
50:43-53 (1962).
174. Charles F. Fell and Wendell A. Johnson, Effective Lifetime, a Figure of Merit for
Nanosecond Diodes, IEEE Trans. Electron Devices, Ed-II :306-308 (1964).
175. M. Zerbst, Relaxationseffekte an Halbleiter-Isolator-GrenzfUichen, Z. Angew. Phys.,
22:30-33 (1966).
176. Horst Preier, Different Mechanisms Affecting the Inversion Layer Transient Response,
IEEE Trans. Electron Devices, ED-15:990-997 (1968).
177. R. J. Bassett, Observation on a Method of Determining the Carrier Lifetime in p+-v-n+
Diodes, Solid State Electron., 12:385-391 (1969).
178. Max Brousseau and Roland Schuttler, Use of Microwave Techniques for Measuring
Carrier Lifetime and Mobility in Semiconductors, Solid State Electron., 12:417-423
(1969).
179. S. C. Choo and A. C. Sanderson, Bulk Trapping Effect on Carrier Diffusion Length
as Determined by the Surface Photovoltage Method: Theory, Solid State Electron.,
13:609-617 (1970).
180. P. Tomanek, Measuring the Lifetime of Minority Carriers in MIS Structures, Solid
State Electron., 12:301-303 (1969).
 Lifetime 129

181. S. C. Choo and R. G. Mazur, Open Circuit Voltage Decay Behavior of Junction Devices,
Solid State Electron., 13:553-564 (1970).
182. J. S. T. Huang, Bulk Lifetime Determination Using an MOS Capacitor, Froc. IEEE,
58:1849-1850 (1970).
183. R. B. Renbeck and L. P. Hunter, Measurement of the Effective Carrier Lifetime by
a Distortion Technique, Solid State Electron., 13:394-395 (1970).
184. D. K. Schroder and H. C. Nathanson, On the Separation of Bulk and Surface Compo-
nents of Lifetime Using the Pulsed MOS Capacitor, Solid State Electron., 13:557-582
(1970).
185. Raymond H. Dean and Charles J. Nuese, A Refined Step-Recovery Technique for
Measuring Minority Carrier Lifetimes and Related Parameters in Asymmetric p-n
Junction Diodes, IEEE Trans. Electron. Devices, ED-18:151-158 (1971).
186. C. J. Hwang, An Improved Phase Shift Technique for Measuring Short Carrier Lifetime
in Semiconductors, Rev. Sci. Instr., 42:1084-1086 (1971).
187. J. L. Lindstrom, Flash X-ray Irradiation of p-n Junctions: A Method to Measure
Minority Carrier Lifetimes, Diffusion Constants and Generation Constants, Solid State
Electron., 14:827-833 (1971).
188. R. Van Overstraeten, G. Declerck, and R. Mertens, Measurement of the Carrier Lifetime
by an Impedance Technique, Solid State Electron., ED-14:289-294 (1971).
189. W. Murray Bullis, National Bureau of Standards, Tech. Note 754, 1972.
190. P. U. Calza1ari and S. Graffi, A Theoretical Investigation on the Generation Current
in Silicon p-n Junctions under Reverse Bias, Solid State Electron., 15: 1003-1011 (1972).
191. W. H. Hackett, Jr., Electron-Beam Excited Minority-Carrier Diffusion Profiles in Semi-
conductors, J. Appl. Phys., 43:1649-1654 (1972).
192. W. E. Phillips, Interpretation of Steady-State Surface Photovoltage Measurements in
Epitaxial Semiconductor Layers, Solid State Electron., 15:1097-1102 (1972).
193. B. L. Smith and M. Abbott, Minority Carrier Diffusion Length in Liquid Epitaxial GaP,
Solid State Electron., 15:361-370 (1972).
194. K. L. Ashley and James R. Biard, Optical Microprobe Response of GaAs, IEEE Trans.
Electron. Devices, ED-14:429-432 (1967).
195. R. A. Logan and A. G. Chynoweth, Charge Multiplication in GaP p-n Junctions, J. Appl.
Phys., 33:1649-1654 (1962).
196. J. L. Moll and S. A. Hamilton, Physical Modeling of the Step Recovery Diode for Pulse
and Harmonic Generation Circuits, Froc. IEEE, 57:1250-1257 (1969).
197. C. J. Hwang, S. E. Haszeko, and A. A. Bergh, UV Microprobe Technique for Measure-
ment of Minority Carrier Diffusion Length in GaP p-n Junction Material, J. Appl. Phys.,
42:5117-5119 (1971).
198. Jayaraman and C. H. Lee, Observation of Two-Photon Conductivity in GaAs with
Nanosecond and Picosecond Light Pulses, Appl. Phys. Lett., 20:392-395 (1972).
199. Kathleen A. Carroll and Karl J. Casper, Separation of Surface and Bulk Minority
Carrier Lifetimes in Silicon, Rev. Sci. Instr., 45:576-579 (1974).
200. Gaberiel Lengyel, Effect of Spot Size on the Determination of the Diffusion Length
of Minority Carriers in p-n Junctions Using Scanned Light or Electron Beam Tech-
niques, Solid State Electron., 17:510-511 (1974).
 5
Mobility, Hall,
and Type Measurements

S.l MOBILITY

The carrier drift velocity v (much less than the actual carrier velocity, since the
carrier traces out a much more lengthy, nearly random path) is proportional to the
field E and is described by
(5.1)
where JLd is the carrier drift mobility.1 Alternately, JL may be defined and measured
from
(5.2)
where n is the carrier density. In this case, JL e is referred to as the conductivity
mobility and in principle should be the same as JLd' The resistivity is given by l/JLenq,
so that a resistivity measurement coupled with a value of n will give the mobility
for majority carriers.
The most common method of determining n, and the one most applicable over
a wide range of materials and temperatures, is through the Hall coefficient* R, and
as a matter of convenience, yet another mobility, the Hall mobility JLH' is defined
through
(5.3)
If the very simplest theory is assumed, JLH is equal to (3n/8)JLe, but in fact, because
of the complex behavior of most semiconductors, there may be appreciably more
variation between the two.
Since JL relates two vectors, it is a second-rank tensor and in all but cubic crystals
will be direction-dependent. Even then, if the current flow is restricted to very thin
sheets, as, for example, in inversion layers, the mobility becomes anisotropic;2 so
measurements must comprehend this. For bulk majority carriers, Eqs. (5.2) and (5.3)
are normally used. The mobility of inversion layers can be determined by measuring
the characteristics of an MOS transistor which uses the inversion layer as its channe1. 2

*RH is sometimes used instead of R to avoid confusion with resistance R. In this chapter resistance
will be designated differently.

131
132 Semiconductor Measurements and Instrumentation

Such measurements must of necessity examine only inversion layers which produce
working devices, but since those are the layers of most practical interest, such a
restriction is not serious.
For minority carriers, the classical measurement of Haynes and Shockley3 shown
in Fig. 5.1 determines /L directly. The procedure is as follows. An electric field is
established along a length of the semiconductor. A point-contact emitter is pulsed
to inject minority carriers into the bar at point A. When the extra packet of carriers
reach the collector at point B, they can be extracted and will show as a pulse on
the oscilloscope. The mobility is given by
d d cm2/(V-s) (5.4)
/LD = Et = (VI L)t
where V is the applied sweep voltage, t the time between pulse injection and its
appearance at the collector, d the emitter-collector separation, and L the length of
the bar.
As the arrival time increases, the pulse amplitude decreases, and the pulse width
increases. The decrease in amplitude is primarily because of carrier recombination
and can be used to deduce lifetime. The increase in width occurs because the carriers
do not remain closely bunched but diffuse out from the high-concentration central
region. 4 Note that if the emitter-collector spacing is too great, the carriers will all
have recombined before reaching the collector. For Ge, whose lifetime may be in
the millisecond range, spacings of up to 1 cm can be conveniently used. Materials
with lower lifetimes and mobilities require commensurately lesser spacings. There
are a number of experimental variations which may afford advantages in special
circumstances. For example, instead of using the emitter contact of Fig. 5.1, partially
injecting end contacts5 or light flashes 6 can be used for carrier injection and the
sweep field can be pulsed. 4 ,5
Possible sources of error are conductivity modulation caused by the carrier injec-
tion, trapping, distortion of the field because of imperfect contacts, and injection
level. By making measurements at several injected pulse heights and extrapolating
to zero amplitude, the first can be minimized. When trapping is present, the value
determined will be less than that actually displayed by an individual carrier during
the time it is untrapped. 8,9 Shining a steady light on the surface may fill the traps
and minimize their effect. 10 The greater the collector-emitter separation to area ratio
and the greater the end contact-to-collector and end contact-to-emitter ratio, the

I
Injection .J"L.
Emi~er
!
voltage L-IL..-*____---'
I
Sweep
'. d
voltage (0 )

1
I

+ :
I I I

---.Jfi1:L-li'-l"l\--.-+-
I I
i
I I
Fig. 5.1. Geometry for direct
Timet - - measurement of mobility
(b) (Haynes-Shockley experiment).
 Mobility, Hall, and Type Measurements 133

smaller the chance for field distortion to cause errors. If the injected carriers have
a concentration which is an appreciable fraction ofthe majority-carrier concentration,
the pulse moves at a rate determined by the ambipolar mobilityll /La [see Eq. (4.8)].
There are also various device-related measurements that can be used to deduce
mobility. Examples are transistor-base transit time (if diffusion-controlled), and the
behavior of pulsed PIN diodes or particle detectors. 12,13 Unlike other methods, this
one allows the mobility of both holes and electrons to be determined in the same
sample. The method is also applicable to mobility measurements under high-field
conditions, since until the carrier pulse is injected, the reverse-biased diode is dissi-
pating very little power. The carrier pulse may be initiated by a burst of relatively
low energy electrons (so they will have limited range in the semiconductor) or by
a flash of high-intensity light.14 Examples of its use include measurements of
mobilities in Se and CdS. 15

5.2 HALL EFFECTl,16,17,ASTM F76

Hall measurements are widely used in the initial characterization of semiconduc-

tors to measure carrier concentration and/or carrier mobility. As a given semi-
conductor becomes more widely used and better understood, simpler techniques such
as four-point resistivity measurements are usually substituted.
Unlike some of the measurements discussed, the Hall effect has been known for
nearly 100 years, and has been used and written about ever since. When a magnetic
field is applied at right angles to current flow, an electric field EH is generated which
is mutually perpendicular to the current and the magnetic field, and is directly
proportional to the product of the current density and the magnetic induction. Thus
E - RIB
H- A
(5.5)
- RIB
v;H-
w
where R is the Hall coefficient, I the current through the sample, A the sample cross
section, w the thickness, and B the magnetic induction. * Figure 5.2 shows the
geometry, sign convention, etc.

*There are actually several related galvanomagnetic effects, but the Hall effect is the one most used.
Further, they are all tensors and may depend on crystal orientation. There may also be voltages generated
for conditions other than ER , H, and I mutually orthogonal. Sometimes these are also referred to as
Hall voltages. One example is the planar Hall voltage, which is observed when the magnetic field lies
in the plane ABeD of Fig. 5.2.

B
Hall lead (+) for n-type material

D
/.."L-_ _ Current lead

L = total length
Hall lead, (-) x = distance of
for n-type material Hall electrode
Fig. 5.2. Sign and dimension ter- from contcct
minology for Hall bars. RHBI/w
134 Semiconductor Measurements and Instrumentation

Abbreviated Interpretation. Very simple theory predicts that R as defined in Eq.

(5.5) is given by
R - -I _I (5.6)
- nq , pq
where q is the electronic charge and n or p the density of carriers. Thus the carrier
type as well as concentration can also be determined from the Hall coefficient, since
if the sign convention of Fig. 5.2 is followed, R is negative for n-type and positive
for p-type. More elaborate theory predicts that

R - -rn 2 (5.7)
- nq' pq
where r is a constant, usually between 0.5 and 1.5, that depends on the specific details
of conduction in a given material. For spherical energy bands,

rn = rp = 83'77'
By making measurements at high enough magnetic field, r can be reduced to I,
regardless of the conduction mechanism. * In any event, the error introduced by
determining n directly with no prior knowledge of r is not gross. This fact and the
relative simplicity of Hall measurements have accounted for its widespread usage
in the study of semiconductor materials.
For the case of mixed conduction (i.e., an appreciable number of both holes and
electrons), the Hall coefficient has a contribution from each. For the small-field case
R = (llq)(p - b2 n)
(5.8)
(bn + p)2
where b is the ratio of electron-to-hole conduction mobility. Examination of Eq.
(5.8) shows that for n-type material, as the pin ratio increases from zero, R becomes
progressively smaller than would be predicted by supposing that only n-type carriers
were present. For p-type material, as the nip ratio increases, R will be zero when
~n=p ~~
> >
and for b2 n p, R will change from + to - assuming b 1, which it usually is.
From this behavior it is clear that a single measurement of R, without some
background knowledge of the region in which the measurements were made, is very
risky. Ordinarily, one should examine the material as a function of temperature.
If the material is intrinsic, R will decrease as the temperature increases, as shown
by curve a in Fig. 5.3. Its value is obtained by setting n = p = ni in Eq. (5.8) and
is given by
(1/niq)(1 - b)
Ri= I+b (5.10)

If the material is extrinsic, the R will be independent of temperature, as shown by

curve b of Fig. 5.3. The behavior of the transition from extrinsic to intrinsic is

*There may be an oscillation of the magnetic susceptibility of the material as a function of magnetic
field. This is the de Haas-van Alphen effect and will lead to similar oscillations of the Hall voltage,
magnetoresistance, etc. It is observed, however, only at temperatures below perhaps lOOK.
 Mobility, Hall, and Type Measurements 135

(0) liT

/
Overshoot /

/'(
/
\".. / n -type
- a: / p-type
b < 3.7 a: 1.46<b<3.7
'"
0 '"
0
-' -'

( b) liT (e) liT

a:

0'"
-'

(c) liT
n -type
b > 3.7
-
a:
'"
0
-'
!
(f) liT
p-type
b> 3.7

Overshoot I
I
p-type
/
a: b < 1.46
Fig. 5.3. Behavior of R in the
transition region from extrinsic to
intrinsic. (Adapted from Putley 16
'"
0
-'
I' liT
and Hunter. 18) (d)

illustrated in Fig. 5.3b to j18. If b is a function of temperature, it is possible to

have Eq. (5.10) satisfied for more than one nip ratio, in which case multiple R = 0
points are possible (tellurium shows two zero points). Another way to display the
overshoot, as well as other relations, is to use the "Dunlap ellipse," which is obtained
by combining Eq. (5.8) with the comparable expressions for conductivity and plotting
it along with R = /LH/o on /LH' 1/0 coordinates. 19 Because of the overshoot, an
extrapolation or calculation of the intrinsic slope must be done only after the curve
is extended far enough for the effect to become negligible.
One possible source of error in the use of Eq. (5.10) arises because of the finite
and sometimes quite long carrier-diffusion length in semiconductors. 25 Equation
(5.8) and those following were derived assuming zero lifetime. The carrier lifetime
enters into the expression because the equilibrium carrier concentration is upset when
the sample is in the magnetic field. For p ~ n or the reverse there is little error
regardless of the lifetime. When p is comparable with n, there is a difference of
a factor of 2. If the ratio of the drift mobilities is different from the Hall mobility
ratio, the difference may be somewhat more. 21 For cases intermediate between zero
and infinite lifetime, if
S> (b + 1) /L/BEI
where S is the surface recombination velocity, /Lp the hole mobility, and El the
longitudinal electric field, little error will occur.22 Typically for Si and Ge, Sneed
136 Semiconductor Measurements and Instrumentation

only be greater than a few hundred centimeters per second. Thus a surface which
has had light sandblasting or grinding will generally be acceptable.
As Hall measurements in extrinsic specimens are extended to lower temperatures,
the carriers from the doping impurities will begin to freeze out and R will no longer
be temperature-independent. The number of carriers in that temperature region
is given by23

(5.11 )

where NA is the number of acceptor impurities and KA is the equilibrium constant.

If r is temperature-independent (which it may not be) R vs. liT can be converted
directly to a logp or n vs. liT plot, which can then be interpreted in light of Eq.
(5.11). If the excess impurity is predominantly of one atomic species, the slope of
the curve will allow the activation energy and the degree of compensation to be
determined. 16,23-26
Calculations and Consistent Units. For either the meter-kilogram-second (mks)
or centimeter-gram-second (cgs) system,
_ RBI
v;H-
w
However, in the more commonly used practical units (Table 5.1),

Table 5.1. Units and Calculations

MKS SYSTEM
~agnetic induction B = tesla = I volt-s/meter2
Electric field E = volts/meter
Current I = amperes
Current density J = amperes/meter2
Hall coefficient R = meters 3 /coulomb

PRACTICAL CGS UNITS

~agnetic induction B = gauss
Electric field E = volts/cm
Current I = amperes
Current density J = amperes/cm2
Hall coefficient R = cm3 /coulomb
Carrier mobility f.L = cm2/volt-s
Carrier diffusion coefficient D = cm2 /s

ELECTROMAGNETIC CGS UNITS

Magnetic induction B = gauss
Electric field E = abvolts/cm
Current I = abamps
Current density J = abamps/cm2

CONVERSION FACTORS
I tesla = 104 gauss = I weber/meter 2
I volt = 108 abvolts
I amp = 0.1 abamps
I volt-amp-sec = I watt-s = I joule = 107 ergs
k = 1.38 X 10-16 erg;oK
q = 1.6 X 10-19 coulombs/electron
 Mobility, Hall, and Type Measurements 137

where VB is in volts, R in cubic centimeters per coulomb, B in gauss, I in amperes,

and the thickness w in centimeters.
In calculations involving the effect of surface recombination, in practical units,
S> 1O- 8f.L2BEj (b + 1)
where B is in gauss, f.L in square centimeters per volt-second, E j in volts per centime-
ter, and S in centimeters per second.
The Hall angle is given by

8B = tan-I (10- 8 ~B)

where R is in cubic centimeters per coulomb, B in gauss, and p in ohm-centimeters.
There are a number of spurious voltages which will be included in the value read
at the Hall terminals, but most of them can be eliminated by making a series of
readings with the various combinations of current and magnetic field. In particular,
with
+B,+I Vmeas - VI = VB + VE + VN + VRL + VM + VT
-B,+I ~~ ~=-~-~-~-~+~+~ (5.12)
+B, -/ Vmeas V3 = - VB - VE + VN + VRL - VM + VT
-B,-I Vmeas - V4 = VB + VE - VN - VRL - VM + VT
where VB is the true Hall voltage, VE the Ettingshausen voltage, VN the Nernst
voltage, VRL the Righi-Leduc voltage, VM the voltage generated because the Hall
probes are not exactly electrically opposite each other, and VT any thermoelectric
voltage generated because of an externally imposed thermal gradient between the
probes. By combining them,

~+V4-~-~
(5.13)
4
This is the established method of making dc Hall measurements and is the one
recommended in ASTM F 76. As can be seen from Eq. (5.13) it does not separate
out the Ettingsliausen voltage, but that voltage is ordinarily quite small and can
be neglected.
If alternating current of frequency w is used,27,28

RBIo .
VB=--smwl
w

VE = Al exp ( ~: ) sin wI
(5.14)
VM = A2 sin wt
VN , VR, VT are all dc

Ai are constants, and Wo is a time constant which depends on the properties of the
material being measured. If the frequency is high enough, VE can be reduced to
as small a value as desired. By this means VB + VM can be separated from all the
terms without the time-consuming current and field reversals necessary to obtain
138 Semiconductor Measurements and Instrumentation

the results described in Eq. (5.13). VM is independent of the field except for the
magnetoresistance effect changing the IR drop.
For the case of constant current and alternating field (an unlikely experimental
choice),
R1Bo .
VH=--smwt
w
VE , VN , VRL - sin wt (5.15)
VM - W2
In addition, because of the alternating magnetic field, an induced voltage ~, pro-
portional to dB/dt (i.e., w sin w t), will be observed unless extreme care is taken in
arranging leads, or unless a variable bucking coil is used. 97
Should both alternating field and current be used, there will be a dc component
of Hall voltage as well as one which occurs at double the frequency. Except for
VE , the others will all be of frequency w. For different frequencies and specifically
for the current frequency w1 greater than the field frequency w2 (usually the case
since it is difficult to produce high-frequency alternating magnetic fields of the
required magnitude),
VH = 2: IoBo[sin(wl - ( 2 )t + sin(wl + ( 2 )t] (5.16)

All the other voltages occur at different frequencies from VH except for VE , and it
is attenuated by a factor dependent on the ratio of the w's. If the Hall voltage is
balanced against the voltage developed across a variable resistor z which has the
sample current flowing through it, R = zw/ B and I need not be accurately measured.
If the voltage between two contacts along the length of the sample is also IlJeasured
in order to determine resistivity, and if both that measurement and the Hall-voltage
measurement are made with the same sample current,
R VHd1
iLH - P = VpBd 1
(5.17)

where d1 is the separation of the resistivity contacts and Vp is the voltage measured.
Again, the current need not actually be measured, other than to ensure that the
longitudinal electric field is within bounds.
Experimental Procedures Based on ASTM F 76. *,t In making resistivity and Hall-
effect measurements, spurious results can arise from a number of sources.
1. Photoconductive and photovoltaic effects can seriously influence the ob-
served resistivity, particularly with nearly intrinsic material. Measurements
should be made in a dark chamber unless experience shows that the material
is insensitive to ambient illumination.
2. Minority-carrier injection can occur because of the electric field in the
specimen. With material possessing high minority-carrier lifetime and high
resistivity, such injection can result in a lowering of the resistivity for a
distance of several millimeters along the bar. Carrier injection can be
detected by repeating the measurements at lower applied voltages. In the
absence of injection no increase in resistivity should be observed.
*This includes the more salient features of F 76. The reader may wish to consult the complete
procedure, however.
tCopyright ASTM. Permission to reprint granted by the American Society for Testing and Materials.
 Mobility, Hall, and Type Measurements 139

3. Semiconductors have a significant temperature coefficient of resistivity.

Thus the temperature of the specimen should be known and the current
used should be small to avoid resistive heating. Resistive heating can be
detected by a change in readings as a function of time starting immediately
after the current is applied.
4. Spurious currents can be introduced in the testing circuit when the equip-
ment is located near high-frequency generators .
. c5. High contact resistances may lead to spurious results.
6. Surface leakage can be a serious problem when measurements are made
in the high-resistivity range. Surface effects can often be observed as a
difference in measured value of resistivity or Hall coefficient when the
surface condition of the specimen is changed.
7. In measuring high-resistivity samples, particular attention should be paid
to possible leakage paths in other parts of the circuit such as switches,
connectors, wires, and cables, which may shunt some of the current around
the sample. Since high values of lead capacitance may lengthen the time
required for making measurements on high-resistivity samples, connecting
cable should be as short as practicable.
8. Inhomogeneities of the specimen impurity concentration or of the magnetic
flux will cause the measurements to be inaccurate.
9. It is essential that in the case of parallelepiped or bridge-type specimens,
measurements must be made on side contacts far enough removed from
the end contacts that shorting effects can be neglected.
lO. Thermomagnetic effects, with the exception of the Ettingshausen effect, and
effects due to misalignment of the side contacts (in parallelepiped or
bridge-type specimens) can be eliminated by suitable averaging of the
measured Hall emfs. In general, the error dole to the Ettingshausen effect
is small and can be neglected, particularly if the sample is in good thermal
contact with its surroundings.
11. For materials which are anistropic in Hall coefficient such as p-type ger-
manium and n-type silicon, Hall measurements are affected by the orienta-
tion of current and magnetic field with respect to the crystal axes.
12. Spurious emfs which may occur in the measuring circuit, e.g., thermal emfs,
can be detected by measuring the emf across the potential leads with no
current flowing or with the potential leads shorted at the sample position.
Most measurements required in calculating the Hall effect should be measured
to -+-1 percent. Flux uniformity should also be -+-1 percent over the sample area.
Dewars inserted into the magnetic field should not alter it more than -+-1 percent.
Current in the specimen should be restricted so that the associated electric field is
less than 1 V/ cm.
Samples should be single-crystal. They should be mounted in the Hall fixturing
so that mechanical stress does not occur, either from clamping or from differential
expansion if measurements are to be made at temperatures different from room.
If the contact arrangement allows measurement of Hall voltage at more than one
position on the sample, readings should agree within 10 percent. Otherwise in-
homogeneity is a problem and the sample should be discarded.
Effect of Inhomogeneous Sample. The measurements defined by Eq. (5.5) are
predicated on a sample with uniform properties. Actually, there are numerous cases
in which it is desirable to make measurements on samples whose properties are
140 Semiconductor Measurements and Instrumentation

inhomogeneous. These may be divided into four categories: those which are
uniform in two dimensions, such as diffused layers;29-33 those which are composed
of a matrix of one property and inclusions of another;34 those in which the mate-
rial to be measured varies in a random manner so the best that can be done is to
measure an average value;35 and those which have radial gradients (e.g., coring in
slices).98,99 Specific directions may be found in the references indicated.
Effect of Sample Size, Shape, and Electrode Placement. Equation (5.5) assumed
a rectangular sample with uniform end contacts, and the Hall electrodes several
sample widths away from either contact. If the latter condition is not met, the
contacts will partially short out the Hall voltage. In the event that only short, stubby
samples are available, corrections36-39 can be applied. However, the smaller the L/d
ratio, the greater the sensitivity to errors in determining the sample dimensions, and
the smaller the Hall voltage measured.
In the simple theory the Hall contacts are assumed to be infinitely small so that
they do not distort the current flow. However, unless the Hall angle (tan- 1 RH/p)
is very large, the error is still relatively small. Experimentally, contacting can be
by sharp tips or very small (e.g., Imil) alloyed-wire contacts. More often, though,
ears on the sample are used (Fig. 5.4). The ears serve two purposes. First, they
allow a large area to be used for contacting without severely distorting the lines
of current flow in the sample. Second, a contact made directly to the side of the
bar will in general be noisier than one using an ear. 46 ,47 The multiplicity of contacts
allows resistivity to be simply measured on the sample [required if the mobility is
to be calculated by Eq. (5.6)] and affords redundancy in case one contact is broken.
If it is inconvenient to cut out rectangular bars, thin samples of arbitrary shape
such as platelets or slices can be used if contacts are made at four places around
the periphery as shown in Fig. 5.5.40 ,41 If Vs / Is is measured with and without a
magnetic field,
R = _(d_V_I_I)_d (5.18) ,
B

where d V is Vs measured with the field minus Vs measured without the field, and

dl
~L

Point contacts
Fig.5.4. Common Hall-bar configurations with ASTM F
76 suggested dimensions.
 Mobility, Hall, and Type Measurements 141
B

(0 )

D. R/R =-2R11TD

(b)

Fig. 5.5. Use of an arbitrarily shaped

sample with randomly placed contacts for
determining the Hall coefficient. (b) The
error in the Hall coefficient if the probes
are finite sized or misplaced. (van der
Pauw. 41 ) (c)

I is held constant for both measurements. The resistivity must also be measured
on the same sample. The details of this procedure are discussed in Chap. 3.
A square array of contacts can be made inside but close to the perimeter of thin
lamellae. Correction factors are available for rectangles, half-planes, quarter-planes,
full, half-, and quarter-circles. Such an arrangement allows four-point Hall meas-
urements much in the manner of four-point resistivity measurement. Such probes
can be spaced very closely together and thus can be used when only a limited area
is available. *42-44 As the probe spacing to sample lateral dimensions become small
(i.e., a sheet of infinite expanse), the method fails, but as a possible alternative, a
hole can be cut in the sheet, and the probes placed around it or else the probes
can be placed close to an edge. 43 The general concept can also be extended to make
test structures on slices being used for device manufacture.
It is not necessary to have the Hall contacts exactly opposite each other, since
a reversal of magnetic field will cancel out any initial unbalanced voltage. However,
if the unbalanced voltage is much greater than the Hall voltage, error can be
introduced, since VH will be the small difference between two large numbers.
Further, if electronic instrumentation is used, large unbalances may cause amplifier
saturation. Several prebalancing schemes are available. One Hall contact may be
used, along with a virtual contact generated by an external voltage divider. This
method reduces the Hall voltage by a factor of 2 and may generate additional noise.

*Remember, however, that the theory is developed on the assumption that the probe spacing is large.
compared with the thickness of the sample.
142 Semiconductor Measurements and Instrumentation

Two contacts on one side plus a potentiometer between them may be used, but there
will be some distortion of the current lines because of current flow between the two
contacts. Current can be fed into corners of the sample, and the relative amount
adjusted to provide balance at the Hall electrodes.48
Sample Preparation. Because of the complex shape of Hall bars they are most
conveniently cut with an ultrasonic machine, although a fine-nozzle sandblaster or
spark erosion can also be used. If the sample is very thin, it may be etched to shape.
For epitaxial and diffused layers isolated from their substrates by p-n junctions,
etching defined by standard photolithography techniques down through the junction
to the substrate will suffice.49 For built-in test structures in integrated-circuit slices
p-n-junction sidewall isolation can be used. p-n-junction isolation places restrictions
on the amount of current that can be passed through the sample without forward-
biasing the junction and reducing isolation,50 but fortunately Hall measurements
are relatively insensitive to such leakage.
If the material has high carrier mobility and a long lifetime, the surface should
be treated (e.g., sandblasting) to increase the surface-recombination velocity. Surface
conduction or inversion layers can also radically change the measured value of the
Hall coefficient. Materials such as high-resistivity silicon are particularly susceptible
to surface conditions, and a series of treatments in boiling water5 2 can change the
calculated mobility by factors of 10.
Equipment. Fields in the few kilogauss range for good sensitive and labora-
tory-quality magnets are commonly used. The requirements for magnetic-field
homogeneity are not severe; so no special care in pole-piece design such as is
common in nuclear magnetic resonance (NMR) work is necessary. If extraordinarily
inhomogeneous fields are used, corrections can be calculated. 53
The Hall voltage can be measured by a simple potentiometer* and galvanometer,
and the current flow by an ammeter. For high-resistivity samples the simple equip-
ment fails for many reasons. Sensitivity will be reduced because of the low-
impedance detector, and noise becomes more pronounced. Stray signals also cause
more difficulty, and surface leakage across the sample holder may cause erroneous
readings. 54 All leads need to be carefully shielded, and the fact that it is hard to
ground one end of the sample and one terminal of the detector simultaneously makes
external noise a real problem. By using only one Hall probe, the difficulty can be
avoided, but then the sensitivity is reduced by a factor of 2.
The introduction first of vibrating-reed electrometers and then of high-input-
impedance stabilized differential amplifiers has greatly simplified high-impedance
instrumentation. 16,55,56 If a single-ended electrometer and both Hall probes are used,
potentiometers can still be used to allow a low-impedance path to ground for both
the sample and the detector. 57 More desirable is the use of a differential amplifier. 55
It will allow both sample and voltmeter to be grounded and will reject a large
percentage (depending on the common-mode rejection ratio) of any extraneous noise
which is simultaneously induced in both leads. Some additional improvement in
signal to noise can often be obtained by integrating the signal over a several-minute
intervaP5 If long leads are involved, the time constants associated with the lead
capacitance-sample resistance may require inordinately long wait times between
*In Hall's first reported experiment [Am. J. Math., 2:287 (1879)] he used only a galvanometer to observe
the polarity of the voltage and did not measure its value. It is also of interest to note that in order
to get the small value ofw needed for a detectable Hall voltage, he used gold foil, since that was one
of the few techniques then available for obtaining very thin metallic layers.
 Mobility, Hall, and Type Measurements 143

measurements. To minimize this time, the shielded-lead effective capacitance can

be reduced by means of unity-gain high-input-impedance amplifiers driving the
shields.
When dc equipment is used over an extended temperature range, data acquisition
becomes a very time-consuming process. As a consequence, a variety of automatic
methods have been devised. 16,58-6o The temperature may be allowed to drift slowly
to room temperature, with data being recorded as it drifts, or low-inertia holders
can be combined with a temperature controller. Control of the sequencing can be
by timer, local minicomputer, or off-site time-shared computer.
There are many variations of ac, dc field measurements dating back to at least
1912.61 The earliest ones were made in order to study the dependence of the Hall
effect on frequency. Many of the later ones, however, have used alternating current
in order to simplify measurements. Alternating current will eliminate or attenuate
most of the spurious voltages. Amplification is always easier with alternating than
with direct current, and the noise figure of amplifiers generally improves as the
frequency increases from zero to a few hundred hertz. Circuit variations have
differed primarily in the method of bucking out the unbalance due to probe mis-
placement, and in the method of providing a narrow-band detector. 62 -67 The sign
of the Hall voltage is not directly available for those systems using simple voltmeters
for detection, but an oscilloscope may be used to compare the phase of VH with
the sample current, or the balance network can be deliberately unbalanced. De-
pending on the sign of VH , the sum of that voltage and VH will be either greater
or less than the voltage at balance ( VH alone). If a phase-sensitive detector rather
than a voltmeter is used, it will give the phase directly.
Probably the most popular ac system is that of Dauphinee a:--d Mooser.68 It uses
a dc field and low-frequency alternating current for the sample. It depends on a
series of synchronized choppers for simultaneously converting the sample current
to alternating current and rectifying the Hall voltage. There may be problems with
excessive stray capacitance or rectifying contacts, since either of these will change
the balance point. 69 When the choppers open and close, additional noise is gener-
ated, but if a low-noise amplifier is used and then gated so that it is inoperative
during the time switching occurs, the overall signal-to-noise ratio can be improved. 70
The use of an ac field affords the same advantage of yielding an ac signal as does
alternating current. In addition, the probe-misplacement voltage will have two terms,
dc and 2w, which can easily be separated from the Hall frequency w. The major
difficulty is in providing the alternating magnetic field. One way of accomplishing
it is to rotate the sample within a fixed field.71 This necessitates slip rings and their
attendant noise, but a low-noise preamplifier mounted to rotate with the sample
can minimize the noise.72 Another, which obviates slip rings, is to rotate a permanent
magnet about the sample. 71
Should both alternating current of frequency WI and alternating field frequency
W 2 be used, all the spurious voltages ofEq. (5.12) can be eliminated. Therefore, for
those cases where the Hall voltage is small and where noise is a problem, the
double-frequency method may be advantageous. 28,48,73-79 The frequencies used are
generally quite low. The magnetic field, for example, may range from a fraction
of a hertz to 60 Hz, and the current from 10 to 100 Hz. If the same frequency for
both field and sample current is used, many of the advantages disappear, but the
Hall voltage will have a dc term. When VH as a function of frequency is to be studied
and no good ac voltmeters are at hand, the dc term is extraordinarily useful; this
144 Semiconductor Measurements and Instrumentation

is probably why the alternating-field-alternating-current method was used as early

as 1901.80
The various alternating-current and -field methods are unfortunately not a com-
plete panacea, since such things as vibration and amplifier distortion can still produce
voltages of the same frequency as the Hall voltage. As an example, using double
alternating current, if the field is driven by 60 Hz and the sample-current power
amplifier is powered by 60 Hz, any amplifier 60-Hz intermodulation will produce
sum and difference sample currents which will in turn cause a VM contribution of
the same frequency as VH .81 If the sample and heads are not very carefully anchored,
a variety of voltages can be generated which will be indistinguishable from VH in
cases where dc field or fractional-hertz square-wave fields are used. 82 The user of
the ac variations should therefore examine his particular circuitry very carefully
before assuming that all competing voltages have been eliminated.
Special Equipment. For specialized application, still more variations have been
devised. For example, if there is difficulty in making ohmic contacts, the sample
can be cut in a ring shape and rotated in the field.71 This will induce current directly
into the sample so that only voltage contacts are required. When slip rings are
undesirable, an ac field can be used to induce the sample current. Irregularly shaped
samples can sometimes be more advantageously evaluated by using the magneto-
resistance of a spreading resistance probe. 10o
For some materials, e.g., liquid metals and semiconductors, and amorphous
semiconductors, it may be more advantageous to use the Corbino effect to measure
mobility. No voltage contacts are necessary. The values are independent of sample
thickness, and no independent measurement of resistivity is required. The current
is fed into a disk sample coaxially, and the voltage is obtained by inductive cou-
pling. 83 ,84 In the low-frequency region where sample thickness is much less than
skin depth the voltage induced in a single turn is proportional to the product of
the Hall mobility, the frequency, the sample current, the field, and the sample
geometry. However, because of difficulties in analytically evaluating the complete
expression, a standard sample of the same geometry and known mobility can be
used for calibration. 83 For details concerning the application of conventional Hall
measurements to melts, see Ref. 85 and others therein.
Photoconductors are generally characterized by high resistivity and nonohmic
contacts. Nonohmic contacts in turn can cause space-charge effects large enough
to prevent meaningful Hall measurement. To minimize these problems, various
combinations of alternating or steady magnetic field, 87,88 electric field, and inci-
dent-light source have been used. 65
Hall voltage may be measured for fields orders of magnitude greater than the
volts per centimeter recommended for normal usage. Under such circumstances,
pulsed current is required to prevent excessive heating. For very short pulses, a
sampling scope may be used as the Hall-voltage detector. 88 The frequencies of
measurement can also be extended far beyond the few hertz ordinarily used, and
have in fact been made well into the microwave region. 89

S.3 CONDUCTIVITY TYPE

Unlike the other measurements in this chapter, conductivity type is routinely

determined and can be done with quite simple equipment. There are several basic
methods. The choice will largely depend on the specific material and the resistivity
 Mobility, Hall, and Type Measurements 145

range of interest. In some cases, two modes of operation can be combined into one
instrument in order to extend the range.
Rectification. If a dc microammeter is placed in series with an ac source (60-Hz
transformer, for example) and contacts are made to the semiconductor as shown
in Fig. 5.6a,90 the direction of current flow will indicate type. One contact must
be ohmic, and the other rectifying. The rectifying contact is a metal point. The
ohmic contact may be more difficult to arrange but is often just a large-area clamp. *
An oversize battery clip can be used for Si and Ge, although more elegant methods
are preferable.
The difficulty of the ohmic contact can be eliminated by the three-probe con-
figuration of Fig. 5.6b. 91 ,92 To check the performance of either of these variations,
it may be necessary to observe the waveform on an oscilloscope. If the trace is
symmetrical, some other typing system must be used. Such symmetry may occur
because the resistivity is very low or, in the case of Fig. 5.6a, because both contacts
are rectifying equally as well. A hot probe will be less rectifying than a cold one;
so an arrangement similar to Fig. 5.6a can be used with a hot probe replacing the
ohmic contact as in Fig. 5.6c (see the following discussion for hot-probe details).
Thermal EMF. A hot probe touching an n-type semiconductor becomes positive
with respect to an ambient-temperature contact placed on the same materiaPO For
p-type it will be negative. A small heating coil can be placed around one of the
probes, or a miniature soldering iron can itself be used. A simple millivoltmeter
may suffice for a measuring instrument, or more sensitive electronic instrumentation
may be used if required. A collinear four-point-probe system can also be used in
such a fashion that current flow between an end probe and one adjacent generates
a thermal gradient in the semiconductor. The other two probes will then be at
different temperatures and can be used for typing. 91 These possibilities are sketched

*Perfect ohmicity is not required. As long as the point contact is a better rectifier than the other
one, the method will work. However, the less the difference, the poorer the sensitivity.

The center zero meter will read

+ for p-type material if paint
contact is connected to
positive terminal

-.
Applied voltage
(a) n-type p-type

The voltage probe will be

+ for n-type

(b)

r-~---"------, The center zero meter

wi II read + for p-type
if the hot probe is
connected to the neg
terminal

Fig. 5.6. Rectification for type checking.

146 Semiconductor Measurements and Instrumentation

in Fig. 5.7. The thermal emf system is generally restricted to low-resistivity material,
and indeed, if the resistivity becomes high enough, the hot probe may make it
intrinsic. Then, any material which has a higher electron than hole mobility will
always read n-type. To prevent this occurrence, a cold probe, e.g., one thermo-
electrically cooled, may be used instead of a hot one.93
Combinations. If four probes are used, for example, a four-point resistivity probe
head, they may be connected as in Fig. 5.6b for rectification or as in Fig. 5.7c for
thermal emf.91 For Si, thermal emf is applicable over the resistivity range of from
10-3 to 10 2 or 103 Q-cm while rectification is applicable from 10- 2 to 103 Q-cm or
higher. 91
The thermal voltage as in Fig. 5.7 and the rectification of Fig. 5.6a are additive,
so that in fact Fig. 5.6c really represents a combination of Figs. 5.6a and 5.7a. It
is suggested for wide bandgap semiconductors and has been used for checking
108 Q-cm GaAs.94
Hall Effect. As discussed above, the sign of the Hall voltage is a direct indication
of conductivity type. However, since the equipment involved is more complex than
the methods just described, it is recommended only should they fail.
Staining. Chapter 7 describes various chemical stains that may selectively decorate
one type.
Photovoltaic Effect. A photocurrent will flow between an illuminated rectifying-
point contact and an ohmic contact. Its direction will depend on the material type
and can in principle be used for type checking.91 Practical difficulties, mostly
associated with surface preparation, have thus far prevented any widespread usage.
MOS Capacitor. If an MOS capacitor such as that shown in Fig. 5.8a is available,
the nature of its capacitance-voltage dependence is determined by the conductivity
type of the semiconductor. Figure 5.8b shows deta,ils of the C-Vapparatus, and
Fig. 5.8c shows the profiles to be expected for n- or p-iype material. The requirement
for a capacitor is not necessarily restrictive, since they are often either already
available or can be easily added. For example, if oxidized slices are to be checked,
a mercury probe can be used instead of a metal dot and a process step saved. When
very thin inversion layers are to be typed, there are some difficulties because the

External heater wrapped Soldering iron used as hot

a round probe probe
(a) ( b)

~ A B
Probe A will be
Fig. 5.7. Thermal-probe-type
These two probes
used to heat surface hotter than probe B checkers. Hot probe will be +
(c) for n-type material.
 Mobility, Hall, and Type Measurements 147

Insulator

Semiconductor

(a)

-5to+5V 1 MHz

Sweep
generator

-v +V -v +V
Fig. 5.8. Use of C- V plot for type n-type p-type
checking. (c)

space-charge region may move through it too quickly. However, they can usually
be detected by examination of the detailed shape of the C-V curve95 or the shift
of the curve as a function of incident light intensity.96
ASTM Recommendations. Three alternates are recommended.
1. Hot probe for n- and p-type Ge less than 50 fl-cm and nand pSi less than
1,000 fl-cm.
2. Cold probes for n- and p-type Ge less than 20 fl-cm and n or p Si less than
1,000 fl-cm.
3. Rectification for n- and p-type Si between 1 and 1,000 fl-cm. Not recom-
mended for Ge.
Probe temperature should be held in the 40 to 80°C range. All methods are subject
to misreading if probe pressure is too small. The hot-probe material is preferably
stainless steel or Ni, and should be terminated with a 60 ° cone. Shielded leads should
be used for resistivities greater than 1 fl-cm. The center-zero meter should have
a sensitivity of at least 200 flA full scale.

REFERENCES

1. R. A. Smith, "Semiconductors," Cambridge University Press, London, 1959.

2. D. Colman, R. T. Bate, and J. P. Mize, Mobility Anisotropy and Piezoresistance in
Silicon p-type Inversion Layers, J. Appl. Phys., 39:1923-1931 (1968).
3. J. R. Haynes and W. Shockley, The Mobility and Life of Injected Holes and Electrons
in Germanium, Phys. Rev., 81:835-843 (1951).
148 Semiconductor Measurements and Instrumentation

4. J. P. McKelvey, Diffusion Effects in Drift Mobility Measurements in Semiconductors,

J. Appl. Phys., 27:341-343 (1956).
5. A. Many, Measurement of Minority Carrier Lifetime and Contact Injection Ratio on
Transistor Materials, Proc. Phys. Soc. London, 867:9-17 (1954).
6. R. Lawrance and A. F. Gibson, The Measurement of Drift Mobility in Semiconductors,
Proc. Phys. Soc. London, 865:994-995 (1952).
7. M. B. Prince, Drift Mobilities in Semiconductors, I Germanium, Phys, Rev., 92:681-687
(1953).
8. W. Shockley, "Electrons and Holes in Semiconductors," D. Van Nostrand Company,
Inc., Englewood Cliffs, N.J., 1950.
9. H. Y. Fan, Effect of Traps on Carrier Injection in Semiconductors, Phys. Rev.,
92:1424-1428 (1953).
10. R. Lawrance, The Temperature Dependence of Drift Mobility in Germanium, Phys.
Rev., 89: 1295 (1953).
11. J. R. Haynes and W. C. Westphal, The Drift Mobility of Electrons in Silicon, Phys.
Rev., 85:680 (1952).
12. C. B. Norris, Jr., and J. F. Gibbons, Measurement of High-Field Carrier Drift Velocities
in Silicon by a Time-of-Flight Technique, IEEE Trans. Electron Devices, ED-14:38-43
(1967); A. G. R. Evans, and P. N. Robson, Drift Mobility Measurements in Thin
Epitaxial Semi-conductor Layers Using Time-of-Flight Techniques, Solid-State Elec-
tron., 17:805-812 (1974).
13. C. Canali, G. Ottaviani, and A. Alberigi Quaranta, Drift Velocity of Electrons and Holes
and Associated Anistropic Effects in Silicon, J. Phys. Chern. Solids, 32: 1707-1720 (1971);
and references contained therein.
14. P. A. Tove, G. Andersson, G. Ericsson, and R. Lidholt, Measurement of Drift Velocity
of Electrons in Silicon by Exciting a Diode Structure with Short Superradiant Laser
Pulses, IEEE Trans. Electron Devices, ED-17:407-412 (1970).
15. W. E. Spear and J. Mort, Electron and Hole Transport in CdS Crystals. Proc. Phys.
Soc. London, 6: 130-140 (1963).
16. E. H. Pudey, "The Hall Effect and Semiconductor Physics," Butterworth & Co. (Pub-
lishers), Ltd., London, 1960; Dover Publications, Inc., New York, 1968.
17. Albert C. Beer, "Galvanomagnetic Effects in Semiconductors," Academic Press, Inc.,
New York, 1963.
18. L. P. Hunter, Graphical Representation of the Semiconductor Hall Effect, Phys. Rev.,
94:1157-1160 (1954).
19. W. C. Dunlap, Jr., Some Properties of High Resistivity p-Type Germanium, Phys. Rev.,
79:286-292 (1950).
20. Rolf Landauer and John Swanson, Diffusion Currents in the Semiconductor Hall Effect,
Phys. Rev., 91 :555-560 (1953).
21. L. Hunter, E. HuIbregtse, and R. Anderson, Current Carrier Lifetimes Deduced from
Hall Coefficient and Resistivity Measurements, Phys. Rev., 91: 1315-1320 (1953).
22. P. C. Banbury, H. K. Kenisch, and A. Many, On the Theory of the Isothermal Hall
Effect in Semiconductors, Proc. Phys. Soc. London, A66:753-758 (1953).
23. G. L. Pearson and J. Bardeen, Electrical Properties of Pure Silicon and Silicon Alloys
Containing Boron and Phosphorus, Phys. Rev., 75:865-883 (1949).
24. P. A. Lee, Determination of the Impurity Concentrations in a Semiconductor from Hall
Coefficient Measurements, Brit. J. Appl. Phys., 8:340-343 (1957).
25. Claude A. Klein and W. Deter Straub, The Hall Effect as an Analytical Tool in Ultrapure
Silicon and Germanium, in Marvin S. Brooks and John K. Kennedy (eds.), "Ultra-
purification of Semiconductor Materials," The Macmillan Company, New York,
1962.
26. Krzysztof Pigon', A Graphical Method for Determination of Mobility Ratio in the
Semiconductors from Hall Effect Measurements Only, J. Appl. Phys., 32:2369-2371
(1961).
 Mobility, Hall, and Type Measurements 149

27. Olaf Lindberg, Hall Effect, Proc. IRE, 40:1414-1419 (1952).

28. B. Lundberg and G. Backstrom, Hall Voltage and Magnetoresistance of Bi Measured
by a Sum Frequency Method in a Belt Apparatus, Rev. Sci. Instr., 43:872-875 (1972).
29. Richard L. Petritz, Theory of an Experiment for Measuring the Mobility and Density
of Carriers in the Space-Charge Region of a Semiconductor Surface, Phys. Rev.,
110: 1254-1262 (1958).
30. O. N. Tufte, The Average Conductivity and Hall Effect of Diffused Layers on Silicon,
J. Electrochem. Soc., 109:235-238 (1962).
31. I. Hlasnik, Influence of Carrier Concentration Gradients and Mobility Gradients on
Galvanomagnetic Effects in Semiconductors, Solid State Electron., 8:461-466 (1965).
32. Williams Johnson, Numerical Corrections for Hall Effect Measurements in Silicon
Containing Gaussian Dopant Distributions, Solid State Electron., 13:951-956 (1970).
33. V. K. Subashchiev, and S. A. Poltinnikov, Determination of Carrier Mobility and
Density in the Surface Layer of a Semiconductor, Soviet Phys. Solid State, 2:lO59-lO66
(1960).
34. H. J. Juretschke, R. Landauer, and J. A. Swanson, Hall Effect and Conductivity in
Porous Media, J. Appl. Phys., 27:838 (1956); Moni G. Mathew and Kenneth S. Mendel-
son, Hall Effect in the "Composite Sphere" Material, J. Appl. Phys., 45:4370-4372
(1974).
35. Conyers Herring, Effect of Random Inhomogeneities on Electrical and Galvanomag-
netic Measurements, J. Appl. Phys., 31:1939-1953 (1960).
36. I. Isenberg, B. R. Russell, and R. F. Greene, Improved Method for Measuring Hall
Coefficients, Rev. Sci. Instr., 19:685-688 (1948).
37. J. Volger, Note on the Hall Potential across an Inhomogeneous Conductor, Phys. Rev.,
79:1023-lO24 (L) (1950).
38. R. F. Wick, Solution of the Field Problem of the Germanium Gyrator, J. Appl. Phys.,
25:741-756 (1954).
39. V. Frank, On the Geometrical Arrangement in Hall Effect Measurements, Appl. Sci.
Res., 83:129-140 (1953).
40. L. J. van der Pauw, A Method of Measuring Specific Resistivity and Hall Effect of
Discs of Arbitrary Shape, Philips Res. Repts., 13:1-9 (1958).
4l. L. J. van der Pauw, A Method of Measuring the Resistivity and Hall Coefficient on
Lamellae of Arbitrary Shape, Philips Tech. Rev., 20:220-224 (1959).
42. M. G. Buehler and G. L. Pearson, Magnetoconductive Correction Factors for an
Isotropic Hall Plate with Point Sources, Solid State Electron., 7:395-407 (1966).
43. M. G. Buehler, A Hall Four-Point Probe on Thin Plates, Solid State Electron., 10:801-
812 (1967).
44. M. A. Green and M. W. Gunn, Four-Point Probe Hall Effect and Resistivity Measure-
ments upon Semiconductors, Solid State Electron., 15:577-585 (1972).
45. Julius Lange, Method for Hall Mobility and Resistivity Measurements on Thin Layers,
J. Appl. Phys., 35:2659-2664 (1964).
46. H. C. Montgomery, Electrical Noise in Semiconductors, Bell System Tech. J., 31 :950-975
(1952).
47. Francis L. Lummis and Richard L. Petritz, Noise, Time Constant, and Hall Studies
on Lead Sulfide Photoconductive Films, Phys. Rev., 105:502-508 (1957).
48. G. L. Guthrie, Sensitive AC Hall Effect Circuit, Rev. Sci. Instr., 36:1177-1179 (1965).
49. C. C. Allen and E. G. Bylander, Evaluation Techniques for and Electrical Properties
of Silicon Epitaxial Films, in John B. Schroeder (ed.), "Metallurgy of Semiconductor
Materials," Interscience Publishers, Inc., New York, 1962.
50. W. J. Patrick, Measurement of Resistivity and Mobility in Silicon Epitaxial Layers on
a Control Wafer, Solid State Electron., 9:203-211 (1966).
51. A. B. M. Elliot and J. C. Anderson, An Investigation of Carrier Transport in Thin
Silicon-on-Sapphire Films Using MIS Deep Depletion Hall Effect Structures, Solid State
Electron., 15:531-545 (1972).
150 Semiconductor Measurements and Instrumentatian

52. D. Colman and Don L. Kendall, Effect of Surface Treatments on Silicon Hall Measure-
ments, J. Appl. Phys., 40:4462-4463 (1969).
53. W. F. Flanagan, P. A. Flinn, and B. L. Averbach, Shorting and Field Corrections in
Hall Measurements, Rev. Sci. Instr., 25:593-595 (1954).
54. J. Dresner, The Photo-Hall Effect in Vitreous Selenium, J. Phys. Chern. Solids, 25:505-
511 (1964).
55. Sol E. Harrison, George H. Heilman, and George Warfield, Measurement of the Hall
Effect in Metal-Free Phthalocyanine Crystals, Phys. Rev. Lett., 8:309-311 (1962).
56. Derek Colman, High Resistivity Hall Effect Measurements, Rev. Sci. Instr., 39: 1946-
1948 (1968).
57. G. Fischer, D. Greig, and E. Mooser, Apparatus for the Measurement of Galvano-
magnetic Effects in High Resistance Semiconductors, Rev. Sci. Instr., 32:842-846 (1961).
58. R. C. Eden and W. H. Zakrzewski, Semiautomatic Hall Effect Measurement System,
Rev. Sci. Instr., 41:1030-1033 (1970).
59. J. Shewchun, K. M. Ghanekar, R. Yager, H. D. Barber, and D. Thompson, A Computer
Controlled Automatic System for Measuring the Conductivity and Hall Effect in
Semiconducting Samples, Rev. Sci. Instr., 42:1797-1807 (1971).
60. W. Bullis, W. R. Thurber, T. N. Pyke, Jr., F. H. Ulmer, and A. L. Koenig, "Use of
a Time-shared Computer System to Control a Hall Effect Experiment," National Bureau
of Standards, Tech. Note 510, 1969.
61. Alpheus W. Smith, The Hall Effect in Bismuth with High Frequency Currents, Phys.
Rev., 35:81-85 (1912).
62. J. J. Donoghue and W. P. Eatherly, A New Method for Precision Measurement of the
Hall and Magneto-resistive Coefficients, Rev. Sci. Instr., 22:513-516 (1951).
63. S. W. Kurnick and R. L. Fitzpatrick, Galvanomagnetic Measurement in Highly Con-
ducting Semiconductors, Rev. Sci. Instr., 32:452-453 (1961).
64. Eugene E. Olson and John E. Wertz, A High Impedance AC Hall Effect Apparatus,
Rev. Sci. Instr., 41 :419-421 (1970).
65. J. Ross Macdonald, and John E. Robinson, AC Hall and Magnetostrictive Effects in
Photoconducting Alkali Halides, Phys. Rev., 95:44-50 (1954).
66. Jerome M. Lavine, Alternate Current Apparatus for Measuring the Ordinary Hall
Coefficient of Ferromagnetic Metals and Semiconductors, Rev. Sci. Instr., 29:970-976
(1958).
67. P. E. Bierstedt and J. E. Hanlon, Apparatus for Measuring the Normal Hall Coefficient
in Magnetic Conductors, Rev. Sci. Instr., 42:1674-1976 (1971).
68. T. M. Dauphinee and E. Mooser, Apparatus for Measuring Resistivity and Hall Co-
efficient of Semiconductors, Rev. Sci. Instr., 26:660-664 (1955).
69. L. J. van der Pauw, An Analysis of the Circuit of Dauphinee and Mooser for Measuring
Resistivity and Hall Constant, Rev. Sci. Instr., 31:1189-1192 (1960).
70. H. H. Soonpaa, C. D. Motchenbacher, and H. Dohl, Zero-Point Detector for the
Dauphinee-Mooser Circuit, Rev. Sci. Instr., 34:1341-1344 (1963).
71. F. M. Ryan, Rotating Sample Method for Measuring the Hall Mobility, Rev. Sci. Instr.,
33:76-79 (1962); J. Yahia and G. Perluzzo, A Two Frequency ac Hall Apparatus for
Measurements in Metals, Rev. Sci. Instr., 44:335-337 (1973).
72. A. M. Hermann and J. S. Ham, Apparatus for the Measurement of the Hall Effect
in Semiconductors of Low Mobility and High Resistivity, Rev. Sci. Instr., 36:1553-1555
(1965).
73. Robert G. PoW, Hall Effect Measurements in Semiconductor Rings, Rev. Sci. Instr.,
30:783-786 (1959).
74. J.-P. Jan, Galvanomagnetic and Thermomagnetic Effects in Metals, in Frederick Seitz
and David Turnbull (eds.), "Solid State Physics," vol. 5, Academic Press, Inc., New
York, 1957.
75. B. R. Russell and C. WaWig, A New Method for the Measurement of Hall Coefficients,
Rev. Sci. [nstr., 21:1028-1029 (1950).
 Mobility, Hall, and Type Measurements 151

76. E. M. Pell and R. L. Sproull, Sensitive Recording Alternating Current Hall Effect
Apparatus, Rev. Sci. Instr., 23:548-552 (1952).
77. H. Rzewuski and Z. Werner, New Double Frequency Method for Hall Coefficient
Measurements, Rev. Sci. Instr., 36:235-236 (1965).
78. John L. Levy, Sensitive Hall Measurements on NaCl and on Photoconductive PbTe,
Phys. Rev., 92:215-218 (1953).
79. N. Z. Lupa, N. M. Tallan, and D. S. Tannhauser, Apparatus for Measuring the Hall
Effect of Low-Mobility Samples at High Temperatures, Rev. Sci. Instr., 38:1658-1661
(1967).
80. Des Coudres, Phys. Z., 2:586 (1901).
81. Rudolf G. Suchannek, Effect of Intermodulation of Measurement of Small Hall Co-
efficients with Double AC Method, Rev. Sci. Instr., 37:58a-59x (1966).
82. H. L. McKinzie and D. S. Tannhauser, Systematic Errors in Alternating Current Hall
Effect Measurement, J. Appl. Phys., 40:4954-4958 (1969).
83. G. P. Carver, A Corbino Disc Apparatus to Measure Hall Mobilities in Amorphous
Semiconductors, Rev. Sci. Instr., 43:1257-1263 (1972).
84. P. W. Shackle, Measurement of the Hall Coefficient in Liquid Metals by the Corbino
Method, Phil. Mag., 21 :987-1002 (1970).
85. N. E. Cusack, J. E. Ederby, P. W. Kendall, and Y. Tieche, The Measurement of the
Hall Coefficient of Liquid Conductors, J. Sci. Instr., 42:256-259 (1965).
86. Harold E. MacDonald, and Richard H. Bube, Apparatus for Measuring the Temperature
Dependence of Photo-Hall Effects in High-Resistivity Photoconductors, Rev. Sci. Instr.,
33:721-723 (1962).
87. I. Eisele and L. Kevan, Double Modulation Method for Hall Effect Measurements on
Photoconducting Materials, Rev. Sci. Instr., 43: 189-194 (1972). (See also other refer-
ences contained therein.)
88. E. Muller and D. K. Ferry, Hall Studies of Instabilities Occurring in Impact Ionization
of N-type Indium Antimonide, J. Phys. Chern. Solids, 31:2401-2404 (1970).
89. Y. Nishina and G. C. Danielson, Microwave Measurement of Hall Mobility: Experi-
mental Method, Rev. Sci. Instr., 32:790-793 (1961).
90. G. Knight, Jr., Measurement of Semiconductor Parameters, in L. P. Hunter (ed.),
"Handbook of Semiconductor Electronics," McGraw-Hill Book Company, New York,
1956.
91. W. A. Keenan, C. P. Schneider, and C. A. Pillus, Type-All System for Determining
Semiconductor Conductivity Type, Solid State Tech., 14:51-56 (March 1971).
92. Hakan Hakansson, Conductivity Type Determination for Different Semiconductor
Materials, Rev. Sci. Instr., 43:1380-1381 (1972).
93. Standard Method F 42-69, "ASTM Book of Standards," Part 8, American Society for
Testing and Materials, Philadelphia, 1971.
94. K. B. Wolfstirn and M. W. Focht, Thermoelectric n-p Tester Using AC Bias for Gallium
Arsenide and Gallium Phosphide, Rev. Sci. Instr., 42:152-154 (1971).
95. F. P. Heiman, K. H. Zaininger, and G. Warfield, Determination of Conductivity Type
from MOS-Capacitance Measurements, Proc. IEEE, 52:863-864 (1964).
96. Lowell E. Clark, Determination of Conductivity Type from Capacitance Measurements
on MOS Diodes, IEEE Trans. Electron Devices, ED-12:390-391 (1965).
97. V. M. Cottles and A. M. Hermann, Hall Probe Loop for Nulling Induced Voltages from
a.c. Magnetic Fields, Rev. Sci. Instr., 44:334 (1973).
98. C. M. Wolfe, G. E. Stillman, and J. A. Rossi, High Apparent Mobility in Inhomogeneous
Semiconductors, J. Electrochem. Soc., 119:250-255 (1972).
99. R. D. Westbrook, Effect of Semiconductor Inhomogeneities on Carrier Mobilities by
the van der Pauw Method, J. Electrochern. Soc., 121 :1212-1215 (1974).
100. L. Gutai, Determination of Galvanomagnetic Coefficients by a One-Point Method,
Solid-State Electron., 16:395-406(1973).
 6
Thickness Measurements

6.1 INTRODUCTION

Thickness measurements can be broken into three general categories involving

(1) the total thickness of a slice or block of semiconductor, (2) the thickness of
variously doped regions within the semiconductor, (3) the thickness of external layers
of foreign material such as dielectric or metal films deposited on the semiconductor
surface. Total thickness may be measured by conventional machine-tool-industry
equipment if care is taken not to damage the surface excessively. Semiconductor
and dielectric layers are most often measured by optical methods. For the plan view
of Fig. 6.la, measurements will depend on the optical constants of each layer being
different from the others. If it is viewed on edge, as in Fig. 6.lh, or if the wedge
of Fig. 6.lc is of very low angle, the problem becomes one of delineating the
boundaries and then making lateral measurements. Various stains or etchants are
often used to improve contrast. When steps such as those in Fig. 6.ld are available,
optical methods are sometimes abandoned in favor of purely mechanical profilome-
ters which may be drawn across the surface to indicate the step. These same methods
may be used for metal layers, but for them a variety of instruments which depend
on electrical conductivity are also available.
Tables 6.1 and 6.2 summarize various possibilities and can be used as a guide
in choosing the proper method. Table 6.3 gives conversion factors between some
of the more common units of thickness. They are by no means metric standards
but do conform to the useful philosophy of providing units that will allow most
dimensions to be expressed in numbers between 1 and 10.

(0) ( b) (c) (d)

Fig. 6.1. Various views of a layered structure.

153
1S4 Semiconductor Measurements and Instrumentation

Table 6.1. Methods of Measuring Thickness

Method Applicable to Advantages

Mechanical micrometer Slices, dice, Hall bars, etc. Simplicity

Electrical micrometer Slices, dice, Hall bars Less likely to produce damage
Air gage Slices, dice, Hall bars Does not produce damage
Absorption Slices, dice, etc., silicon on Nondestructive, not sensitive
sapphire to particles on surface
Ellipsometry Epitaxial layers, oxide, Nondestructive, rapid
nitride, or other dielectric
layers on semiconductor
surface
Interferometry Epitaxial layers, oxide, Nondestructive, rapid
nitride, or other dielectric
layers on semiconductor
surface
Interferometry + lap and Epitaxial layers, diffused Convenience, wide application
stain layers
Interferometry + step Metal over oxide, oxide
over semiconductor
Light section + step Metal over oxide over Simplicity
semiconductor
Mechanical profilometer + step Metal over oxide over Simplicity
semiconductor
High-power microscope + step Metal over oxide over Availability
semiconductor
High-power microscope + Transparent layer of known Availability
visible boundaries refractive index
Weight differential Deposited layers
Eddy current Metal layer
Beta-ray backscattering Metal layer
X-ray fluorescence Thin metal films Nondestructive, very local
Crystallographic defects Epitaxial layers Nondestructive
Device performance Base and collector widths Can be used on completed
devices
Capacitance bridge Low-loss materials of known Noncontacting
dielectric constants

6.2 MICROMETERS AND OTHER GAGES

Conventional hand-held micrometers are available which will read directly to the
nearest thousandth inch, and with vernier will read to 0.0001 in. Such tools are
therefore suitable for measuring slice thickness, although they have several disad-
vantages. The two major ones are the likelihood of fracturing brittle slices and the
fact that the anvils are usually approximately %in in diameter so that dust and/or
grit may add to the measured thickness. The addition of ball anvils will minimize
the particle problem, but the smaller contact area increases the chance of mechanical
damage.
A better choice is a dial-gage indicator mounted over a flat work surface which
has a small spherical protrusion directly below the indicator, as shown in Fig. 6.2.
Only the spherical tip rises above the work surface a few mils, so that for slices
of reasonable size the error because the slice is not perpendicular to the instrument
centerline is negligible. Dial indicators use a gear train for magnification and are
spring-loaded. However, this loading is usually less than that exerted by a hand
 Thickness Measurements 155

Table 6.2. Guide to Applicable Methods

Problem Possible approaches

epi on n+ Infrared spectrophotometer*

epi on p+ Angle lap and stain, stacking-fault dimensions'
Very thin epi Infrared ellipsometer; angle lap and stain; overcoat on
material of different index of refraction, plus visible spec-
trophotometer
Very thin Si epi on sapphire or Visible spectrophotometer, visible-light absorption
similar substrate
Oxide layer Color chart; ellipsometer; visible spectrophotometer;
VAMFO; etched step plus profilometer or microscope;
interferometer
Nitride layer Color chart; ellipsometer; visible spectrophotometer;
VAMFO; etched step plus profilometer or microscope;
interferometer
Nitride over oxide Ellipsometer, plus program for computing double-layer
thickness
Metal layer Angle lap, etched step plus profilometer or interferometer,
beta-ray gage, eddy-current gage
Transistor base width Angle lap and stain, base transit time
Collector width Angle lap and stain, breakdown voltage (applicable only
over certain combinations of resistivity, base width, and
collector width)

*l\pplies to both epi on n+ and epi on p+.

micrometer. Alternatives include electronic, optical, and air gages. Some electronic
instruments have a stylus coupled to the movable core of a differential transformer
(Fig. 6.3). Very small displacements can be readily measured, and because of the
small size of the armature and stylus, quite light loading is possible. Others use
the slice to vary the gap between plates and relate the capacitance change to
thickness. 1 Optical gages contact the surface with a stem much like a dial indicator,
but use an opticallever for magnification. The air gage is shown schematically in

Table 6.3. Thickness Conversion Factors

0.1 mil = 100 /Lin

2. 54 /Lm
25,400 A
9.3 Hg lines (5,460 A)
8.6 Na lines (5,896, 5,890 A)
1 /Lm = 0.04 mil
= 1O,OOOA
= 3.66 Hg lines
= 3.39 Na lines
1 Hg line = 0.011 mil
= 0.27 /Lffi
= 2,700 A
= 0.9 Na lines
1 Na line = 0.012 mil
= 0.29/Lm
= 2,900 A
= 1.06 Hg lines
156 Semiconductor Measurements and Instrumentation

Fig. 6.2. Use of a dial indicator for measuring slice

thickness.

Fig. 6.4. The back pressure caused by the variable spacing between a gas jet and
a fiat surface is sensed. Thus, if samples are inserted between the jet and reference
(Fig. 6.4a), the distance between the jet and the slice surface can be measured.
Should the slice be bowed upward as in Fig. 6.4b, a false reading will be obtained;
so for slice measurements it is customary to use two opposing jets as shown in Fig.
6.4c. However, the air-gage jets should be turned off before thin slices are slipped
between them to reduce the likelihood of breakage. When electronic or air gages
are used on very sensitive scales, the total range is normally quite small (e.g., 0.3 mil
for a 0.005-mil-per-division gage); so reference blocks will be required for zero
setting. Because of the great sensitivity of these instruments, they were sometimes
used in the early days of silicon epitaxy for layer-thickness measurements. 1 This
involved keeping track of individual slices and making measurements before and
after growth, as well as minimizing growth on the back of the slice. Such applications
have now been superseded by more elegant and more practical methods such as
infrared interferometry.
Should slices be slightly tapered, the location of the measurements must be
standardized if comparisons between, for example, the manufacturer and the user
are to be made. One procedure suggests a center measurement and four additional
ones Ys in from the circumference. 2 If the slice has a fiat, it is labeled 6 o'clock,
and the readings are taken at the 2, 4, 8, and 10 o'clock positions.

6.3 ABSORPTION METHODS

The reduction in intensity of a plane wave passing through a material is given

by
(6.1)

Voltmeter

To stylus

Fig. 6.3. Use of a differential transformer to measure me-

chanical displacement. Such instruments can be designed to
measure step heights of only a few hundred angstroms.
 Thickness Measurements 157

Orifice ~
r,:::::::::==:::;;::::::::=== ~ ~
Gage Zero set

Differential
pressure

Yl~
Orifice orific;1
Sample

Reference surface ~
(0)

Fig. 6.4. Air gage for measuring

slice thickness. (c)

where 10 is the original intensity, 1 the value after passing through a thickness t,
and a the absorption coefficient. If the sample has an appreciable reflection co-
efficient R, the basic equation above must be modified to

1 = loe-at(l - R)2
(6.2)
1 - R2 e-2at

Therefore, if a and R are known for a given radiation, a measurement of 1 and

10 allows the thickness t to be calculated. Depending on whether x-ray, /3-ray,
infrared, or visible light is used, the absorption coefficient will vary over many orders
of magnitude. Some, such as x-rays, and light of wavelength larger than the band-
edge wavelength, are appropriate for thicknesses of millimeters to centimeters. X-ray
measurements have been used3 for germanium wafers but for most applications have
no advantages and the disadvantage of expensive and specialized equipment. Long
wavelengths (greater than l.l ,um in the case of silicon) have absorption coefficients
that depend on the impurity level. Because of this, thickness measurements cannot
be independently made. For short wavelengths, a is relatively independent of
impurity concentration. Thus, for thin layers either self-supporting or on transparent
substrates, e.g., Si on sapphire, short-wavelength light might be used, and even if
the absorption coefficient is in the 105 to 106 per centimeter range, there will be
sufficient transmission for satisfactory measurements. Visible-light absorption can be
used for estimating the thickness of very thin metal films. Most films (e.g., Pt,
Au, and AI) will have transmissions in the 20 to 80 percent range when they are
a few hundred angstroms thick. 4
Should the absorption coefficient be so low that exp( -at) at t = ;\/4 is greater
than perhaps 0.1, the thickness will be a multivalued function of transmission, and
interferometry rather than absorption should be used. An additional complication
that must be considered is the fact that some films (e.g., Ag) have such a marked
change in optical constants in the 50- to 2oo-A-thick region that a peak in the
absorption-thickness curve may arise and two thickness values can correspond to
158 Semiconductor Measurements and Instrumentation

a single value of transmission.4 If an absorption band is present, operating at its

wavelength can substantially increase a and thus effectively increase the sensitivity
in the very thin layers. Similarly, it can be used to minimize interference effects
in thicker layers. The 9- and l2-,um bands in Si0 2 have, for example, been used
to measure the thickness of Si0 2 films on silicon. 5
A spectrophotometer is not necessarily required for either visible or infrared
absorption measurements. It is, for example, possible to use a laser light source
instead of a monochrometer, a simple converging lens for the optical system, and
a photodiode for detection. 6 In some systems, even the monochromatic laser light
is dispensed with in favor of a broad-band incandescent source. Simple densitome-
ters can in fact be used for many measurements. An intermediate range of com-
plexity uses the broad-band source and an interference filter, although for some
infrared ranges the latter are not readily available. There are /3-ray instruments
that will work with reasonable success in the millimeter and less range for many
semiconductors but have not been widely used.

6.4 ELLIPSOMETRy7-30

Ellipsometry is most applicable to the thickness measurement* of thin films of

a dielectric on a highly absorbing substrate when viewed as in Fig. 6.la. The general
principles have been known since before 1900, although the name itself is relatively
new (1944).13,14 Because of the complexity of interpretation, however, the ellipsome-
ter has until recently been used only for very specialized applications. The present
availability of high-speed computers makes the equations much easier to deal with,
either by allowing many curves covering a wide variety of circumstances to be readily
generated, or by coupling the ellipsometer directly into a computer.
General Theory. After light is reflected from a single surface, it will normally
be reduced in amplitude and shifted in phase. If multiple reflecting surfaces are
involved, as in Fig. 6.5, the various reflected beams will further interact and, depend-
ing on relative amplitudes, path differences between the surfaces, and phase shifts
at the surfaces, give maxima and minima of intensity (interference effects) ~s a
function of either wavelength and/or spatial position. Should the incident light have

*ElJipsometry is also useful for measuring the optical constants of either the substrate or the layer.

Fig. 6.5. Multiple reflections from a layered structure.

 Thickness Measurements 1 59

been plane-polarized (which may be resolved into a component p parallel to the

plane of incidence and a component s perpendicular to the plane) before impinging
on a surface (Fig. 6.6), the two components will usually experience different amounts
of phase shift upon reflection and have different reflection coefficients. This phase-
shift difference introduces an additional component polarized 90° to the incident
beam and thus produces elliptically polarized light as in Fig. 6.6c. Projected onto
a plane perpendicular to the reflected ray, the resultant E vector of the elliptical
light will trace out an ellipse (hence the term elliptical).
Both polarization and interference changes are now widely used to determine
various properties of the materials between the reflecting surfaces and give rise to
the distinctively different techniques of ellipsometry and interferometry. The former
is most widely applied to the study of very thin «one wavelength) layers on thick
substrates. Interference effects, which are the subject of the next section, are used
most often for studying layers which are from one-eighth to four or five wavelengths
thick.
The angles ~ and 'I' are the most commonly discussed parameters in ellipsometry
and are
~ = differential phase change = ~p - ~s
(6.3)
'I' = tan- 1 (~:)
where Rp is the reflection coefficient of the p component, Rs is the reflection coefficient
of the s component, and ~p,s are the respective phase shifts introduced during
reflection. If there were no phase shift, only a difference in reflection coefficients,
the light would remain plane-polarized after reflection, but the plane could be
rotated. Thus the change of analyzer angle required to produce extinction after the
sample was introduced would be a measure of (R/ Rs) or '1'. * Similarly, the amount
of phase shift introduced by an additional optical component necessary to compen-
sate for ~p - ~s and again produce linear polarized light is a direct measure of Il.

*-Several conventions have been used in the literature (see, for example, Ref. 15). The reader should
take this into account when attempting to compare various references.

Plane
polarized ~_----'",<!"

I R Elliptically polarized. The two

Incident Normal Reflected
beam beam perpendicular components
differ both in phase and
Lines (ra) and (OR) define the plane of amplitude.
incidence. cp is the angle of incidence.

(a) (b) (c)

Fig. 6.6. Details of polarized light reflection. (a) For plane-wave propagation
the E vector must lie perpendicular to the direction of travel but may have
any orientation in that plane. Usually there will be E vectors with many
different directions. (b) and (c) For purposes of analysis, polarized light is
considered in terms of sand p projections which are in phase but usually differ
in amplitude. Component p lies in the plane of incidence, and component
s is perpendicular to p.
160 Semiconductor Measurements and Instrumentation

Having obtained 'l' and 11 experimentally (as will be described later), the problem
of equating them to film thickness still remains. This can be accomplished by
calculating the reflection coefficients at each interface from Fresnel's equations, the
°
phase shift which the light experiences in traversing the film or films, and com-
bining them to give an overall reflection coefficient and phase shift ('l' and 11). The
film thickness enters the equations only through 0, given by

(6.4)

where t is the film thickness and n its index of refraction. 'l' and 11 repeat for every
change in 0, which is why the requirement arises for an independent evaluation
'IT
of t to within one order. That is, t must be known to within 11./ (n 2 - sin 2 <p )112.
In principle, simple structures as well as multiple films can be analyzed if all but
two of the parameters are known. One may, for example, calculate
1. n, k of a bare substrate (the only case for which an explicit solution IS
available l l)
2. Thickness and n of a layer on top of a substrate of known n, k
3. Thickness and n of either of two layers if the other layer thickness and
refractive index are known, along with n, k of the substrate 7
The first case is useful because, if no published data are available, it allows the
substrate to be easily characterized. Number two is the most common measurement,
but the third one can arise if silicon nitride, for example, is being deposited over
an Si0 2 layer.
The usual procedure for interpreting the data is to presume that the optical
constants of the substrate are known, and then by computer to generate a family
of curves such as those shown in Fig. 6.7 which give the film index of refraction
and thickness as a function of 'l' and 11. These curves can then be used for routine
thickness measurements.* Over most of the range, given values of'l' and 11 uniquely
* Since the instrument angle of incidence and (he wavelength of light (typically but not necessarily
70° and 5,461 A) both enter into the calculation of the curves, be sure to use a set which matches the
instrument.

360

:w
320

280

240

:G
l' 200
0
'"
Q)

<i 160

120

80
Fig. 6.7. 'If, Ll for lossless films on
40 a silicon substrate. The solid lines
are iso-dielectric-constant curves.
0
0 The dotted ones are for constant
Ij! ,Degrees thickness.
 Thickness Measurements 161
360
~/
1.0061.. .....----
320
~./' ~

/'
280
,;-
I
240
!
i
200
II 0
e'"'" 160
o'" \ \

\
<1 120 ,
"'- " "I',
80 , ,,~oo1..
3.0~~~
-
"',\
40 "
v:,) ..+-2.000 A
( 'f:
~,
--" /1 1
)
Fig. 6.S. '1', jj. as a function of thickness for an o
-~
absorbing film on silicon. This particular curve
assumes that the film index of refraction is 120
o 4
'----- 8 12 16 20 24 28
2.2 - i0.22. (After Archer. 10 ) 0/, Degrees

determine nand t. However, very high index curves (e.g" n > 9 on a Si substrate)
may overlap the curves for n very close to 1. Again, some background information
regarding the film must be available to prevent misinterpretation, although the
likelihood of having such index films is rather remote.
If the film is absorbing, 'l' and Ll depend on k as well as nand t, and the 'l',
Ll curve t~kp<; on a much different character, as shown in Fig. 6.8. It now converges
to the values appropriate for the "film" behaving as a substrate (case 1) as the optical
thickness increases, rather than being cyclic. Also, a unique set of properties are
not defined by a set of 'l', Ll readings, since there are now the three unknowns n,
k, and t. This problem can be resolved by taking readings at two different values
of cp,l1 but of course the difficulty of interpretation is considerably increased.
Case 3 and others of similar complexity are best handled by feeding the ellip-
someter angles and other pertinent data into a computer and directly performing
the calculations.
The optical elements required of an ellipsometer to measure the necessary angles
are shown in Fig. 6.9 and include a monochromatic light, polarizer, * quarter-wave
compensator, analyzer, and detector. The two operations of compensation and
determining the amount of rotation are not performed separately, since "complete"

*Polarizers are often referred to as "Nicols." The Nicol polarizer was invented in 1828 and for many
decades was one of the most popular. It has now, however, been largely superseded by other types
such as the Glan-Thomson.

Fig. 6.9. Basic ellipsometer optics.

162 Semiconductor Measurements and Instrumentation

extinction is the only condition that can be conveniently measured, * and it will occur
only when both the necessary compensation has been added and the analyzer
properly set. Thus one of the three polarizing elements (polarizer, quarter-wave
plate, and analyzer) is fixed, and the other two are simultaneously varied until a
null (extinction) is produced. The two most common combinations are:
l. The polarizer fixed at 45 and the compensator and analyzer adjusted for
0

extinction
2. The fast axis of the quarter-wave plate fixed at 45 and the polarizer and 0

analyzer adjusted for extinction

In either case, the quarter-wave plate can be put before or after the sample. With
the second combination, if at extinction the polarizer angle is P and the analyzer
angle is A, aR , as, and p are defined through Table 6.4.
The angular convention usually used is that all azimuthal angles are measured
as positive counterclockwise from the plane of incidence (plane lOR of Fig. 6.6)
when looking into the light beam and that the polarizer angle will be adjusted to
read zero when the plane of transmission is in the plane of incidence. There are
actually several sets of readings that should be equivalent. Sixteen of these arise
when the compensator is set at plus and minus 45 and are customarily grouped 0

into the four zones of Table 6.4. 25 Sixteen more readings are obtained if the com-
pensator is also set at -+-135 in addition to -+-45
0 0
•

When the compensator has exactly 90° retardation,

Ll = 90° + 2p (6.5)
'l' = ap = a.
* By the use of an additional optical element, the operations can be sequentially performed. The two
halves of a biplate placed between the reflecting surface and the analyzer will appear equally bright
when the beam is plane-polarized.

Table 6.4. Relation between A, P, as' ap' and p

Zone Compensator p ap a, P A

I _45 0 p A ap
P
P - 180 0 A P + 180 0 ap
P A - 180 0
P ap + 180 0

P - 180 0 A - 180 0
P + 180 0 ap + 180 0

III _45 0 P _ 90 0 180 0 - A P+ 90 0

180 0
- as
P - 270 0 180 0
- A P+ 270 0
180 0
- as
P _ 90 0 360 0
- A P+ 90 0
360 0
- a.
P - 270 0 360 0
- A P+ 270 0
360 0
- a.
n +45 0
90 0
- P A 90 0
- P a.
270 0
- P A 270 0
- P as
90 0
- P A - 180 0
90 0
- P a, + 180 0

270 0 - P A - 180 0 270 0

- P as + 180 0

IV +45 0
180 0
- P 180 0
- A 180 0
- P 180 0
- as
360 0
- P 180 0
- A 360 0
- P 180 0
- a.
180 0
- P 360 0
- A 180 0
- P 360 0
- ap
360 0
- P 360 0
- A 360 0
- P 360 0
- ap

~ = 90 + 2p,
0
'I' = ap = as.
 Thickness Measurements 163

Should the retardation of the compensator not be exactly 90 0, but rather some
value 8,
tan ~ = sin 8 cot (2p) (6.6)
tan 2 '1' = tan (ap ) tan (as)
However, 8 is usually close enough to 90° that Eq. (6.6) reduces to Eq. (6.5).
In principle only one value each for p and a is necessary, but in practice the
calculated values of p and a will generally be slightly different from zone to zone.
It is experimentally observed that averaging values from the appropriate zones will
minimize the errors. 26 Thus
+ p(zone III) = 2p
p(zone I) (6.7)
and p(zone II) + p(zone IV) = 2p (6.8)
In the case of the a's, ap =f. as from zone to zone unless the compensator is exactly
90°, and in zone 1 ap is read, and in zone III, as' They may be combined, however,
through the expression

(tan a p tan as )1/2 = tan ap +2 as = tan 'I' (6.9)

'I' = ap + as = 180 - Am + AI (6.l0)

2 2
For additional details relating to errors, see Refs. 27 and 28.
With the large number of possibilities listed in Table 6.4, there is a very real
problem in determining for any given set of null conditions which set of relations
should be used.
Since 'I' must always lie between 0 and 90 0, the initial search for extinction should
be made with A restricted to the first quadrant (zone I). This will ensure that A = a,
although there will be two values of P(p and p + 'IT). Next look for extinction with
90° < <
A 180°, i.e., at PI - 90° (zone III). In this case, only A = 180 a will
0
-

be found, although again there will be two values of pep + 90° and p + 270°).
F or the correct set,
(6.l1)
where PI is one of the two P values read in zone I and Pm is one of the two P
values of zone III. Should they not be properly matched,
PI +Pm = p + 180° + P + 90° = ~ + 180° (6.l2)
(6.l3)
In case of either Eq. (6.l2) or (6.l3), the thickness-refractive index combination
determined from ~ and 'I' will be of unreasonable value; so if the instrument is
being used for routine checks, it is simple enough to subtract 180° and redetermine
the thickness. A multiplicity of thickness values (orders) for each correct set of ~,
'I' values are given by tactual = mto + tm, where tm is the measured thickness, m is
the order, and to is the order thickness given in Table 6.5. Note that color orders
and ellipsometer orders do not ordinarily coincide and that the thickness must be
approximately known from some independent means.
Instrumentation. The light source for most instruments is the 5,461-A mercury
164 Semiconductor Measurements and Instrumentation

Table 6.5. Ellipsometer Order Thickness

Index of refraction Thickness multiple

1.4 2,627 A
1.5 2,332 A
1.6 2,105 A
1.7 1,925 A
1.8 1,776 A
1.9 1,650 A
2.0 1,544 A
2.1 1,451 A

70° angle of incidence. 5,461 A wavelength (mer-

cury line).

line, but occasionally a sodium line or a laser is used. The latter has the advantage
of requiring no filtering to separate other lines and no collimating lenses. If layers
other than the common transparent dielectrics are to be studied, other wavelengths
may be more appropriate. For example, if a high-resistivity epitaxial silicon layer
on a low-resistivity substrate is to be measured, wavelengths in the 30- to 100-lim
region are required in order to produce a discernible difference in the optical
properties of the substrate and layer. 16
Quarter-wave compensating plates for use in the visible region are standard optical
components and are made of a birefringent material such as mica, quartz, or calcite,
which have a pronounced difference in velocity for the two components of polariza-
tion. The thickness is adjusted so that the phase difference between the slow and
fast directions is 90° for some particular wavelength. If the difference is not exactly
90°, it can still be used and generally will produce negligible errors.
The detector can be the eye, in which case some aids are necessary, or a photo-
detector such as a photomultiplier. The difficulty with visual detection is that the
eye is not very sensitive to the null condition. Accordingly, to compensate for this,
a Nakamura biplate may be inserted between the reflecting surface and the analyzer.
The two halves of the biplate will appear equally bright when the analyzer is adjusted
for extinction, and the eye can judge equal brightness more accurately than it can
pinpoint the null. With a photodetector several levels of sophistication can be used.
The dc output of the detector, combined with a dark-current-suppression circuit,
can be read directly on a rnicroammeter. For limited accuracy like that required
for reading layer thickness to a few angstroms, the null can be found directly. For
increased accuracy, meter readings can be plotted near and on either side of the
null, and the minimum estimated from the curve. The light may be chopped to
give an ac signal, or the plane of polarization may be modulated before it enters
the analyzerP-19 In the latter case, it can be shown that if the angular sweep of
the modulation is centered about the null, only direct current and a double frequency
will be detected; otherwise odd harmonics will also be present and can be used for
balancing. The procedures for the use of the equipment just described are relatively
simple but nevertheless slow and cumbersome. In order to speed up the data taking,
which may be desirable either because of large numbers of samples or in order to
observe layers as they grow, various modifications have developed. They can gener-
ally be grouped into three categories. One has used high-speed stepping motors
and computer control to perform rapidly the same steps that are required in manual
 Thickness Measurements 165

operation. 16,20 A second incorporates optical elements whose plane of polarization

can be rotated electrically, and then uses analog procedures to balance the system
optically. The currents required to provide the necessary rotation are a measure
of the required angles and can be read as desiredp,21,22 The third depends not
on the classical method of interpretation just described but rather on continuously
rotating the analyzer and measuring the amplitude and phase shift of the ac signal
produced. 23 ,24
Should it be necessary to align the instrument, the following procedure can be
followed:
1. Without the quarter-wave plate in the instrument set both analyzer and
polarizer arms to 90° and align the light source with optics.
2. Set polarizer and analyzer arms to the Brewster angle* of incidence of a
reference reflector, e.g., 57 ° for glass.
3. Remove analyzer or set it so that its plane of transmission is approximately
parallel to the plane of incidence. Rotate the polarizer for minimum inten-
sity. This becomes P _ 0 for the polarizer. Adjust the scale accordingly.
4. Relocate polarizer to 90° incidence angle; adjust analyzer for minimum
transmission. Set analyzer scale at 90°, i.e., A 90°.
5. Set polarizer and analyzer arms to the desired angle of incidence, e.g., 70°;
raise or lower sample stage until light is centered.
6. Insert clean semiconductor slice.
7. Set P at zero; adjust A for minimum. If reading is not 90 0, move A in small
increments and readjust P for minimum until the difference of the two
readings is 90°. Reset indexes to reflect 0 and 90°.
8. Place quarter-wave compensator in beam. With P = 0°, A = 90°, adjust
compensator for extinction. Set compensator index to zero.
9. If zones I and III (Table 6.4) are to be used, rotate compensator to 315°.
Check by taking readings. If the reflective surface is a recently cleaned silicon
slice,
PI ~ 41 ° AI ~ 12°
Pm ~ 131 ° Am ~ 168°
If PI and Pm are approximately 10° higher than these numbers, the com-
pensator was aligned along the slow rather than fast axis.t To correct, rotate
it 90° and redo step 8.

6.5 INTERFERENCE EFFECTS

Background. Interference of rays reflected from two different planes can give rise
to pronounced maxima and minima in intensity. These in tum can be correlated
to the separation of the two planes. Consider first the simplest case of Fig. 6.1Oa
in which there is an isolated film surrounded by air. When the path length through

"The Brewster angle 'PB is the angle of incidence which gives a zero reflection coefficient for the
p component of Fig. 6.6. If the reflecting surface is an air-dielectric interface, 'PB = tan-ln. By setting
the angle at 'PB and then adjusting P for a minimum, the polarizer is aligned with its plane of transmission
coinciding with the plane of incidence, and the position P == 0 is defined.
tThe fast and slow axes can also be determined by following the procedure outlined in J. Strong,
"Procedures in Experimental Physics," p. 388, Prentice-Hall, Inc., Englewood Cliffs, N.J., 1945.
166 Semiconductor Measurements and Instrumentation

I I

Fig. 6.10. Reflections from various combinations of inter~

(c) faces.

the sample (neglecting any phase-shift effects at either interface) corresponds to an

integral number of wavelengths, constructive interference will occur, and for paths
of an odd number of half wavelengths, minima of intensity will occur. Thus the
relation between the thickness t and the wavelength Ao where a particular maxima
or minima occurs is given by
mAo
t= (maxima)
2n cos cf/
(6.14)
or
(m + %)Ao (minima)
t=
2n cos <P'
where m is an integer which becomes progressively smaller as A increases and <P'
is the angle of incidence of the beam as it hits the lower reflecting surface. * In
principle these effects can be observed for very thick samples, but because of imper-
fect collimation of the incident beam, the minima become less pronounced as the
thickness increases, and eventually become indiscernible.
The configuration of Fig. 6.10b is a common one, and could be, for example, a
thin dielectric film on a silicon substrate, or a high resistivity silicon epitaxial layer

*It is also the angle of refraction and is given by sin <I> = n sin <1>'.
 Thickness Measurements 167
Sample

Sample
holder

Lens to correct for

add itional path
length

Fig. 6.1 1. Specular reflection attachment. Sample beam

on a low-resistivity silicon substrate. The equations for interference maxima and

minima are the same as the previous one. However, phase-shift differences between
the two interfaces and a change of reflection coefficient with wavelength may need
to be considered. The configuration of Fig. 6.10c is also likely to arise, and if the
top plate is thick enough, interference between rays 1 and 2 will be negligible, and
only the interference between rays 2 and 3 will be observed. In this case, the
"thickness" measured is that of the air gap, i.e., the separation of the plate and the
surface below.
There are numerous optical arrangements that capitalize on interference effects.
Many of them are directly applicable to thickness measurement, but oddly enough
most interferometers were devised for other purposes and are not necessarily suitable.
Spectrophotometer. By using a specular reflection attachment, shown schemati-
cally in Fig. 6.11, to deflect the spectrophotometer beam up to the reflecting surfaces
and then back again into the instrument, the wavelength can be varied. For a fixed
separation [I of Eq. (6.14) and Fig. 6.10)], the reflected intensity will vary cyclically
as in Fig. 6.12. Equation (6.l4) could be applied to one of the peaks or valleys
of the trace. However, for some randomly chosen peak, m will not be known,
although if the recording starts at a long enough wavelength, the first minimum
and the first maximum will be observed. If the first minimum (m = 0) is recorded,
from Eq. (6.14),

1= A (6.15)
4n cos <P'

1.0 1.0

0.90 0.90

0.80 0.80
V ~
0.7 0--"""'" 0.70

1] 0.60 "\ V \ / "- 0.60

10.50
'"
" ---- / \
/
/ \ 0.50

~ 0.40 \ 0.40

0.30
\ / \ f 0.30

0.20
\ V \J 0.20

0.10 0.10

o
350 360 370 380 390400 425'" 450, III'
475
,, "500""525 550,,,"575600
1111
"" 650""700"'750o
III'

Wavelength, fkm

Fig. 6.12. Reflected intensity of an Si0 2 layer on a Si substrate.

168 Semiconductor Measurements and Instrumentation

For transparent films like oxides, which are usually 2,000 to 10,000 A thick, the con-
ditions ofEq. (6.15) are relatively easy to fulfill and can be used for measurement. 3I
If the film is very thin (e.g., a few hundred angstroms), there will be difficulty in
finding an instrument operating at wavelengths short enough to produce even the
first minimum. Then the ratio of the reflectivity of the substrate with .no film on
it to the reflectivity with a film at some fixed wavelength can be used. It is described
in more detail in the next section.
By extending Eq. (6.15), the expression for additional consecutive peaks is given
as in Eq. (6.16) and has more general application,

mAo
t = ---''---
2n cos CP'

t=
(m + I)AI
--'=------'~
2n cos CP'
(6.16)
t = (m + 2)A2
-'------'~
2n cos CP'

(m + i)Ai
t = --=----:'-
2n cos CP'
where Ai is the wavelength at successive maxima and Ao > Al > A2 . . . . From these
expressions, m is given by
iAi
m = .,---------.,.- (6.17)
Ao - Ai
where i is the number of complete cycles from Ao to Ai. Substituting this value of
m back into Eq. (6.14) gives Eq. (6.18), which can be used directly for calculating
thicknesses,

(6.18)

where i is the number of maxima from Ao to Ai. This expression has the additional
advantage of compensating for any phase-shift differences between the two surfaces
as long as they are independent of wavelength. 2n cos CP' is a combined constant of
the machine being used and the index of refraction of the film. If more convenient,
it can also be expressed in terms of the angle of incidence of the beam onto the
first surface (i.e., the beam angle built into the attachment) and replaced by

2(n 2 _ sin2 cp)1/2

Equations (6.16), (6.17), and (6.18) will work equally well for minima or one maxi-
mum and one minimum as for maxima only. The use of adjacent maximum and
minimum positions is of particular importance if the available chart is reduced in
length because of some instrument problem, or if the thickness-available wavelength
combination is such that only one maximum and minimum is recorded.
These kinds of measurements are widely used both because of the availability
of equipment and because they are nondestructive. They have been used for very
thin silicon and germanium slices34 (the configuration in Fig. 6.10a), for dielectric
films on semiconductor substrates33,37 and for semiconductor epitaxial films. 38 - 41
 Thickness Measurements 169

The fact that most epitaxial-layer thicknesses are measured by spectrophotometer

has led to extensive studies of the effects of phase change and substrate resistivity.
The following paragraphs summarize the various procedures directly applicable to
epitaxial-thickness measurements.
Epitaxial-Film Thickness by Spectrophotometer. 38 - 5o The use ofa spectrophotome-
ter for the specific purpose of measuring epitaxial-film thickness poses several
additional difficulties. The major one is that there is little difference in the refractive
index of the layer and the substrate. This leads to a low-amplitude reflection from
the layer-substrate interface. The index difference becomes more pronounced as
the wavelength increases, so that an idealized interference pattern will increase in
amplitude as shown in Fig. 6.13. The amplitude will also increase as the concen-
tration ofthe substrate increases, provided that the concentration of the layer remains
fixed. Therefore, there are substrate-layer combinations that cannot be measured
this way. For example, ASTM, F 95 71 recommends that for Si, the layer have
a resistivity greater than 0.1 Q-cm and the substrate a resistivity of less than
0.02 Q-cm.
Equation (6.14) was predicated on the same phase shift at the air-layer interface
as at the layer-substrate interface, which is not true for epitaxial layers. Equation
(6.18) assumed that the phase shift, although different, was independent of wave-
length. Unfortunately, this is probably not true either, and based on theoretical
calculations, corrections are usually applied. 44 Such corrections are not required
when measuring epitaxial layers overgrown on insulating substrates, e.g., Si on
sapphire or on polycrystalline layers overgrown on amorphous dielectric substrates
(e.g., Si on Si0 2). The revised equation necessary to include the phase shift Bi is*

t = (m2(n- Yz +sin2B/2'TT)Ai
-'--::-:-;o-'-"'---:--'::-:-:~":"
2 _ </»1/2
(6.19)

If m is allowed to be Yz order, e.g., 2Yz, both maxima and minima are combined
into one equation. The ( - Yz) arises because of the phase-shift term. If B is assumed

*Note that these symbols are different from those in some of the literature. In many cases the order
is designated by P, the number of maxima or minima by m, the angle of incidence bye, and the phase
shift by <p.

100r----------------------------------------,

Ql
-g 80
:'=
Ci
E
o
g 60
'"
"in
~
~ 40
e
i(/) 20

Wavelength. jJ- m

Fig. 6.13. Effect of increasing wavelength on the amplitude of

a silicon epitaxial-layer interference pattern.
170 Semiconductor Measurements and Instrumentation

to be 7T (i.e., a perfect reflection) then Eq. (6.19) reduces to Eq. (6.14). An equation
analogous to Eq. (6.18) but including phase shift can be written which does not
require m to be separately determined [Eq. (6.20)]; however, the ASTM procedure
recommends the use of Eq. (6.19) and m as determined from Eq. (6.21)

t __ iAJ..i [1 - (0 0 - Oi)] (6.20)

2(n2 - sin2 <p)1I2(AO - \) 2i7T

_ i Ao [OJ..o - 0iAi ]
m -
Ao - Ai
+ 1// 2 - 27T(Ao - Ai)
(6.21)

The phase shift has been calculated for a range of substrate resistivities and is
available in tabular form.45
The equations have all been developed by assuming an abrupt interface between
the layer and the substrate. If it is not, then the amplitude of reflection will be
reduced. In fact the reduction can be used as an indication of interface grading.
Figure 6.14 shows reflections from epitaxial slices deposited in a horizontal reactor
at different temperatures and illustrates the effect of grading at the higher deposition
temperature.
Automated Thickness Measurements. The use of spectrophotometer readouts such
as the one shown in Fig. 6.12 has some basic disadvantages. One is that for produc-
tion checking of thousands of slices, the instrument is slow and prone to operator
error. To minimize the operator error and calculation time, tables have long been
used. However, automatic readouts are certainly more desirable. 5o,51 Even that,
however, does not solve the wear problem that is inherent in the linkages and drive
mechanisms used in conventional spectrophotometers. Most instruments were de-
signed for laboratory use and not for continuous operation and hence tend to have
a relatively high repair rate.
Use of a Michelson interferometer as a Fourier-transform spectrophotometer
substantially reduces the number of moving parts and the downtime. 52 Figure 6.15a
shows the basic interferometer. For epitaxial-film measurement it may be coupled
to the sample as in Fig. 6.15b. The output (interferogram) of the interferometer
detector as shown in Fig. 6.15c looks nothing like the conventional spectrometer

':],:~12 14 16 18 20 22 24 26 28 30 32 34
J1-m
Film deposited at 1250°C

'::
12 14 16 18 20 22 24 26 28 30 32 34
J1-m
Film deposited at 1150°C

Fig. 6.14. Effect of a diffused interface on a spectrophotometer trace of a silicon

epitaxial slice.
 Thickness Measurements 171

Source Interferometer

Beamspliiter

?---_ Detector

The Michelson interferometer

(a)
(b)

Unprocessed
interferogram of
reflection fram a
12.5 -I-'m epitaxial
film

o
Phase difference
(c)

(d)

Fig. 6.15. Details of Fourier-transform spectroscopy as used for thickness measure-

ment. (After Cox and Stalder. 52)

trace but can be mathematically manipulated to give comparable information. 53

Since there is only one moving part, the mechanical reliability is greatly enhanced.
The computational complexity, however, has been considerably increased, and the
data must be computer-processed. The data-processing-equipment block diagram
is shown in Fig. 6.15d. With proper instruction the computer can perform phase
shift corrections comparable to those discussed in the previous section.
Specialized Spectrophotometers. In a number of applications a complete spectro-
photometer is either not warranted or undesirable. For example, if the wavelength
is fixed, and reflection from a layer is observed as a function of layer thickness,
the intensity will oscillate as shown in Fig. 6.16. Detailed calculations of reflectivity
of Si0 2 and silicon nitride on a silicon surface for several wavelengths are available
in the literature. 33 ,37 By observing this change in amplitude, film-thickness increase
can be monitored, and indeed such equipment has been used for many years during
172 Semiconductor Measurements and Instrumentation

Fig. 6.16. Intensity variation of monochromatic

reflected light as the layer thickness increases. The
peak-to-valley ratio depends on the relative prop-
Thickness erties of the film and substrate.

dielectric-film deposition. 54 For the special case of silicon in thin layers, e.g., growing
on sapphire, the same approach can be used to measure the silicon as it grows. 55
This is unique in that it is one of the few methods by which epitaxial-layer thickness
can be followed during growth.
These techniques can be used with microscope optics so that very small areas can
be examined. 33 ,56 An ordinary spectrophotometer may require anything from 1 mm 2
to 1 cm2 for observation, while with a high-power metallurgical microscope the
thickness of oxide in a single emitter can be measured. For this application, a
detector such as a silicon photodiode can be coupled to the microscope where a
camera would normally be placed. Either a spot-frequency or a graded-spectrum
interference filter can then be inserted in the optical path and the reflectivity
measured.
Variable-Angle Measurements. 57 Instead of changing the wavelength to produce
the intensity variations of Eq. (6.14), the path length can be changed by choosing
different angles of incidence as shown in Fig. 6.17.* In this case Eq. (6.14) still holds
but Eq. (6.16) must be changed to

t= m"A.
-=-.:..:..::.~-
2n cos cf>o
(m + 1)"A.
t = -=------'--
2n cos cf>~
(6.22)
(m + 2)"A.
t = -'-----
2n cos cf>2

(m + i)"A.
t = -'-----'--
2n cos cf>'i
* See Ref. 4, p. 115.

Fig. 6.17. Principle of variable-angle monochrom-

eter. By varying </>, the path length in the dielectric
is changed until the conditions for interference are
fulfilled.
 Thickness Measurements 173

i cos <1>0
now m =--------~-- (6.23)
cos <1>~ - cos <1>0
and the equation analogous to Eq. (6.19) is

t = i"A. (6.24)
2n(cos <1>i - cos <1>0)
where again i is the number of fringes (bright or dark bands) observed as <1>' is
changed from <1>0 to <1>i. Figure 6.18 shows the optical arrangement of one such
equipment, which has been referred to as VAMFO (variable-angle monochrometer
fringe observation).57 In use, the angle <1> is manually varied and the position of
maxima and/or minima recorded. The thickness can then be calculated from Eq.
(6.24), remembering that <1>' is required in the equation and <1> is measured by the
instrument. Alternately, after the positions of two or three maxima/minima have
been recorded, they can be plotted on a slip of paper and slid along a set of previously
calculated curves until the points match. Different curves are required for materials
with differing refractive indices. For other simplifying approaches, see Ref. 57.
Visual Determination. When thin transparent layers are viewed either directly
by eye or through a microscope, interference effects will give the layer a characteristic
color which depends on the film thickness, its index of refraction, and the spectral
distribution of the viewing light. The latter is a very important point, because for
the same thickness, colors viewed under normal laboratory fluorescent lighting and
under an incandescent-lighte~ metallurgical microscope will be appreciably different.
If calibrated color charts are prepared, these interference effects can be accurate
to within 100 to 200 A. Such charts are widely used to evaluate silicon oxide and
nitride thickness. The chart can be descriptive words vs. thickness, as in Tables 6.6
and 6.7 for Si0 2 and Si3N 4 , printed or photographed colors vs. thickness, or a range
of actual samples mounted in such a way that the unknown can be placed beside
it for comparison. The latter is, of course, by far the most satisfactory, since printing
or photography does not give accurate color rendition and words are even worse.
When preparing the reference samples, an ellipsometer or spectrophotometer can
be used to measure their thickness. One potential source of difficulty is the fact
that different orders have substantially the same colors; so if other information does
not allow the thickness to be independently estimated to within one order, a gross
error could be made. By careful attention to the exact shades it is in principle
possible to tell the order directly, but this approach is not recommended for the
occasional observer. However, if the unknown and the reference are viewed at angles
other than normal, colors will not match unless they are both of the same order.
When viewed at an angle of incidence (J,
to
t=--
cos (J

~ t ~c,oscope
Fig. 6.18. Optical path for VAMFO. Properly situated,
the fixed mirror-fluorescent bulb combination will provide
Fluorescent
bulb
JD:
I 2:J
cp I
Monochromatic
filte,
lighting independently of the position of the sample. Oth-
erwise it must be adjusted periodically. (After Pliskin and
Mir~~1
-0',\ '- Rotating
sample
Sample mount
Conrad. 57 )
174 Semiconductor Measurements and Instrumentation

Table 6.6. Color Chart for Thermally Grown Si0 2 Films Observed Perpendicularly under
Daylight Fluorescent Lighting

Film Film
thickness, pm Color and comments thickness, pm Color and comments

0.05 Tan 0.63 Violet-red

0.07 Brown 0.68 "Bluish" (Not blue but borderline
0.10 Dark violet to red-violet between violet and blue-green.
0.12 Royal blue It appears more like a mixture
0.15 Light blue to metallic blue between violet-red and blue-green
0.17 Metallic to very light yellow- and looks grayish)
green 0.72 Blue-green to green (quite broad)
0.20 Light gold or yellow-slightly 0.77 "Yellowish"
metallic 0.80 Orange (rather broad for orange)
0.22 Gold with slight yellow-orange 0.82 Salmon
0.25 Orange to melon 0.85 Dull, light red-violet
0.27 Red-violet 0.86 Violet
0.30 Blue to violet-blue 0.87 Blue-violet
0.31 Blue 0.89 Blue
0.32 Blue to blue-green 0.92 Blue-green
0.34 Light green 0.95 Dull yellow-green
0.35 Green to yellow-green 0.97 Yellow to "yellowish"
0.36 Yellow-green 0.99 Orange
0.37 Green-yellow 1.00 Carnation pink
0.39 Yellow 1.02 Violet-red
0.41 Light orange 1.05 Red-violet
0.42 Carnation pink 1.06 Violet
0.44 Violet-red 1.07 Blue-violet
0.46 Red-violet 1.10 Green
0.47 Violet 1.11 Yellow-green
0.48 Blue-violet 1.12 Green
0.49 Blue 1.18 Violet
0.50 Blue-green 1.19 Red-violet
0.52 Green (broad) 1.21 Violet-red
0.54 Yellow-green 1.24 Carnation pink to salmon
0.56 Green-yellow 1.25 Orange
0.57 Yellow to "yellowish" (not yellow 1.28 "Yellowish"
but is in the position where 1.32 Sky blue to green-blue
yellow is to be expected. At 1.40 Orange
times it appears to be light 1.45 Violet
creamy gray or metallic) 1.46 Blue-violet
0.58 Light orange or yellow to pink 1.50 Blue
borderline 1.54 Dull yellow-green
0.60 Carnation pink

After Pliskin and Conrad. 57

where to is the thickness read from the color chart. The charts may also be used
for materials other than the ones for which they were originally intendedP In that
case,
tijno
t=--
n,
where no is the index of refraction of the original film and n, that of the new film.
 Thickness Measurements 175

Table 6.7. Color Chart for Si 3 N 4 • Tungsten

Filament Vertical Illumination and Observation
through Low-Power Microscope

Si3N 4 thickness
Order Si3N4 color range JL

Silicon 0-0.020
Brown 0.020-0.040
Golden brown 0.040-0.055
Red 0.055-'0.073
Deep blue 0.073-0.077
1st Blue 0.077-0.093
Pale blue 0.093-0.10
Very pale blue 0.10-0.11
Silicon 0.11-0.12
Light yellow 0.12-0.13
Yellow 0.13-0.15
Orange-red 0.15-0.18
1st Red 0.18-0.19
Dark red 0.19-0.21
2d Blue 0.21-0.23
Blue-green 0.23-0.25
Light green 0.25-0.28
Orange-yellow 0.28-0.30
2d Red 0.30-0.33

From F. Reizman and W. Van Gelder, Solid State

Electron., 10:625-632 (1967).

6.6 BEVEL MEASUREMENTS BY INTERFEROMETRY AND OTHER METHODS

Interferometry. If the sample has been beveled as shown in Fig. 6.19 to expose
some underlying feature, e.g., a stained junction, a partially reflecting reference plane
extending out over the incline from the original surface will produce interference
fringes between the incline and the reference. 58 The fringe spacing will be very close;

Monochromatic light

llll~
t---------------~~
Fig. 6.19. The use of simple inter-
ference fringes combined with a
bevel to give depth. The mechanics
of beveling and staining are cov- ~
-1
partoftheOriginal
surface must be present
for accurate orientation
Partially reflecting
glass plate placed on
ered in Chap. 7. of the plate top ofsample
176 Semiconductor Measurements and Instrumentation

so a metallurgical microscope with a filter to give reasonably monochromatic light

is used for observation. The reference surface can be a small piece of cover glass
carefully positioned on the sample, or a reference-plane attachment which is avail-
able from some microscope manufacturers. Photographs are usually taken and all
necessary measurements and fringe counting done from them. Such bevel inter-
ferometry is probably the second most widely made measurement in the semi-
conductor industry, following only the four-point-probe resistivity determination.
When the reference plane is in perfect coincidence with the original surface and
if the incline is not skewed, the fringes (lines) will all be aligned parallel with the
line of intersection of the original surface and the incline as shown in Fig. 6.20a.
By counting the number of lines N from the beginning of the incline out to the
point of interest, the vertical depth is determined independently of whether or not
the incline is flat or curved, and without knowledge of the incline angle by

t=NA.
2
If the reference is tilted up as shown in Fig. 6.20b about a line 3-4 which is parallel
to the intersection 1-2, additional fringes will be seen in the region 1-2-3-4, and now
the pattern will appear as shown. Since the reference plane is tilted, the number
of lines counted must be corrected for the amount the reference rises in the horizontal
distance between line 1-2 and the feature of interest. This will be equal to the drop
in a similar distance back from line 1-2 toward the pivot. Thus the true depth is
given by Nx - Nx of Fig. 6.20c. If the reference is tilted down, an analogous situation
exists except that now the back fringes (N) must be added. A basic difficulty with

Fringe lines
~

1111111111111111
Reference
S-foce

(0 )

I 111111111111111111111111111 Fig. 6.20. Effect of reference-plane tilt on

~
N N
interference-depth measurements.
depth Xi is given by (N-N)Aj2 where N, N
The

(c) is the number of fringes in the distance x.

 Thickness Measurements 1 77

this approach is that if the lines really are perfectly aligned as shown, there is no
way of distinguishing between the two cases. As will be described a little later,
if alignment is not perfect, there are procedures for determining the sign of the
correction.
The reference plane can also be tilted as shown in Fig. 6.2la. In that case the
character of the fringes is quite different, as is depicted in Fig. 6.2lh. This is the
configuration normally used when measuring total step height, although it can also
be used for measuring partway down (e.g., Xj of Fig. 6.20). The step height t is
given by the lateral displacement D of a particular fringe as it goes over the step
divided by the normal fringe separation d, all multiplied by Ai2. That is,

t = DA.
2d
When cp ~ 8, the fringes over the bevel (step) will be essentially parallel to line 1-2
of Fig. 6.20, and the fringes look like Fig. 6.22a. The depth at some point A is
determined from the number of fringes between A and B. If there is also tilt up
from the bevel (Fig. 6.20b), the fringes along the flat region will go off at an obtuse
angle as in Fig. 6.22b and the correction of Fig. 6.20b must be made. If the lines
are acute as in Fig. 6.22c, the plane tilts down and a positive correction is required.
Thus the sign of the correction is determined by the angle the fringes make as they
go over the edge of the beveP9 An alternate approach is to plot the fringe number,
starting with some arbitrary value, as a function of distance along a line drawn
perpendicular to the bevel edge. 58 The three shapes corresponding to the three cases
of Fig. 6.22 are shown in Fig. 6.23.
No matter which way the fringes are to be interpreted, the reference ideally would
be carefully adjusted by gentle, judicious movement to give lines like those of Fig.
6.22a. Practically, either ofthe other positions is acceptable and generally much more
quickly obtained. Common procedure is to count the whole number oflines between
the two points of interest, but for shallow junctions or narrow bases the error can

Monochromatic light

1 1 1°1 Reference

,<§Jcl
surfac.:,J

(a)

Bevel

"II -----
'I
'/
I,

The fringes are shown as dashes

Fig. 6.21. Alternate approach for alignment of the
reference plane. (b)
118 Semiconductor Measurements and Instrumentation

I
I
A I
(b)

Fig. 6.22. Effect of double tilt on frin

pattern.

Use this
number of fringes
r-"---~ position of
I
I I lunctlon

I
I
I
"1
1\ \
\
I ~\
-T ~:.

II' o 10 20 30 40
o 10 20 30 40
oo N
10 20 30 40 N (c)
N (b)
(a)
Fig. 6.23. Plotting fringe distance to correct for reference surface tilt. The
portion of the _ e "",..ponding to the fring.. OV« the ,.f«eno< "",..oe
is extrapolated to the depth to be measured. The double value of X for the
same fringe number in (c) occurs because the fringes for that case double
back (Fig. 6.23c) and a line perpendicular to the bevel edge cuts the same
fringe twice. (After Bond and Smits. 58)
 Thickness Measurements 179

be quite large, particularly on a one-line base. Fractions oflines should be estimated

in those cases, and to increase precision, a densitometer can be used to scan the
photograph and more accurately define the fringe position. 60
The fringes have all been depicted on the drawings as very sharp. However, when
both surfaces have very low reflectivity, the lines are actually quite diffuse. If a
reflecting layer such as aluminum is put on the reference surface and its reflectivity
is increased to 90 to 95 percent and the reflectivity of the bottom surface is also
increased, the fringe intensity vs. distance changes character, and the fringes really
do appear as sharp, well-defined lines. Such a procedure, referred to as Tolansky
multiple-beam interferometry, can be used to show exceedingly small steps or thick-
ness variations. 61 ,62
Interference in the Layer. If the sample is transparent and wedge-shaped, so that
t ofEq. (6.18) is changed and A is held constant, interference fringes will be generated
along the wedge. The change in thickness between two consecutive fringes is

tJ.t=~
2n

so that if the index of refraction n is known, the thickness can be determined by

counting the total number of fringes. A metallurgical microscope with a filter can
be used for observation. The wedge needs to have a gentle slope so that there is
enough separation between fringes for easy resolution. While it is sometimes possible
to cleave a silicon slice and have a coincidental fracture of the Si0 2 on top give
sufficient taper, the usual procedure for transparent dielectric layers is to etch the
step. If a mask that adheres poorly is used deliberately, its lifting will allow the
etch to produce the slope necessary to provide adequate fringe separation. For Si0 2
such diverse waxes as Apiezon W in toluene 63 and melted blue china marking
pencils 64 have been recommended. The Monsanto evaluation standards 2 specify
melted Apiezon W wax followed by a 2-min etch in 49 percent HF (more if the
oxide is exceptionally thick). Their procedure for estimating Si0 2 thickness on silicon
closer than -+ 1 line is to note whether the bare silicon is the same color or lighter
than the oxide under the monochromatic light. If it is approximately the same, the
thickness is an integral number of fringes thick. If the oxide is darker, the number
of dark bands between the bare silicon and the last distinct white band are counted.
Then, if an interference filter is used as a monochrometer, it is turned at an angle
to the beam in order to change the wavelength. If the oxide appears darker with
tilting, the thickness is the number of fringes previously counted plus a half or less.
If the oxide gets lighter, it is the count plus a half or more.
Mechanical. If the bevel of Fig. 6.19 is quite flat, the angle e it makes with the
original surface and the lateral dimension can both be measured and the depth Xi
calculated by

Xi = L tan e
The angle may be determined by a gunner's quadrant,65 a microgoniometer, or a
surface profilometer. In the latter case the horizontal and vertical scales of the trace
will be different; so the angle must not be measured directly from the trace.
The lateral measurement can be made by moving the microscope stage and thus
the image across the field of view by means of a calibrated screw or an attached
vernier. In most instruments, toolmaker's microscopes being an exception, the
1 80 Semiconductor Measurements and Instrumentation

graduations are quite coarse and only gross measurements can be made. A more
common approach is to use a filar eyepiece which moves a crosshair across the
real-image plane. A calibration must ordinarily be done by counting the number
of graduations required to move across an accurately engraved scale on which the
objective is focused. Such scales are relatively inexpensive and are a necessity.
Instead of a filar eyepiece, the scale can be photographed at the same magnification
as are pictures of the object. A new scale can then be cut out of the photograph
and used directly as a ruler to measure any desire dimensions on the other photo-
graphs. When this approach is used, however, great care must be taken to make
sure that the focus is very precise in each case, because the apparent separation
of lines will vary with the amount of defocusing. A somewhat more elegant method
is to use image shearing and measure the angular displacement necessary to shift
one of the images by the width of the object to be measured. By using a televi-
sion-screen display, an electronic scale can be superimposed and measurements made
somewhat easier. However, whichever method is used, the accuracy cannot be better
than the limits of resolution of the optics used, no matter how big a photograph
or TV display is used.
There are also beveling configurations which do not require a knowledge of the
bevel angle. For example, if a cylinder66 or sphere67 ,68 of diameter D is used to
grind a depression in the surface as shown in Fig. 6.24, the depth to the demarcation

8 ~ C:)/9
F' /9 F'
~ ------------ \ x;' ~ ---->------- \

Using spherical grinding tool Using cylinder grinding tool

Using a cylindrical
tool with axis not
parallel to the
sample surface

Fig. 6.24. Use of spherical and

cylindrical beveling for depth meas-
urements.
 Thickness Measurements 181

line Xj is given approximately by

xy
D
where x and yare defined in the figure. The lateral measurements can be made
by any of the methods just discussed. The mechanics of the grinding operation is
not particularly critical, but the abrasive should be very fine, e.g., Linde B. The tool
diameter can conveniently be in the Y4- to ~-in-diameter range, and for the cylin-
drical groover, the tool axis may be a few degrees away from parallelism with the
surface without producing excessive error.

6.7 STEP-HEIGHT MEASUREMENTS

If the layer can be stripped away in one area so that a step is available (con-
figuration d of Fig. 6.1), several mechanical and optical measurements are available.
With Microscope. If the step is large enough, a microscope with a high-power
objective and calibrated vertical motion can be focused on each surface and the
height measured.
With Light-Section Microscope. Such a microscope is applicable only for steps
greater than approximately 1 p.m. See Chap. 8 for further details.
With Profilometer. A mechanical stylus drawn across the step affords a rapid and
simple way of measuring height of from a few hundred angstroms up to several
micrometers. For precise location of the stylus, a stereoscopic microscope is used
for positioning the sample under the stylus. Should the step be made by etching
a narrow groove or small hole in the layer, consideration should be given to the
relative size of the groove and the stylus. With the kinds of micro definition available
in microcircuit technology it is quite possible to produce grooves so narrow that
the stylus cannot reveal the bottom. This method is applicable to epitaxial layer
thickness measurements since steps can be generated by locally masking the original
surface with an oxide! or silicon nitride layer 74 and then removing the overgrowth.

6.8 HIGH-POWER MICROSCOPE PLUS VISIBLE BOUNDARIES

If the layers are thicker than a few micrometers and transparent, a microscope
can be focused on first one surface and then the other. The thickness is then
calculated by multiplying the index of refraction by the measured separation. Either
a conventional microscope with calibrated vertical motion or a toolmaker's micro-
scope with dial indicator can be used. In order to reduce the depth of field and
thus more accurately define the two surfaces, high-power objectives should be used.
For looking at silicon, e.g., Si on Si0 2 on polycrystalline silicon (DI), or GaAs, an
infrared microscope can be used. In general it is not possible, however, to see
epitaxial- or diffused-layer boundaries by this method, although on occasion the
interface may be so poor that some trace will be visible.

6.9 WEIGHT DIFFERENTIAL

By weighing a substrate before and after a layer is deposited, the average thickness
can be calculated if the area and the density are known.! In the case of epitaxial
layers, the density will be known very accurately, but because of the difficulty in
preventing all growth from the backside (assuming the slice lies on some sort of
182 Semic:onductor Measurements and Instrumentation

heater), the area is seldom known. Conversely, for thin metal deposits by vacuum
techniques, the density may not be accurately known, but the areas are generally
well defined. By continuously weighing slices during deposition (more applicable
to hot-wall systems where the slice can be suspended and simultaneously deposited
on both sides), the film thickness vs. time can be measured. 69
Despite the fact that this system is in principle very simple, it has several rather
serious disadvantages such as: (1) It gives only an average value. (2) It requires
maintaining the identity of all slices from first weighing through the deposition
process to final weighing (very difficult in large-quantity production). (3) It requires
control or measurement of the film area. (4) For very thin layers on thick substrates
a combination of the sensitivity required and total range may be difficult to achieve
in one instrument. (5) When used for epitaxy, it precludes the use of in situ substrate
etching prior to deposition.

6.10 CRYSTALLOGRAPHIC METH0071-73

Stacking faults originating during epitaxial growth have a predictable geometry.

(See Chap. 2.) The size of their outline on the surface is directly proportional to
thickness and can be used to calculate the thickness oflayers which grew after their
inception. Occasionally some difficulties will arise during deposition and initiate
additional faults. These will not be as big as the ones which nucleated at the
beginning; so before a particular stacking fault is chosen for measurement, the area
should be scanned and only the largest ones considered.
The perpendicular distance from the surface to the point of origin of the fault
is given by the length of a side of the polygonal fault outline multiplied by the
appropriate number from Table 6.8. Except for (111) and (100) surfaces, the sides
will not be of equal length. Thus more than one multiplication factor is given in
those cases. However, any side multiplied by its own factor will give the same answer
as any other. If perchance a layer of orientation other than one of those of Table
6.8 is being measured, Ref. 73 gives details for calculating the appropriate dimen-
sions. There will occasionally be linear faults which will have the same dimensions
as a similarly oriented side of a polygon and can also be used * as long as care is
taken to understand what their orientation is [no problem on (100) and (111) surfaces,
since all sides are of equal length].
Under most growth conditions, stacking faults can be seen with a phase- or
interference-contrast microscope without any additional surface treatment. In such
cases the method is nondestructive. Should a light etch be required to define them,
the details may be found in Chap. 2. If the etch removes a substantial thickness
of the film, that amount must be added to the thickness determined from the fault
dimensions. To estimate the amount removed, the etch rate is determined in a
separate experiment and combined with the sample etch time. The primary disad-
vantage of using stacking faults is that high-quality depositions have few of them
and they may thus be virtually impossible to find. The calculated value differs from
almost all other methods in that it measures from surface to the actual epitax-
ial substrate interface, and not to some other region defined by substrate out-
diffusion. There may therefore be correlation problems between this and other
methods.

* ASTM Tentative Test Method F l43-7lT recommends against using dimensions from incomplete
polygons.
 Thickness Measurements 1 83
Table 6.8. Multiplication Factors
to Be Used for Layer Thickness
from Stacking-Fault Dimensions

Multiplication factor

Orientation a b

(111) 0.816
(100) 0.707
(110) 0.5 0.577

For additional orientations see Ref. 73.

Thickness = (length of side) X multiplica-
tion factor.

(110)

6.11 MISCELLANEOUS METHODS FOR METALLIC FILMS

There are numerous methods which depend on conductivity or magnetic induction

which can be used for metal-film-thickness measurement. 70 Most of them are
applicable to relatively thick films of considerable lateral extent. Electron backscat-
tering has also been used, as has x-ray fluorescence. The latter does not necessarily
depend on the metallic properties but works best on heavy elements and is ordinarily
applied to metallic films. The x-ray microprobe allows measurements to be made
over exceedingly small areas. Beam size can be as small as a few micrometers in
diameter, and sensitivity is such that it can be used to estimate the thickness of Ni/Cr
films in the lOo-A range.

REFERENCES

l. C. C. Allen and E. G. Bylander, Evaluation Techniques for and Electrical Properties

of Silicon Epitaxial Films, in John B. Schroeder (ed.), "Metallurgy of Semiconductor
Materials," Interscience Publishers, Inc., New York, 1962; Robert C. Abbe, Semiconduc-
tor Wafer Measurements, Solid State Tech., 17:47-50 (March 1974).
2. Monsanto Evaluation Standards, Electronic Materials Division, Monsanto, St. Peters, Mo.
3. A. R. Moore, A Method of Accurate Thickness Determination of Germanium Wafers
Suitable for Transistor Production, IRE Trans. Electron Devices, ED-4 309-310 (1957).
4. O. S. Heavens, "Optical Properties of Thin Solid Films," Dover Publications, Inc., New
York, 1965.
5. J. E. Dial, R. E. Gong, and J. N. Fordemwalt, Thickness Measurements of Silicon Dioxide
Films on Silicon by Infrared Absorption Techniques, J. Electrochem. Soc., 115:326-327
(1968); C. J. Mogab, Measurement of Film Thickness From Lattice Absorption Bands,
J. Electrochem. Soc., 120:932-937 (1973).
6. S. D. Mittleman and L. Bess, Nondestructive Thickness Measurement in Thin Sections
of Ge, Rev. Sci. Instr., 39:838-840 (1965).
7. H. Yokota, M. Nishibori, and K. Kinosita, Ellipsometric Study of a Thin Transparent
Film Overlaid on a Transparent Substrate Having a Surface Layer, Surface Sci.,
16:275-286 (1969); Leif Lundkuist, Ellipsometry of Multilayered Dielectrics on Silicon,
Applied to MNOS Structures, J. Electrochem. Soc., 120:1140-1142 (1973).
184 Semiconductor Measurements and Instrumentation

8. E. Passaglia, R. R. Stromberg, and J. Kruger (eds.), "Ellipsometry in the Measurement

of Surfaces and Thin Films," National Bureau of Standards, Misc. Pub. 256, 1964.
9. William A. Shurc1iff, "Polarized Light," Harvard University Press, Cambridge, 1962.
10. R. J. Archer, Determination of the Properties of Films on Silicon by the Method of
Ellipsometry, J. Opt. Soc. Am., 52:970-977 (1962).
11. K. H. Zaininger and A. G. Revesz, Ellipsometry-A Valuable Tool in Surface Research,
RCA Rev., 25:85-115 (1964).
12. H. E. Bennett and Jean M. Bennett, Precision Measurements in Thin Film Optics, in
Georg Hass and Rudolf E. Thun (eds.), "Physics of Thin Films," vol. 4, Academic Press,
Inc., New York, 1967.
13. Paul Drude, "The Theory of Optics," Longmans, Green & Co., Ltd., New York, 1907.
14. Alexandre Rothen, Measurements of the Thickness of Thin Films by Optical Means,
from Rayleigh and Drude to Langui, and the Development of the Present Ellipsometer,
in E. Passaglia, R. R. Stromberg, and J. Kruger (eds.), "Ellipsometry in the Measurement
of Surfaces and Thin Films," National Bureau of Standards, Misc. Pub. 256, 1964.
15. Rolf H. Muller, Definitions and Conventions in Ellipsometry, Surface Sci., 16:14-33
(1969).
16. A. R. Hilton and C. E. Jones, Measurement of Epitaxial Film Thickness Using an Infrared
Ellipsometer, J. Electrochem. Soc., 113:472--478 (1966).
17. A. B. Winterbottom, Increased Scope of Ellipsometric Studies of Surface Film Formation,
in E. Passaglia, R. R. Stromberg, and J. Kruger (eds.), "Ellipsometry in the Measurement
of Surfaces and Thin Films," National Bureau of Standards, Misc. Pub. 256, 1964.
18. Jerome M. Weingart and Alan R. Johnston, Electronic Polarimeter Techniques, in
E. Passaglia, R. R. Stromberg, and J. Kruger (eds.), "Ellipsometry in the Measurement
of Surfaces and Thin Films," National Bureau of Standards, Misc. Pub. 256, 1964.
19. H. G. Jerrard, A High Precision Photoelectric Ellipsometer, Surface Sci., 16:137-146
(1969).
20. J. L. Ord, An Ellipsometer for Following Film Growth, Surface Sci., 16: 155-165 (1969).
21. Ingo Wilmanns, A Double-Modulation Photoelectric Ellipsometer, Surface Sci.,
16:147-154 (1969).
22. Layer, Howard P., Circuit Design For An Electronic Self-Nulling Ellipsometer, Surface
Sci., 16:177-192 (1969).
23. A. K. N. Reddy and J. O'M. Bockris, Ellipsometry in Electrochemical Studies, in
E. Passaglia, R. R. Stromberg, and J. Kruger (eds.), "Ellipsometry in the Measurement
of Surfaces and Thin Films," National Bureau of Standards, Misc. Pub. 256, 1964.
24. B. D. Cahan and R. F. Spanier, A Highspeed Precision Automatic Ellipsometer, in
E. Passaglia, R. R. Stromberg, and J. Kruger (eds.), "Ellipsometry in the Measurement
of Surfaces and Thin Films," National Bureau of Standards, Misc. Pub. 256, 1964.
25. Frank L. McCrackin, Elio Passaglia, Robert R. Stromberg, and Harold L. Steinberg,
Measurement of the Thickness and Refractive Index of Very Thin Films and the Optical
Properties of Surfaces by Ellipsometry, J. Res. Nat!. Bur. Std., 67A363-377 (1963).
26. Frantisek Lukes, The Accuracy of the Measurement of the Ellipsometric Parameters ~
and '1', Surface Sci., 16:74-84 (1969).
27. Paul H. Smith, A Theoretical and Experimental Analysis of the Ellipsometer, Surface
Sci., 16:34-66 (1969).
28. H. G. Jerrard, Sources of Error in Ellipsometry, Surface Sci., 16:67-73 (1969).
29. "Ellipsometer Manual AME-500-1," Applied Materials Technology Inc., Santa Clara,
Calif., 1970.
30. R. J. Archer, "Manual on Ellipsometry," Gaertner Scientific Corporation, Chicago, Ill.
31. Lawrence A. Murray and Norman Goldsmith, Nondestructive Determination of Thick-
ness and Perfection of Silica Films, J. Electrochem. Soc., 113:1297-1300 (1966).
32. N. Goldsmith and L. A. Murray, Determination of Silicon Oxide Thickness, Solid State
Electron., 9:331,332 (1966).
 Thickness Measurements 185

33. Myron J. Rand, Spectrophotometric Thickness Measurements for Very Thin Si0 2 Films
on Si, J. Appl. Phys., 41:787-790 (1970).
34. W. C. Dash and R. Newman, Intrinsic Optical Absorption in Single-Crystal Germanium
and Silicon at 77°K and 300 o K, Phys. Rev., 99:1151-1155 (1955).
35. Edwin A. Corl and Hans Wimpfheimer, Thickness Measurement of Silicon Dioxide
Layers by Ultraviolet-Visible Interference Method, Solid State Electron., 7:755-761
(1964).
36. F. Reizman, Optical Thickness Measurement of Thin Transparent Films on Silicon,
J. Appt. Phys., 36:3804-3807 (1965).
37. I. Franz and W. Langheinrich, A Simple Non-destructive Method of Measuring the
Thickness of Transparent Thin Films between 10 and 600 nm, Solid State Electron.,
11 :59-64 (1968).
38. W. G. Spitzer and M. Tanenbaum, Interference Method for Measuring the Thickness
of Epitaxial Grown Films, J. Appl. Phys., 32:744-745 (1961).
39. M. P. Albert and J. F. Combs, Thickness Measurement of Epitaxial Films by the Infrared
Interference Method, J. Electrochem. Soc., 109:709-713 (1962).
40. Warren Groves, Measurement of Thickness of Gallium Arsenide, Epitaxial Films by the
Infrared Interference Method (Nondestructive), Semicond. Prod., 5:25-28 (1962).
41. Robert J. Walsh, Measurement of Layer Thickness of Silicon Epitaxial Wafers, SCP and
Solid State Tech., 7:23-27 (August 1964).
42. P. J. Severin, On the Infrared Thickness Measurement of Epitaxially Grown Silicon
Layers, Appl. Opt., 9:2381-2387 (1970).
43. P. A. Schumann, Jr., The Infrared Interference Method of Measuring Epitaxial Layer
Thickness, J. Electrochem. Soc., 116:409-413 (1966).
44. P. A. Schumann, Jr., R. P. Phillips, and P. J. Olshefski, Phase Shift Corrections for Infra-
red Interference Measurement of Epitaxial Layer Thickness, J. Electrochem. Soc.,
113:368-371 (1966); P. J. Severin, On the Infrared Thickness Measurement of Epitaxially
Grown Silicon Layers, Appl. Opt., 9:2381-2387 (1970); P. J. Severin, Interpretation of
the Infrared Thickness Measurement of Epitaxially Grown Layers, Appl. Opt., 11 :691-692
(1972).
45. P. A. Schumann, Jr., and R. P. Phillips, Phase Shifts for Epitaxial Layer Thickness
Measurements by the Infrared Interference Method, IBM. Tech. Rept. 22.182 (1965).
46. P. A. Schumann, Jr., Thickness Measurements of Very Thin Epitaxial Layers by Infrared
Reflectance, in Charles P. Marsden (ed.), "Silicon Device Processing," National Bureau
of Standards, Spec. Pub. 337, 1970.
47. Toshio Abe and Taketoshi Kato, Infrared Reflectivity of N on N+ Si Wafers, Japan. J.
Appl. Phys., 4:742-751 (1965).
48. K. Sato, Y. Ishikawa, and K. Sugawara, Infrared Interference Spectra Observed in Silicon
Epitaxial Wafers, Solid State Electron., 9:771-781 (1966).
49. P. A. Schumann, Jr., Current Problems in the Electrical Characterization of Semicon-
ducting Materials, in Rolf R. Haberecht and Edward L. Kern (eds.), "Semiconductor
Silicon," Electrochemical Society, New York, 1969.
50. Thomas E. Reichard, Through Thick and Thin with Infrared Beams, Electronics,
41:101-105 (Mar. 18, 1968).
51. Allison Roddan and Vitali Vizir, An Instrument for Automatic Measurement of Epitaxial
Layer Thickness, in Charles B. Marsden (ed.), "Silicon Device Processing," National
Bureau of Standards, Spec. Pub. 337, 1970.
52. Paul F. Cox and Arnold F. Stalder, Fourier Transform Method for Measurement of
Epitaxial Layer Thickness, in Huff and Burgess (eds.), "Semiconductor Silicon," Electro-
chern Society, Princeton, 1973; P. J. Severin, The Influence of the Phase Shift on Thick-
ness Measurements of Silicon Epitaxial Layers with a Fourier Transform Spectrometer,
J. Electrochem. Soc., 121 :150-158 (1974).
53. Gary Horlick, Introduction to Fourier Transform Spectroscopy, Appl. Spectroscopy,
22:617-626 (1968).
186 Semiconductor Measurements and Instrumentation

54. R. T. Kampwirth, An Optical Thickness Monitor for Thin Film Vacuum Deposition
Control, Rev. Sci. Instr., 43:740-743 (1972).
55. D. J. Dumin, Measurement of Film Thickness Using Infrared Interference, Rev. Sci.
Instr., 38:1107-1109 (1967).
56. I. Franz and W. Langheinrich, Nondestructive Thickness Measurement of Thin Films
on Microstructures, Solid State Electron., 11 :987-991 (1968).
57. W. A. P1iskin and E. E. Conrad, Nondestructive Determination of Thickness and Refrac-
tive Index of Transparent Films, IBM J. Res. Develop., 8:43-51 (1964); W. A. P1iskin
and R. P. Esch, Refractive Index of Si0 2 Films Grown on Silicon, J. Appl. Phys.,
36:2011-2013 (1965).
58. W. L. Bond and F. M. Smits, The Use of an Interference Microscope for Measurement
of Extremely Thin Surface Layers, Bell System Tech. J., 35:1209-1221 (1956).
59. Martin G. Buehler, personal communication, 1967.
60. R. H. Dudley and T. H. Briggs, Rapid Photometric Method for Increasing Precision of
Layer Thickness Measurement by Angle Lap Technique, Rev. Sci. Instr., 37:1041-1044
(1966).
61. S. Tolansky, "Interferometry," John Wiley & Sons, Inc., New York, 1954.
62. Philip S. Flint, Optimization of the Tolansky Technique for Thin Film Thickness Meas-
urements, in Bertram Schwartz and Newton Schwartz (eds.), "Measurement Techniques
for Thin Films," The Electrochemical Society, New York, 1967.
63. G. R. Booker and C. E. Benjamin, Measurement of Thickness and Refractive Index of
Oxide Films on Silicon, J. Electrochem. Soc., 109: 1206-1212 (1962).
64. Murray Bloom, Formation of Wedges in the Measurement of Oxide Films on Silicon,
Semicond. Prod., 6:26 (1963).
65. R. M. Burger and R. P. Donovan (eds.), "Fundamentals of Silicon Integrated Device
Technology," Prentice-Hall, Inc., Englewood Cliffs, N.J., 1967.
66. B. McDonald and A. Goetzberger, Measurement of the Depth of Diffused Layers in
Silicon by the Grooving Method, J. Electrochem. Soc., 109:141-144 (1962).
67. I. Lagnado and S. M. Po1cari, Spherical Drilling, A New Method for the Measurement
ofJunction Depths in Semiconductor Devices, Solid State Electron., 10: 1219-1220 (1967).
68. S. D. Rosenbaum, Junction Depth Measurement by Spherical Contouring, Solid State
Electron., 11:711-712 (1968).
69. Don W. Shaw, Epitaxial GaAs Kinetic Studies {DOl} Orientation, J. Electrochem. Soc.,
117:683-687 (1970).
70. D. J. Gillespie, A Survey of Thin Film Thickness Measurement Methods, in Bertram
Schwartz and Newton Schwartz (eds.), "Measurement Techniques for Thin Films," The
Electrochemical Society, New York, 1967.
71. T. B. Light, Imperfections in Germanium and Silicon Epitaxial Films, in John B.
Schroeder (ed.), "Metallurgy of Semiconductor Materials," John Wiley & Sons, Inc.,
New York, 1962.
72. William C. Dash, A Method for Measuring the Thickness of Epitaxial Silicon Films,
J. Appl. Phys., 33:2395-2396 (1962).
73. S. Mendelson, Stacking Fault Nucleation in Epitaxial Silicon on Variously Oriented
Silicon Substrates, J. Appl. Phys., 35:1570-1581 (1964).
74. F. C. Eversteyn and G. J. P. M. van der Heuve1, Method For Determining the Metal-
lurgical Layer Thickness of Expitaxially Deposited Silicon from SiH4 Down to 0.5 p.m,
J. Electrochem. Soc., 120:699-701 (1973).
 7
Preparation of Samples
for Microscopic Examination*'t

This chapter deals almost exclusively with the preparation of semiconductor

materials and devices for microscopic examination. The microscopic and photo-
graphic techniques themselves are covered in another chapter. The preparation can
in turn be subdivided into two parts. One is concerned with the mechanics of
obtaining the right surface for viewing and the other with various etch, stain, and
decoration treatments to cause the desired detail to become visible.

7.1 SECTIONING

Sectioning is used in the examination of transistors and integrated circuits to

expose the region below the surface so that metallic interfaces can be seen or so
that it can be stained or etched to define p-n junctions or regions of differing
crystallographic perfection. In principle, a right-angle section as illustrated in Fig.
7.la should be appropriate. Unfortunately many of the things of interest are so
thin that additional magnification is desirable (particularly true of base regions and
ion-implanted layers). Such magnification can be achieved by using angle sectioning
(beveling) as in Fig. 7.lb to obtain vertical magnification. The magnification is given
by l/sin (} as defined in the figure and can be substantial, since angles ofless than
a degree are quite feasible.~ Sectioning is not without its pitfalls, however, since
interpretation is more difficult, and if the substructure of interest is of limited
horizontal extent, the section may not show its full depth. However, there is often
a series of adjacent, repetitive substructures, so that a low-angle section will capture
different portions of each as shown in Fig. 7.2 and allow the whole structure to be
visualized. Sequential (serial) sectioning as commonly practiced in anatomy and
pathology is seldom done intentionally, but the effect just described in Fig. 7.2 is
certainly closely akin to it, and the techniques developed in those fields can some-
times be used to advantage. 1,2

* This ~hapter was ~oauthored by Sta~y B. Watelski.

t Contrary to the precedent established in the other chapters, specific manufacturers' products are
mentioned in this one. This does not indicate the authors' endorsement, but rather that these products
are known to work and may be used as a starting point for further experimentation.
*Magnification along the incline. When viewed normal to the original surface, it is l/tanO.
187
188 Semiconductor Measurements and Instrumentation

Surface exposed
by a right-
angle section

Fig. 7.1. Use of angle sectioning to

(0) (b) obtain magnification.

The samples to be sectioned fall into two categories. 3 One includes devices in
various stages of assembly. These may range in complexity from a semiconductor
die with some monometallic metallization deposited on it (e.g., Al on Si) to a die
with metallization, attached to a header with solder, eutectic alloy, or organic adhe-
sive, and connected with various. small (often less than I mil diameter) wires. The
other category is the semiconductor by itself, either before the addition of all its
metallic and dielectric accouterments or after they have been stripped away. Clearly
the first category will require certain precautions not needed on the second because
of the presence of soft metals which smear easily and the likelihood of breaking
unsupported wires during sectioning. The second category more often requires
low-angle bevel lapping for magnification and subsequent etching and/or staining,
and in general is handled differently. In particular, those with metallization are
almost always potted in a supporting plastic, and those without are usually not
potted. Further, subsequent thickness measurements are often made on the latter,
and as is described in Chap. 6, one of the more common methods of doing it is
by interferometry. Such a procedure requires that a portion of the original surface
be left for a reference as illustrated in Fig. 7.3. Should the details of a metal-metal
bond interface be desired, however, the whole sample could be sectioned with no
regard for the original surface.
Bevel Polish. There are several variations of the beveling technique, but the fixture
shown in Fig. 7.4 will serve as a basic tool. The size of the fixture may be changed
to accommodate different sample sizes. The outer ring is made of brass or soft iron.
Either of these metals will glide over the glass lapping surface with minimum drag.
The circular format further ensures a smooth glide. Of the two metals, brass is

(0)

Fig. 7.2. Effectofthepositionofthe

D c B A section plane on the projected shape
(b) of the buried structure.
 Preparation of Samples for Microscopic Examination 1 89

Fig. 7.3. Thesubsequentuseof

an angle-lapped specimen for ~_-_-_-~~~D!.~-=-"~t___-_-_--=-~
Partially reflecting
thickness measurements may glass plate placed

~ ~ ontop of sample
require some of the original Part of original surface
must be present for accurate
surface to be left. orientation of the plate

preferred because of its rust-free nature. If, however, iron is used, it may be left
in an aqueous ammoniacal solution to prevent rusting when not in use. The insert
is most conveniently made of stainless steel. The sample is affixed to the insert by
use of an adhesive. Several acceptable ones are Apiezon W wax, 70C cement, * and
Tan wax. t The first is soluble in chlorinated hydrocarbons, the other two in alcohol.
The Apiezon wax can be obtained with a range of melting points. For example,
W-40 melts at 45°C, W-lOO at 55°C, and W at 85°C. The melting points of the
other two are 75 and 76°C, respectively.
The choise of adhesive is usually not critical. Each will adequately secure the
sample to the insert, although prolonged exposure of the adhesive to etch ants (i.e.,
staining and delineating acidic solutions) will weaken them. This is evidenced by
the adhesives lightening in color. The least affected is Apiezon W. Extremely small
samples will best be secured by use of Tan wax or 70C cement. The latter is more
easily removed from a delicate sample with alcohol; however, the former is less likely
to allow the sample to part from the insert under stress. Also, the Apiezon W may
be used at a lower temperature than the others; specific samples may require this.
Before mounting the sample, one must decide which bevel should be used. This
choice· of angle is dependent on the sample size, the depth to be measured or
observed, the magnification desired, and somewhat on the sample resistivity. If the
sample is very small, a small-angle bevel (i.e., 1°) might utilize all the top surface
in order to obtain a sufficient bevel depth. This would be unacceptable if thickness
measurements were to be made. The distance lapped back on the top surface and
the magnification is approximately 60, 20, and 10 times the depth for 1°, 3 0, and
7° bevels, respectively. If the resistivity of the material is greater than 1.0 Q-cm,
a delineation stain may not be very dark in color; in fact it may be a faint gray
and extremely difficult to see when magnified sufficiently and superimposed with
interference-fringe lines. If a larger angle is used, the critical area expansion is

*Hugh Courtright & Co., Vincennes Ave., Chicago, Ill.

tFred Lee & Co. Ltd.

Fig. 7.4. Bevel-polishing fixture. ( oj ( bJ

190 Semiconductor Measurements and Instrumentation

Fig. 7.S. Two-piece insert.

sacrificed, but the stain occurs in a narrower region and hence appears darker. If
a larger angle cannot be used, the smaller one is used, the faint resulting stain is
photographed without the fringe lines, and another photograph is made at the same
magnification with the fringe lines. Physical distances from the first photograph are
transferred to the second to obtain a proper fringe-line count. The second decision
prior to sample mounting is whether to use a one- or two-piece insert. If at all
possible, the two-piece insert (Fig. 7.5) is preferred. Because it is very short, it can
be easily positioned on a microscope stage. The one-piece insert (Fig. 7.4a), because
of its height, requires the use of a modified or inverted microscope stage.
If the bevel is to reveal a routine-type delineation in which a large beveled area
is not necessary, the sample may be cut and positioned as shown in Fig. 7.6a. Only
the pointed tip is polished, and because it is a small area, the job is quickly accom-
plished. Other samples requiring larger areas are cut and positioned such that the
bevel will pass through the sample at the desired angle.
After the particular insert to be used has been heated on a hot plate, it is removed
and a thin layer of adhesive is melted on its surface. The sample is then placed
on the waxed insert end and seated properly by pressing down and at the same
time moving the sample in a circular motion. This is easily accomplished by using
a pair of tweezers. The tweezer points allow the sample to be properly positioned
prior to cooling. The circular sample movement will expel trapped gas and excess
wax under the sample. If the wax film is kept very thin and uniform, the subsequent
beveling operation will produce a sample with a beveled surface approximately equal
to the bevel angle of the insert. The insert is now ready to be cooled. Too rapid
cooling will allow some adhesives to craze and the sample will not be tightly secured;

( oj ( bJ
Fig. 7.6. Mounted sample.
 Preparation of Samples for Microscopic Examination 191

however, cooling may be hastened on an insert by placing the bottom end of it in

cool water. After a few seconds the whole insert may be slowly immersed.
The process of sample mounting and positioning usually results in unwanted
adhesive around the edges of the sample. This will prevent the polishing of the
sample if not removed. A razor blade is used to remove the adhesive from the sides
and top of the sample. If the semiconductor material is easily scratched, extreme
care must be exercised in mounting and/or cleaning. Silicon samples will not be
scratched by scraping their tops with a razor blade to remove excess wax. Ger-
manium, however, will be damaged, and any excess wax should therefore be removed
by gently wiping with a cotton swab which has been dipped in a suitable solvent.
When most of the excess wax has been removed, the final traces are removed by
using a damp swab. Wipe only in one direction, tum the swab top 180 and wipe 0
,

again. Discard the swab after this double use. The cleanliness of the surface can
be observed by watching the solvent evaporate. The evaporation of the solvent on
a wax-free surface will show no residual wax-colored spot as the last traces evaporate.
The polishing plate to be used may be an ordinary piece of plate glass; however,
better results are obtained by using a glass plate that has been precision-finished
flat to a centerline average (CLA) index of 4.5 p.m or better. This surface will allow
the bevel fixture to glide with uniform ease when polishing. If an unfinished glass
plate has a high or a low spot on its surface, this may cause the polishing fixture
to drag, and in tum tilt and bump the sample on the glass surface. Fracturing of
the sample then usually occurs. The glass plate should be a minimum size of 9
by 9 in.
The sample is usually polished in an aqueous slurry. An acceptable one is
1 g of Linde A (0.3 p.m alumina abrasive)*
2 ml of Joy or other liquid detergent
15 ml of water
This slurry is stirred for rather uniform consistency using the fingers. The insert
is then introduced into the fixture and the assembly carefully placed in the polishing
slurry. The insert is positioned to touch the glass plate with the sample away from
the plate. The fixture is then slowly set upright on the plate. Some of the slurry
is added to the top of the fixture and allowed to run down the fluted sides of the
insert prior to polishing.
Polishing is accomplished by applying moderate pressure to the insert with one
finger while using the remaining fingers to move the fixture in a large figure eight
pattern or by using a very gentle mechanical polisher of the vibrating variety.
Additional slurry is made at the beginning of each evaluation by adding the separate
components to the top of the fixture after it is positioned with the insert on the
polishing plate, or by picking up slurry with the fingers and placing it on the top
of the insert.
For optimum results:
1. Mix fresh slurry for each sample or two.
2. Clean plate often.
3. Replace a badly scratched plate.
4. Use only one abrasive per plate.
*For the less hard semiconductors such as InSb, softer polishing compounds like magnesium and
iron oxide are more appropriate.
192 Semiconductor Measurements and Instrumentation

5. Keep larger-grit abrasive away from plate. Larger grit could come either
from chance contamination or from edges of the sample breaking away.
6. Completely clean fixture often.
Polishing times may range from a few minutes to more than an hour, depending
on the size of the beveled face and the depth of bevel required. The bevel polished
surface is periodically inspected to see when it is polished deep enough and that
it is relatively free of scratches. For demanding subsequent examinations, the
polished surface should be observed under dark field to verify that it is quite free
of scratches before leaving this operation. This freshly polished surface is ready to
be chemically treated and/or microscopically inspected. Procedures for staining the
sample will be found in a later section.
To remove the sample from the insert, heat until the adhesive is soft and slide
the sample from the insert or cut under the sample with a razor blade. The latter
usually destroys the sample but is a quick, effective removal scheme to be used when
the sample is no longer needed.
Alternate abrasives which can be used to produce a polished surface are Linde B, *
AB Metadit 3-p,m, and AB Metadit %-p,m diamond polishing compounds. Linde B,
a powder, is used exactly the same as Linde A powder. Either of the two diamond
polishing compounds is supplied in an oil base. It is advisable to dilute this thick
oil with enough light machine oil to allow easy movement of the polishing fixture
on the polishing plate. This will also reduce the tendency of the fixture to drag
and bump.
Sectioning at Very Small Angles. Occasionally there will be a requirement for
even greater magnification. By using lapping blocks with diamond stops, it is possible
to mount large-area flat samples, e.g., solar cells or large portions of slices, and lap
rather closely to predetermined angles of a few minutes. Polishing must be subse-
quently done without the stops, but if the block has been filled with dummy slices,
the original angle can be reasonably maintained. If any of the original surface is
left, the actual angle can be estimated by running a profilometer such as a Rank
Talysurf over it and down the bevel. If there is no requirement on the angle other
than that it be small, a straightforward polish of the sample and dummy fillers will
almost certainly result in a final surface nonparallel with the original one.
Perpendicular Sectioning. Semiconductor material may be perpendicularly sec-
tioned in a manner similar to the bevel polish technique, but using one of the types
of modified inserts shown in Fig. 7.7. The modified insert shown on the left can

* Union Carbide Corp. Linde Div., Crystal Products Dept., East Chicago, Ind.
tBuehler, Ltd., Greenwood St., Evanston, Ill.

Fig. 7.7. Modified inserts for perpendicular

sectioning.
 Preparation of Samples for Microscopic Examination 193

facilitate a larger sample than the one shown on the right and is often necessary.
The time required to polish a large sample to some predetermined position will
usually be in excess of 2 h. The sample is mounted so that a portion of it extends
beyond the top of the insert. The insert is heated and an adhesive* is melted on
only the face of the insert which is parallel to its long axis. The sample is placed
on the molten adhesive and pressed with a circular motion to expel the excess gas
and adhesive and seat itself against the insert. While still hot, the fixture is inverted
such that it rests on a glass microscope cover glass and the sample is positioned
to rest its edge on the surface which supports the cover glass.
Thus the sample will overhang the insert top face by an amount equal to the
thickness of the cover glass. This procedure also facilitates polishing by fixing the
sample edge parallel to the insert edge. Excessive adhesive must be removed from
the top edge of the sample and from the top face of the insert so as not to impede
the subsequent polishing step. It is preferable to remove the excess adhesive by
dissolving it using a cotton swab and a suitable solvent. Because of the large surface
area presented to the polishing plate, and the polishing time required, it may be
desirous to lap the sample prior to polishing using an 1,800-grit abrasive. The
abrasive and water are put on a separate lapping plate whose surface is prepared
similar to the polishing plate and mixed to a smooth consistency with the fingers.
If too little water is used, the slurry will be thick and the lapping fixture will not
move easily through it. If the slurry is too thin, very little material will be removed
per unit time. A normal slurry (the consistency of thin syrup) will be colored by
the semiconductor being lapped. This darkening of the slurry is normal and gives
an indication as to when the slurry should be replaced with a fresh batch. The sample
is lapped to expose a region ahead of the desired target region. For silicon, stop
I to 2 mils ahead; for germanium, stop 3 to 4 mils ahead. For a sample containing
a device or fabricated pattern (diffusion, selective epitaxy, alloy, etc.) stop before
engaging the pattern. Final polishing should be continued only after the insert and
fixture are thoroughly washed free of the large-grit abrasive. Small quantities of
large abrasive carried to the polishing plate not only will scratch the plate and the
sample but may be responsible for causing chipping of the sample being polished.
Approximate polishing times, excluding lapping, are:
1. lO-mil-thick sample 250-mil wide, 5 min
2. lO-mil-thick sample 500-mil wide, 10 min
These are optimum times assuming no difficulties are encountered. Sometimes
scratches, chipping, and sample breakage may prolong these times to several hours.
Cleaving. This process allows a slice of semiconductor material to be sectioned
by breaking rather than polishing in order to reveal an almost perpendicular sec-
tion. 50 The cleaving procedure can be varied considerably, but a workable one is
as follows:
1. Scribe line across the backside of the slice at the desired cleaving position.
2. Spray both sides of the semiconductor slice with a solution of Apiezon W
dissolved in trichloroethylene (0.1 g/ml). Upon drying, this thin wax film
will protect both semiconductor surfaces from subsequent scratching.

*Because perpendicular sectioning exerts a greater force on the sample than bevel sectioning, only
70C cement or Tan wax should be used.
194 Semiconductor Measurements and Instrumentation

frsamPle

:==J=1: I ):

Fig. 7.S. Sample prepared for cleaving.

3. Sandwich the coated slice between pieces of microscope slides as shown in

Fig. 7.8.
4. While holding the sample sandwich with both hands, apply a breaking
pressure.
Potting in Lucite. Some samples may be extremely fragile, secured to a header,
or in some way fixed to a mount such that bevel or perpendicular sectioning as
just described would be impossible because of the inability to secure the sample
and prevent its breakage during sectioning. Such samples may be potted in Lucite
using a specimen-mount press and a metallurgical-grade thermoplastic powder such
as AB Transoptic Powder No. 20-3400 (Buehler, Ltd.).
Detailed instruction sheets are given with each press. Following these instructions
will assure an acceptable mounted specimen. In addition to mounting irregular-
shaped objects, flat specimens, such as a semiconductor slice with one face exposed,
may also be mounted within the plastic. An acceptable technique for mounting a
slice or slice section and maintaining the slice face parallel to the Lucite face is as
follows. Using the manufacturer's instructions, make two blank disks of potting
compound each about Ys to ~ in thick. Place them on either side of the slice or
slice section in the cylinder on the baseplate. Position the plunger on this assembly,
place on press insulating plate, lower heater to position, and start heating; apply
approximately 700 Ib/in 2 pressure and maintain until the temperature reaches 80°C;
then increase pressure to 4,000 Ib/in 2 , remove heater, position cooling blocks, and
maintain pressure of 4,000 Ib/in 2 until the temperature reaches SO°c. Then use the
recommended procedure to remove the mounted specimen. The advantages of this
technique over one employing the slice or slice section surrounded by the plastic
powder are (1) positive slice alignment and (2) a very small chance of breaking the
slice by excessive pressure applied during the mounting operation.
The mold defects most usually encountered in slice and device mounting and their
causes are:
1. Improper wetting of specimen by plastic caused by insufficient temperature.
2. Frosted area around specimen caused by insufficient temperature or time
at a proper temperature. Figure 7.9 shows examples of these difficulties.
Precautions to be taken are:
1. Exercise extreme care in orienting sample for ease of future sectioning.
2. Keep specimen clean and dry.
3. Eliminate sharp corners if possible.
Some disadvantages of this form of potting are that the extreme pressure may
fracture the sample, and it is difficult to orient the sample and polish it flat. Section-
ing. details are presented below.
Potting in Teflon. For those samples to be subjected to very strong etchants, potting
in Teflon powder has been used. The suggested procedure4 is to compact Teflon
 Preparation of Samples for Microscopic Examination 195

®
Radial
®
Circumferential Crazing
Unfused
split spl it

~
Edge
~
Burst Burst Cotton boll
shrinking (bottom) (Top)

Fig. 7.9. Compression-molded specimens. (From The Metal Analyst, Buehler Ltd.,
Evanston, Ill., 1965.)

No.8 granular TFE resin at 5,000 Ib/in 2, then sinter in nitrogen 2 h at 380°C. The
heating and cooling cycle must be very slow «50°C/h) between 280 and 38°C
to prevent cracking.
Potting in Casting Resin. Such potting is relatively easily accomplished and may
be used for samples either header-mounted or without mount. Some casting resins
expand excessively during the curing operation and some tend to crack. There is
also a wide range of curing times and temperatures available; so the particular resin
used should be carefully evaluated. The sample should be dry and free of any oil
or grease. The mold may be either of plastic and expendable, i.e., lapped along
with the sample, or of metal coated with a suitable mold release. To simplify lapping
to some approximate predetermined angle, a wedge-shaped preform may be posi-
tioned in the bottom to support the sample. 5 ,6 In the subsequent lapping and
polishing operation, rounding of the sample is likely to occur unless an outer ring
of a harder material such as ceramic is also cast into the resin. 6 This can slow the
polishing operation, however, and unless specifically needed, should not be used.
The actual potting technique is as follows:
1. Mix 7 parts (by volume) of epoxy* with I part (volume) of hardener.t
2. Stir slowly for I min to prevent bubbles.
3. Pour over sample in plastic holder.
4. Place in small vacuum chamber and apply three to five short bursts of
vacuum such that gas bubbles are evolved.
5. Cure at room temperature for 24 h, or at 70°C for 20 to 30 min-light yellow
color when cured.
Sectioning Potted Samples

1. Rough-lap the potted sample on a slow belt surface, having a 180-grit (80-p.m)
belt. Rinse thoroughly.
2. Medium-lap the sample at slow speed (163 r/min) on a low-speed grinder
using (50-p.m) 320-grit abrasive. Rinse thoroughly.

*502 ARALDITE Epoxy, ClBA.

t951 Hardener, CIBA, Summit, N.J.
196 Semiconductor Measurements and Instrumentation

3. Fine-lap the sample at fast speed (1,200 r/min) on a high-speed grinder using
(25-/tm) 600-grit abrasive. Rinse thoroughly.
4. Final-polish the sample at fast speed (1,200 r/min) on a high-speed grinder
using a polishing cloth and 0.03 to 0.05 alumina abrasive. This final polishing
step should be kept to as short a time as is necessary to give a polished
surface. Prolonged polishing will result in undesired rounding of the sample
surface. For very exacting work, a vibrating polisher may be preferred for
the final step. For alternate procedures, see Refs. 5, 6, 53, 54.
5. Etch or stain the sample if required (procedures described later).
6. Using a glass slide, some clay, and the prepared sample, mount for micro-
scope viewing using a hand-alignment press to ensure that the polished
surface is normal to the microscopic optical axis. If an inverted microscope
or an adjustable stage such as is available from various microscope manufac-
turers is used, the mount operation can be eliminated.

7.2 CHEMICAL TREATMENTS

In addition to or instead of the mechanical sectioning just discussed, a wide variety

of chemical treatments are often necessary prior to microscopic examination.
Chemical Safety. When working with the various formulations described, it is
advisable to remember that unless properly handled, acids and solvents are danger-
ous and can be a health hazard. Table 7.1 lists precautions and noticeable results

Table 7.1

Chemical Precautions Noticeable results on contact

Hydrofluoric acid Avoid getting under fingernails* First pain felt within the hour.
Maximum pain occurs in 12 h
Nitric acid Immediate burning sensation.
Rapid blistering. Skin is colored
brown
Acetic acid Burning sensation. Blistering.
White coloration of skin
Hydrochloric Burning sensation. Blisters fast
acid
Sulfuric acid * Burning sensation. Blisters fast.
Slight blackening of skin
Phosphoric acid * Burning sensation. Slow to blister
Chromic acid Avoid breathing dust, will react Discolor and burns
with moisture in respiratory
system and· produce severe
burns
30% hydrogen * Delayed burning. White dis-
peroxide coloration of skin
Solvents * Mild skin irritation; prolonged
breathing may produce after-
effects. Chlorinated solvents are
particularly hazardous

*Concentrated vapors can cause irritation to eyes, nose, and throat. Use with adequate ventilation.
Avoid prolonged or repeated breathing of vapor. Avoid contact with skin, eyes, and clothing.
 Preparation of Samples for Microscopic Examination 197

of contact for most of the chemicals mentioned in this chapter. The most immediate
action required in case of accident is flushing with copious quantities of water.
Should the bum appear severe, or if HF is involved, medical attention is advisable.
Eyeglasses* should be worn during mixing, and rubber gloves can be used to prevent
hand bums. The gloves should never be considered as adequate protection for
immersing hands in corrosive liquids, but rather only as splatter protection, since
a small hole can allow chemicals to get inside the glove unnoticed and produce severe
burning.
Acids and organic solvents should be kept separate during disposal, as they may
react with one another and cause fires or explosions. Seventy percent perchloric
acid (not suggested in any of the formulations in this chapter) should be treated
with extreme care in this regard. The mixing of the etchants should proceed care-
fully, and of course, concentrated acids should be slowly added to water or more
diluted solutions in order to prevent a rapid heat buildup and possible explosion.
When new formulations are investigated, the choice of chemicals should be carefully
reviewed, because it is possible to produce potentially explosive or poisonous mix-
tures. For example, glycerin is often used with various etchants to adjust the
viscosity. However, when nitric acid, which is a prime constituent of most etchants,
is mixed with glycerin, nitroglycerin may be formed. 7 In particular 100 percent white
fuming nitric acid, or nitric acid plus sulfuric acid, combined with glycerin is to be
avoided. Cyanide-metal-plating solutions are reasonably safe when alkaline but if
they should be combined with acids may evolve deadly hydrogen cyanide gas. Some
of the etch components themselves, particularly H 2 0 2 , may decompose rather vio-
lently.s More insidious is the possibility of a delayed reaction such as has been
reported for the mixture 5 HN0 3 , 2 H 2 0, 1 HF, 5 lactic acid. It is unstable because
of an autocatalytic reaction between the lactic acid and the HN0 3 which causes
a delayed (by up to 12 h) rise in temperature and gas evolution sufficient to rupture
storage bottles. 9
Solution Preparation. When mixing etches, be sure to use the correct method for
determining the proportion of each chemical used. The most common method of
expressing composition lists the constituents by parts, e.g., I part HF, 3 parts HN0 3 ,
and 10 parts H 2 0. However, two additional things must be considered: (I) is it
parts by volume or parts by weight; (2) is it I part pure HF, or I part 49 percent
HF, 51 percent H 2 0, and is it constant-boiling nitric acid, dilute nitric acid, or fuming
nitric acid? Considerable confusion can arise concerning the latter point because
of the various commercially available mixtures of most acids. Table 7.2 lists some
of these and illustrates the range possible.
Other possible ways of expressing composition are in terms of normal solutions,
molar solutions, and molal solutions. A one molar solution contains one mole
(gram-molecular weight) of solvent per liter of solution, while a one molal solution
contains one mole per 1,000 g of solvent. A one normal solution is one gram-
equivalent weight (GEW) of solvent per liter of solution. For acids, a GEW is defined
as the gram-molecular weight divided by the number of available H+ ions per
molecule, while for bases, it is the gram-molecular weight divided by the number
of available (OH) ions per molecule. Thus one mole of HCI is one GEW while
one mole of H 2 S04 is 2.0 GEW, and one mole of H 3 (P04 ) is 3.0 GEW.

*The frames of some eyeglasses are themselves a fire hazard, and when combined with organic solvents
are particularly dangerous.
198 Semiconductor Measurements and Instrumentation

Table 7.2

Acetic acid Commercial 36% acetic acid, remainder water

(CH 3COOH) Glacial 99.5-100% CH 3COOH
Acetic (CH 3CO)P, slowly soluble in water to form
anhydride acetic acid

Hydrochloric acid Gas 100%HCl

(HCI) Constant-
boiling 20% HCI, remainder H 2 O
Commercial 38% HCI, remainder water

Hydrofluoric acid Gas 100%HF

(HF) Commercial 49% HF, remainder H 2 O
Commercial 53% HF, 47% H 2 O

Hydrogen peroxide Anhydrous 100%H2 0 2

(H 20 2) USP 2.5-3.5% by wt. of H2 0 2, remainder HP
Hydrogen 30% by wt. H 2 0 2 , remainder H 2O
peroxide
30%

Nitric acid Constant- 68-70% HN0 3, remainder H 2O

(HN0 3) boiling
Dilute Commonly 10%, but may be different
Fuming 87-92% HN03, with some N 2 0 4 , remainder H 2 O

Phosphoric acid USP 85% H 3P04, remainder H 2 O

Diluted USP 10% H 3P0 4 , remainder H 2 O
Glacial 100% HP0 3, sometimes called meta phosphoric acid

Sulfuric acid Commercial 93-98% H 2S04 , remainder H 2O

(H 2 SO4 ) Dilute Commonly 10% H 2S0 4 , but may be different
Fuming H 2SO M free S03' Composition varies, available
up to 80% S03

HF will attack glass; so any etchants using it must be measured, mixed, and
used in containers other than glass. Graduated cylinders, beakers, etc., must be made
of materials such as Teflon or polypropylene. During etching, the temperature rise
of the solution may be enough to soften some plastics; therefore, either cooling or
the use of alternate containers may be necessary. Should it be desirable to maintain
a reasonably fixed pH during etching, buffering can sometimes be used. This is
accomplished by dissolving a salt of the acid (usually a weak acid) in the same
solution so that it can react with small quantities of either acids or bases without
changing the pH appreciably. One of the more commonly used buffered etchants
is the familiar HF-H 20-NH4 F solution.
Etchants for Specific Applications. Table 7.3 gives the composition of the various
etches referred to by name only in other chapters, and Table 7.4 gives some etches
useful for chemically polishing semiconductor surfaces. These are usually required
before etching to reveal dislocations. Samples to be used for transmission electron
microscopy must be thinned; however, the various etchants used for that purpose
are summarized in the electron-microscopy portion of Chap. 9.
 Preparation of Samples for Microscopic Examination 199

Table 7.3. Composition of Etchants

Composition (parts by volume

Name unless otherwise indicated) Reference

A-B etch I ml HF, 2 ml H 20, I g Cr0 3, 8 mg AgN03 10

ASTM etch Modified copper etch No. l. See "Silicon Dislocation
Density Determination," according to ASTM F 47, for
details
Copper etch No. I 20 ml HF, 10 ml HN03, 20 ml H 20, I g 11,52
Cu(N0 3h . 3 H 20. Same as Purdue etch
Bell No.2 54% H 20, 36% NH4F, 10% HF
(buffered
etch)
Copper etch 40 ml HF, 35 ml HN0 3, 10 ml acetic, 25 ml H 20, 1 g 12
No.2 CU(N0 3)2 • 3 H 20
CP-4 (chemical 3 HF, 5 HN0 3, 3 acetic, 0.06 Br2 13
polish No.4)
CP-4a 3 HF, 5 HN0 3, 3 acetic
Cyanide etch 8 g K 3Fe(CN)6' 12 g KOH, 100 ml H 20 14
(ferricyanide)
Dash etch 1 HF,3 HN0 3, 10 acetic, sometimes referred to by ratios, 15
e.g., 1-3-10. Other ratios are also used
Dow 44 g K 2Cr20 7 , II H 20, mix 1 volume of solution with 16
(Secco) 2 volumes HF
Iodine etch 50 ml HF, 100 ml HN03, 110 ml acetic, 0.3 g 12 17
Mercury etch 3 ml HF, 5 ml HN0 3, 3 ml acetic, 2-3% Hg(N0 3)2 (aged 18
in closed bottle for 6 weeks)
p etch 3 ml HF, 20 ml HN0 3, 60 ml H 20 51
Planar etch 2 ml HF, 15 ml HN0 3, 5 ml acetic
Purdue etch See copper etch No.1 11, 52
Richards-Crockers 2.4 X 10-3 molar solution of AgN0 3, in 2 ml HF, 3 ml 20
(modified) HN0 3, 5 ml H 20
Russian etch 10 ml HF, 15 ml HN0 3, 5 ml acetic, 20 ml H 20, 8 mg 12 , 21
2mgKI
Sailor's etch 60 ml HF, 30 ml HN0 3, 0.2 ml Br2, 2.3 g Cu(N0 3h. 22
Dilute 10: I with water before using
Schell 1 ml HN0 3, 2 ml H 20 23
Sirtl etch 50 g Cr0 3, 100 ml H 20; mix with 100 ml HF just before 24
using (rate may be varied by adjusting amount of HF)
Superoxol 1 ml HF, 1 ml H 2 0 2 , 4 ml H 20 (proportional variation 25
sometimes indicated as, e.g., 1-1-4 Superoxol)
WAg 4 ml HF, 2 ml HN0 3, 4 ml H 20, 0.2 g AgN03 26
White etch 1 HF, 4HN0 3 19
W-R 2 HCI, 1 HN0 3, 2 H 20 27

All formulas are for 30% H 20 2, 49% HF, 70% HN0 3, glacial acetic.

Table 7.4. Semiconductor-Polish Etches

Si CP-4; CP-4a; planar

Ge CP-4a; CP-4 (will simultaneously show dislocations)
GaAs I ml HF, 3 ml HN03, 2 ml H 20; 20 ml H 2S04, 75 ml H 20, 5 ml H 20 2
lnAs 99.6 ml acetic, 0.4 g Br 2
InSb CP-4a; 1 ml HF, 1 ml HN0 3 for (TIT) and (110) only
GaSb 1 ml HF, 9 ml HN0 3

All formulas are for 30% H 20 2, 49% HF, 70% HN0 3, glacial acetic.
200 Semiconductor Measurements and Instrumentation

7.3 DELINEATION

This section will treat the art and science of revealing such qualities as p-n
junctions; damaged and polycrystalline regions; and insulating and conducting layers
in metallographically sectioned material as well as on the surface by staining, etching,
and/or plating techniques. The word art is used here in the true sense, for the person
who masters delineation is indeed an artist.
Enough detail will be included in describing each operation so that the required
artistic qualities of the operator will be minimized. To date there is no substitute
for experience; the more samples one investigates, the more proficient he becomes.
Soon, with practice, even those occasional samples of considerable difficulty become
more or less routine. At last one gains the confidence to tackle any problem and,
using a logical sequential approach, usually is rewarded with predictable success or
the discovery of a modified approach yielding superior results. Specific informa-
tion relating to germanium and silicon will be given; however, the technique of
delineation will suffice for other materials. Some delineations need only be made
good enough to reveal qualitative information when viewed macroscopically; others
will be required to be extremely sharp in the 500 to 1,000 X microscopic range so
that quantitative data may be obtained from them.
In some instances, many delineates will be known. Although only a few choice
ones are considered of value, all will be listed. With the very nature of the delinea-
tion and the many sample variables that are possible, a seldom-used delineate may
prove invaluable, since the performance of the delineant is strongly dependent on
the makeup of the sample and the desired results. It will not be necessary to know
the mechanism associated with delineation staining or plating to produce excellent
results, that is, as excellent as the process will allow. *
Table 7.5 lists the surface qualities and references the prescribed delineation
treatment. Except for faults and dislocations, which are covered in a separate
chapter, each quality listed in the table has pertinent notes, hints, and precautions
in the text.

*For information concerning probable stain composition and various mechanisms for the formation
see, for example, P. J. Archer, Phys. Chern. Solids, 14:104-110 (1960); D. R. Turner, J. Electrochern.
Soc., 105:402-408 (1958); R. Memming and G. Schwandt, Surface Sci., 4:109-124 (1966).

Table 7.5. Quick Guide to Slice-Surface Delineation for Si or Ge*

Quality Stain-Etcht

p-n junction or impurity-concentration Etch, 1-3-10; stain, 50-6, 1-3-10

region
Scratches and mechanical damage Etch; Sirt!, 1-3-6 (see Chap. 2)
Resistivity striations Etch; Sirt!, HF-Cu, electropolish
Polycrystalline material Etch; Sirt!, lap (see Chap. 2)
Stacking faults Etch; Sirt! (see Chap. 2)
Dislocations Etch; Sirtl, copper etch, 1-3-10 (see Chap. 2)
Incomplete polishing (Si) Copper-displacement platings, oxidation
Diffusion pipes Stain; 50-6, 1-3-10, anodic oxidation; etch, Sirt!
Oxide pinholes Copper decoration

* See text and following tables for more choices.

tCompositions are listed in Tables 7.3 and 7.7.
 Preparation of Samples for Microscopic Examination 201

Junction and/or Localized High-Impurity-Concentration Delineation. Junction

delineation can be by noting a difference in etch rate between the two types, by
selectively staining one side, or by selective plating metal onto one side. The
reactions involved may be either electrolytic or displacement,28 and the various
solutions reported have been in general chosen to favor one or the other of them.
The surface preparation is touchy, and some procedures require surface abrasion. 29
Further, it has been demonstrated that the stains are so surface-dependent that
selective staining can be made to delineate abraded-unabraded regions of the same
type. Thus their performance often appears to depend much more on art and
temperament than on good scientific principles. This is primarily because competing
reactions are involved in most stains and the results can vary radically with the
dominant reaction. Ambient light, temperature, volume of etchant per unit area,
residual surface oxides, adsorbed impurities, and surface damage have all been
demonstrated to affect the relative behavior of the reactions. Ordinarily, with p+ Ip,
or n+ In, the more heavily doped region will stain darkest, and with p-n junctions,
the p region will usually be the dark one. Reverse staining is not too common, but
does happen. Should it occur, additional information, either physical or electrical,
may be necessary to interpret the delineated results accurately. The exact metal-
lurgical position of the line of demarcation is also of concern, since if it does not
closely coincide with the metallurgical junction, the results can be misleading. The
most common cause of shift is the fact that staining or plating does not occur over
the space-charge region. There can be an appreciable distance between the edge
of the stain and the metallurgical junction, particularly for the higher-resistivity
samples. Also, just because of beveling alone, without any extraneous surface effects,
the space-charge position is distorted and in some cases the junction is displaced
as shown in Fig. 7.10. 30 The effect will be more pronounced the higher the resistivity.
The use of light during staining, which is recommended in almost every case, will
forward-bias the junction and reduce the width of the space-charge region. Based
on simultaneous capacitance measurements, the intensity of light ordinarily used
will usually keep the space-charge width narrow enough to make the errors negligi-
ble. 31 Multiple junctions, particularly PIN structures, 55 may pose additional inter-
pretation difficulties; so an independent check of the junction position should be
made until the idiosyncrasies of the particular procedure used are well understood.

/-
/ .....

'~
---________ynctlon
p+
Metallurgical

(0 )

Fig. 7.10. Effect of angle bevel on the zero-

voltage space-charge position. (b)
202 Semiconductor Measurements and Instrumentation

Fig. 7.11. Localized high-surface-impurity

concentration region delineated by 50-6
etch. Magnification is 34 X .

A typical example to be delineated would be selectively diffused n+ or p+ areas

into a polished slice of Si or Ge. Oxide or nitride masking as well as any metalliza-
tion which may have been employed in fabricating this structure should be removed.
After water rinsing and drying the sample, it should be masked using Apiezon W
wax so that one-fourth of the active area is initially exposed. This allows up to four
different delineation methods to be used. The first and most preferred is 50-6. The
sample is held within 5 in of a high-intensity tungsten lamp such as a DFA * operated
to 90 V ac. A cotton swab is used to paint the unmasked area with 50-6 etch while
the surface is observed through a 10- to IS-power microscope. Either silicon or.
germanium can be stained by this method (Fig. 7.11). When the stain occurs, usually
within 15 s, the sample is quickly quenched in water and dried. This stain is very
tenacious and can be wiped without rubbing off. Some surfaces are such that the
50-6 etch has no effect and no stain occurs. Should that happen, the area is again
painted as before but with a different stain, 50-6 Cu. Stain or mild plating should
occur within 5 s (Fig. 7.12). This plated surface is water-rinsed and dried by blowing
air over it. It should not be wiped, because the copper will rub off.
If no delineation occurs, the second fourth of the surface is exposed. This necessi-
tates complete removal of the wax on the previously masked three-fourths of the
surface. Because surface cleanliness is important, a word of caution is inserted as
a reminder to make sure that all traces of wax are removed from the surface prior
to rewaxing. Any traces of thin wax films will prevent accurate evaluation of

*DFA lamp 120-V, lS0-W General Electric projection lamp.

Fig. 7.12. Localized high-surface-impurity

concentration region delineated by
50-6 eu etch. Magnification is 34 X.
 Preparation of Samples for Microscopic Examination 203

subsequent staining. The next preferred etch is 1-3-10. The sample is again posi-
tioned within 5 in of the light source, and the 1-3-10 etch is squirted on the surface
from a polyethylene squeeze bottle. The surface is microscopically observed. The stain
should occur within 1 to 2 s; after 10 s no stain will occur. This is also a mild etch,
and etching action can be observed by the evolving gas. Rinse quickly and dry after
staining. If the surface remains unstained, another approach is needed.
Another fourth of the surface is exposed and treated as with 1-3-10 but using
1-3-10 Cu. The surface will plate with copper within 5 s, but different concentration
areas will plate differently. This plated surface is water-rinsed and dried by blowing
air over it. It cannot be wiped, because most of the copper will be removed.
Overplating is a common fault and cannot be rectified without repeating the process
in a new area. Results may still be unsatisfactory.
The fourth area is exposed and treated with 1-3-6 etch. The sample is immersed
in 1-3-6 etch for 3 s, rinsed in water, and dried. If the high-concentration areas are
not stained a dark brown, further etching may reveal this. The word "may" is used
here because increasing the etch time will either stain, etch away the critical area,
or not stain at all. Some surfaces will resist staining; however, the low-resistivity
areas in question will be etched more quickly than the surrounding area, forming
a step between the two. This step delineation is also important in detecting area
boundaries. Should troubles still occur, consult the following paragraphs for addi-
tional information.
Delineation of Angle-lapped Specimens. Table 7.6 shows preferred etches for layers
that are epitaxial, diffused, alloyed, or combinations thereof. There is included the
type of etch application, illumination, sectioned angle, perpendicular section type,
visible results, delineation time, usable impurity range, and comments. Table 7.7
gives the composition of these etches, and Table 7.8 is a compendium of additional
formulas to be tried if necessary. Included are a few recipes for electroplating. The'
same general comments made in the previous section are applicable here, and
conversely, most of those to follow can be applied to slice staining.

l. If a section is difficult to stain, do not be discouraged-as many as 10 tries

per etchant may be necessary.
2. Always use a freshly prepared surface for delineating. A surface that is
allowed to remain for several hours prior to staining probably will not stain.
3. Stain all silicon sections dry for best results. If a particular condition
requires a slowing down of the etchants action, a wet section may be used.
Dry using gas jet. Do not wipe dry.
4. Stain all germanium sections wet.
5, In working with epoxy- and Lucite-mounted samples, application of some
etchants may cause the plastic to swell and particles thereof to lie over
the sample~ obscuring the microscopic view. These may be wiped away
using a cotton swab unless the delineation etch contained copper. Swabbing
would remove the copper and perhaps the delineation.
6. If the layer in question is thin, do not use a 7° block for sectioning, for
the layer will appear too small to be adequately measured.
7. A 7° or larger angle will not be illuminated by a vertical illuminating
microscope system along with the unsectioned portion of the sample. If
it is necessary to view (microscopically) both areas, the use of a 5 ° section
or less is recommended.
Table 7.6. Solutions for Delineating Layers in Semiconductors

Method of Visible Layer Delineation Resistivity

Sample Delineant application * Illumination resultst delineated time, s range

Silicon

Diffused
n+/p 1-3-10 1,2,4 Yes 1 p 1-15
50-6
p+/n 1-3-10 1,2,4 Yes 1 p+ 1-15
50-6 <O.OOx/>O.Ox
n+/n 1-3-10 1,2,4 Yes I n+ 1-15
50-6
p+/p 1-3-10 1,2,4 Yes I p+ I-IS
50-6
Alloyed
p+/n 1-3-6 1,2,4 No 3 ... 10-60
Sirt! A I 1-30
n+/p 1-3-6 1,2,4 No 3 ... 10-60
Sirt! A I 1-30
Epitaxial
n/n+ 1-3-10 1,2,4 Yes I 1-15
1-3-10 Cu 2,3,4 Yes 2 1-15
1-3-10 Cu-Mo 4 Yes 2 n+ 1-15 >O.xlsO.Ox
50-6 Cu 2,3,4 Yes 2 I I-IS
1-3-5 1,2,4 Yes I 1-15
1-3-6 3 No I and/or 3 I 10-60
p/p+ 1-3-10 1,2,4 Yes I 1-15
I
1-3-10 Cu 2,3,4 Yes 2 1-15
1-3-10 Cu-Mo 4 Yes 2 p+ I 1-15 >O.Ox/SO.OOx
50-6 Cu 2,3,4 Yes 2 1-15
1-3-5 1,2,4 Yes 1 1-15
1-3-6 3 No 1 and/or 3 10-60
nip 1-3-10 1,2,4 Yes I 1-15
pin 1-3-10 Cu 2,3,4 Yes 2 1-15
1-3-10 Cu-Mo 4 Yes 2 p 1-15
All
50-6 Cu 2,3,4 Yes 2 1-15
1-3-6 3 No 1 and/or 3 10-60
50-6 1,2,4 Yes I 1-15
Miscellaneous
Si-Si0 2 None ... . .. 4
Si-SiC None ... . .. 4
Si-polySi Sirtl A 3 No 3 ... 10-30
Si-ceramic Sirtl A 1 No 3 ... 1-30

Germanium

Epitaxial
n/n+ 50-6 Yes
50-6 Cu 4 No 2 n+ <5
1-3-10 Cu Yes
p/p+ 1-3-10 1,2, 3 4 10-60
1-3-10 Cu 4 2 <5
50-6 Cu 4 Yes 2 p+ <5 >O·x/::;;O.OOx
5-1 4 1 <20
5-1 Cu 5 4 <20
nip 50-6 Cu 2 p <5
HF-H 202 4 Yes 2 n <30
1-3-10 Cu 2 ... <60
1-3-10 3 ... <60
pin 50-6 Cu 4 Yes 2 n <5
1-3-10 Cu 4 2,3 Ge <30
Ge/GaAs 1-3-10 1,2,3 Yes 3 Ge <30 All
Diffused
n'/p
p+/n
n+/n
1 50-6 Cu; 1-3-10 Cu; 4; 4; 5,4 Yes; Yes; Yes
2 and 3;
2 and 3; 2
Plus; Plus; n+ <30; <30; <20
5-1 Cu
p+/p
Alloyed
p+/n 1-3-6 Cu 4 Yes 3 ... <30
n+/p
Combination (diffused and
epitaxial)
n+/(p/p+) 50-6 Cu 4 n+
1-3-10 Cu 4 Yes 2 n+ <30
5-1 Cu 5 3 p, p+
- - '----- -~ - -
Table 7.6. Solutions for Delineating Layers in Semiconductors (Continued)

Method of Visible Layer Delineation Resistivity

Sample Delineant application * Illumination resultst delineated time, s range

p+ /(n/n+) 50-6
1-3-10 Cu 4 Yes 2 n+ <30
5-1 Cu
- - - -_... _ - - - ... _- - - -

InAs, GaAs

Epitaxial
InAs/GaAs 1: 1 1 Yes 1 GaAs 1 All
Clorox: water
GaAs/GaAs(n/n+) 200 g KOH
10 g KAu(CN)4 1 Yes Gold plate n+ 2
H 2 0 to make I liter
GaAs/GaAs(n/n+) I mlHN0 3
5 ml HCI I Yes 1 n+ 900-1,200
Allow to stand 1 h.
3 parts with 2 parts
H 2O
GaAs/GaAs I ml HN0 3
9 ml H 2 O 1 Yes I p 5
0.8 g Fe:j:

Adapted from Charles A. Harper (ed.), "Handbook of Materials and Processes for Electronics," pp. 7-70-7-73, McGraw-Hili Book Company, New York, 1970. Used
by permission.
* Methods of application:
I. Swab with cotton swab dipped in delineate.
2. Squirt delineate on sample, using an acid-resistant squirt bottle.
3. Dip in delineate.
4. Drip delineate on sample, using squirt bottle or cotton swab.
5. Dip swab in 5-1 and then in Cu solution, and allow to drip on sample.
t Visible results are:
'1. Stain will appear.
2. Stain and/or variable-darkness copper plate.
3. Etched step.
4. Color difference.
:j: Sixpenny finishing nail.
 Preparation of Samples for Microscopic Examination 207

Table 7.7. Stain Etchants

Name Composition Semiconductor

50-6 50 ml HF, 6 drops HN03 Si, Ge

50-6 Cu 10 ml (50-6) + 2 drops Cu* Si, Ge
5-1 5 ml HF, I ml HN0 3 Ge
5-1 Cu 10 ml (5-1) + 2 drops Cu* Ge
1-3-5 I ml HF, 3 ml HN0 3, 5 ml acetic Si
1-3-6 1 ml HF, 3 ml HN0 3, 6 ml acetic Si
1-3-10 I ml HF, 3 ml HN0 3, 10 ml acetic Si, Ge
1-3-10 Cu lOml (1-3-10) + 2 drops Cu Si, Ge
1-3-10 Cu-Mo 10 ml (1-3-10 Cu) + 0.1 g Mo03 Si
HF·H 20 2 50 ml HF, 5 drops H 2 0 2 (30%) Ge
Sirt! A 50 g Cr0 3, 100 ml H 20, 75 ml HF Si

*Cu = 20 g CU(N0 3)2' 80 ml H 2 0, 1 ml HF. All formulas are for 30%

H 20 2, 49% HF, 70% HN0 3 0

8. When staining n on p silicon, normally the p layer will stain; however, there
are occasions when the reverse is true and the n layer stains. In most cases
one can observe the p layer staining first very quickly and dark and then
reversing. If the sample is water-quenched during the first darkening, this
combination will remain.
9. Sometimes a stain will quickly form and quickly fade away. Do not attempt
to restain without forming a new surface or using the copper counterpart
of the original delineate.
10. There are cases when the only useful delineate contains copper and plates
very quickly. After rinsing in deionized water, the excess copper is swabbed
off, usually leaving a semistained area.
11. In application of the etchant containing copper, either layer that stains or
copper-plates first, if allowed to remain in contact with the etchant for an
excessive period of time, will be obscured by the complete plating of the
sample. Careful observation will show the first area that was stained/plated
to be the darker one.
12. The application of an etchant containing copper does not necessarily mean
that a copper plating will result. Often only a stain will result. Often a
stain with a copper overplate will result. Sometimes a copper plate will
result with no stain beneath. .
13. Copper-stained samples are the most difficult to interpret because they
usually contain many bright colors and are extremely sensitive to small
surface-variable potentials.
14. In delineating p on p or n on n silicon the use of 1-3-6 is noted as being
used without illumination. It may be necessary to remove the sample from
the etch and subject it to bright illumination, then return it to the etch.
Either the heat of the lamp or the illumination itself seems to enhance the
etching step.
15. Delineant containing copper that will not wet the sectioned surface will not
stain it. Saturation of the delineant with molybdic acid will allow wetting
and enhance staining and/or plating.
16. If an epitaxial n on n+ or p on p+ sample has a very slowly changing
impurity-concentration gradient, it probably cannot be delineated.
208 Semiconductor Measurements and Instrumentation

Table 7.8. Additional Junction Delineants

Mat Composition Comments Reference

Si 10 ml HF, 1-2 drops of red fuming HN0 3 pin, p stains 33

Si 10 g KAu(CN)2' 200 g KOH, deionized H 20 pin, plating 29
to make I liter, temperature 30-70°C, and on n
light. Use lapped surface, 600 or finer
Si 10: 1 dilution of silver fluoride saturated at pin, plating 28
O°C + drop of HF per 5 cm3 of solu- on n
tion + strong illumination. May plate on p
in weak illumination or large volumes of
etchant
Si 50 ml of diluted copper nitrate, 1-2 drops of pin, plating 34
concentrated HF, strong illumination on n
Si Concentrated HF, intense light pin, n-type 34
becomes black
Si 200 g CuS0 4 • 5 H 20, 10 cm 3 HF, 1,000 cm3 pin, plating 35
H 20, bright light. May reverse in dark, or on p-type
if surface is partially polished and partly
lapped
Si 50 ml H 20, 50 ml HF, 0.1 g CU(N03)2 • H 20 36
Si 1 ml HF,20 ml H 20,2 g HI0 4 '2 H 20. Place pin, n bright, 37
drop on surface, watch progress, wash away p dark; p+p,
in 2-3 min p bright; n+n,
n bright
Si 40 ml HF, 20 ml HN0 3, 100 ml H 20, 2 g n+ plates first 38
AgN03 (store under refrigeration). Put
a drop of solution on one surface, await
silver plating, rinse and dry, apply drop of
diluted HN03, rinse, dry
Ge Electrolytic etching in I g NaOH, 10 ml H 20. 39
Use approximately 1 A/cm 2 . p region
etches more rapidly, leaving a step
Ge Place I drop of 1 ml HF, 20 gCuS04 • 5 H 20, pin plating on p 40
80 ml H 20onsurfaceacrossjunction. Apply
voltage across junction in reverse direction.
Should plate on p side. Too high voltage
plate on n, too low, and plating only near
contact
GaAs For junction demarcation, I drop of I ml HF, 41
I ml H 2 0 2 , 10 ml H 2 0 for IS s under intense
white light or, drop of 0.66 g HAuCI4 •
3 H 20, 1,000 ml H 2 0 on surface for I min
under intense light followed by 1 above
GaP 8 ml HF, 40 mg AgN03' 5 g Cr0 3, 10 ml
H 2 0, at 75°C, I to 5 min gives etch step 42
with n of nip etching most rapidly, and n+
of n+/n
GaSb 3 ml HF, 7 ml HN0 3, 10 ml H 20. p region
etches most rapidly, leaving a step at junc- 43
tion
 Preparation of Samples for Microscopic Examination 209

Silicon Epitaxial Depositions. For n-type layers deposited on highly doped n+

substrates, p-type layers deposited on p+ substrates, n-type layers on p-type sub-
strates, and p-type layers on n-type substrates, delineations should offer no difficulty.
Remember that delineated layers less than l/lm thick may be difficult to see if
sectioned at angles greater than 3 When a p-type layer is delineated on a p-type
0
•

substrate or an n-type on an n-type substrate using 1-3-6 or 1-3-10 etchants a white

line will appear at the interface and a light stain will be seen on both layers.
For n on n+, after dripping one of the three recommended etchants on the
sectioned surface; be prepared to quench quickly with water. The reason for the
quick quench is that the n layer plates immediately; prolonged plating will cover
the whole surface, thus obscuring the delineated interface. Water quenching will
stop the plating action. These plated samples may be water-rinsed and dried in
a gas stream; do not swab, blot, or touch the plating, because the copper will be
removed. If interferometric techniques are to be used for thickness measurements,
exercise caution in positioning the cover glass on the plated area.
The first choice of etch ant for p on p+ is a noncopper one, and the p+ region
will turn frosty in appearance within 60 s after application of the etchant. This is
the result of a mild etch on the surface. The p layer will also etch but will not turn
frosty. The other two recommended etches contain copper and hence will plate out
on the p+ regions immediately. As with the n-type material, rapid water quenching
is essential to prevent overplating the sample with a resultant obscuring of the
interface.
The delineation of silicon dioxide, silicon carbide, or silicon nitride requires no
etchant. The interface line between the silicon and dioxide, carbide, or nitride can
be easily seen, as each layer will have a color different from that of silicon. A
polycrystalline silicon layer on an insulating substrate can usually be seen immedi-
ately after sectioning without the use of a de1ineant. However, Sirtl etch will bring
out the polycrystalline silicon grain structure (Fig. 7.13). Quite often this grain
structure is important from a device point of view, a fine grain being more desirable
at times than a coarse grain structure.
Combination of Silicon Diffused and Epitaxial Layer. When delineating a combina-
tion diffused and epitaxial layer with 1-3-10 eu and a cotton swab, constantly swab
off the copper layer as it forms so as to produce a darkened stain area.
Germanium Epotaxial Layers. There is no recommendation for metallographically
sectioning germanium at a 1 angle or less. The germanium is very easily scratched
0

by the polishing abrasive, and these scratches inhibit any staining. Even when using
larger angles, a stain may appear up to a scratch and stop. This is a common effect
and should be taken into consideration before the sample is evaluated. In order

Fig. 7.13. Perpendicular section of poly-

crystalline silicon deposited on silicon diox-
ide. Delineation 5 s in Sirtl A etchant.
Magnification is 135 X .
210 Semiconductor Measurements and Instrumentation

to prevent this partial staining phenomenon, it is suggested that the polishing strokes
be so directed that any scratches formed are perpendicular to the junction or interface
line. Then if the junction or interface line is faint, it can still be used. If the scratches
were parallel to the interface, it would be difficult to differentiate the scratches from
the stain interface.
Damaged Regions (see Chap. 2). Surface damage includes scratches, probe marks,
and areas of improper or incomplete mechanical or chemical polishing. Scratches
may be microscopically observed without delineating. The use of interference
contrast (e.g., the Nomarski interference-contrast attachment used with a Reichert
microscope) reveals scratches very easily. They may also be detected using dark-field
microscopy. In this case the scratch will appear as an illuminated line on a black
background. Although the scratch can be easily seen, not enough detail will be
present to judge the scratch qualitatively in aspects other than relative size. Scratches
may be destructively delineated by etching. Using the etches shown in Table 7.5,
etch time should be kept to a minimum so as not to remove excessive material,
thus making the scratch difficult to see. Scratches on a surface prior to an epitaxial
deposition will usually be propagated through the layer and result in a surface band
which is wider than the original scratch. All the etches shown are acceptable for
(lll)-oriented materia1. Etches such as Sirtl may be used on other than (111) Si
surfaces but do not work particularly well. Germanium etches may be used on all
orientations.
Delineation of thick samples can be accomplished by wax mounting the sample
on a glass slide and etching with agitation. Figure 7.14a shows scratches delineated
in silicon after 6 min in 1-3-6 etchant.
Prior to etching, incompletely polished surfaces appear bright and specular. In
reality there are many unpolished regions which have fine semiconductor and
abrasive particles packed in these regions and polished. Microscopically, the surfaces
look smooth and continuous. A 6-min 1-3-6 etch will remove these packed-in
particles and show the unpolished regions (Fig. 7.14b). An alternate etch for this
purpose is Sirt!; however, the 1-3-6 will delineate without revealing dislocations.
For 1-3-10, use an etch time of 1 h, with agitation each 10 min. The same etchants
may be used for epitaxial layers by reducing the time in order not to etch off the
layer. If the layer is extremely thin (i.e., <2 !Lm), this technique may not be applica-
ble, as no delineation may occur prior to removal of the layer.
To delineate incompletely polished silicon slices without attacking the slice, heat

(a) (b)
Fig. 7.14. Delineation of damaged regions by use of 1-3-6 etch. (a) Polished surface
(magnification is 260X). (b) Scratch (magnification is 126X).
 Preparation of Samples for Microscopic Examination 211

the sample in a 10 percent aqueous sodium tetraborate solution at 80°C for 5 min.
This will remove the packed-in particles and not etch the sample. At the boiling
point, however, the sample will be lightly attacked. Copper-displacement plating
for 1 min in a solution of 1,100 ml water, 5 ml HF, and 5.5 g CuS0 4 -5 H 20 and then
removing the plating in nitric acid is also useful in defining polishing compound
left embedded in the surface and will remove less than 1,000 A of silicon. Viewing
should be with phase or interference contrast.
When polish damage is not gross but is nevertheless present, silicon can be oxidized
(5,000 to 10,000 A) and then etched. The heat treatment will cause the previous
indiscernible defects to become very pronounced. These results should not be
confused with the generation of gross slip patterns which occur during high-
temperature cycles and uneven heating.
Impurity Striations. Most crystals grown from the melt exhibit impurity stria-
tions 44 - 49 which can be displayed by splitting the crystal lengthwise and. treating
the exposed face. Such a procedure also has the advantage of showing the shape
of the growth interface as a function of crystal length. Alternately, a perpendicular
cross section, i.e., a slice, can be examined, in which case spiral or circular patterns
are seen. Ifit is of interest to study the shape of the surface defined by the striations
in more detail, various bevel sections at large angles may also be used. Actual
delineation may be by etching, staining, or plating, an example of which is shown
in Fig. 7.15. Various approaches are summarized in Table 7.9. The striations
revealed are generally referred to as "resistivity striations," but "oxygen swirls" and,
in epitaxial layers, even "stacking-fault swirls" are occasionally mentioned. The latter
may owe their origin to impurities, e.g., carbon, which do not affect etch, plating,
or stain rate and hence do not produce readily observable striations directly, or they
may be due to some swirling surface treatment prior to epitaxy which caused fault
generation. The older literature often considered the resistivity-striation delineation
to be due to multiple p-n junctions. Indeed that may have been true, but they can
also be seen (in silicon at least) when the average resistivity is less than 0.01 Q-cm
and is almost certainly due to variations less than the amount required for type
change.
These techniques by their very nature are subjective and, from the magnitude
of resistivity-variation standpoint, are just an indication of a variation. Attempts
to correlate them with measurements made by very fine spreading-resistance probes

Fig. 7.15. Striations delineated by anodiza-

tion.
212 Semiconductor Measurements and Instrumentation

Table 7.9. Resistivity Striation Delineation

Mat Composition Reference

Si 3 m1 HF, 5 ml HN0 3 , 7 ml glacial acetic. Use on polished surface 44

Si Electrochemical oxidation in 10% KN0 3 ; 0.1 g molybdic acid for a few
minutes. Si is anode, current densities approximately 15 mA/cm 2 •
Best in O.OOx to O.Ox range, will work to 4 n-cm
Si 50 ml HF, 15 mg Cu(N0 3h, remove copper plate with HN0 3 , repeat
twice more.
Si 40 ml HF, I drop HN0 3 every 30 s for 5-15 min under illumination 63
-use chemically polished surface
Si Wet surface with methanol, place in solution of 40 ml HF, I drop of 45
HN0 3 • One additional drop after 30 min, and after 1 h under illu-
mination, remove after 2 h. Works on resistivities of from 10 to
100 n-cm-use chemically polished surface
Si Kamper etch, very complex, see references for details 64
Ge Acid solution of copper sulfate. Adjust electrolyte resistivity, pulse 46
length, and repetition rate for best results. Ge is cathode
Ge For n-type. Alkaline plating solution of 16 g NaOH, 1 g CuS0 4 • 47
5 H 20, 19 g tartaric acid, water to make 100 m!. Use Ge as anode,
1,000 V, 10 pulses/s
Ge 52 ml H 2 S0 4 , 210 g CuS04 • 5 H 2 0, 948 ml H 2 0. Use as an electrolyte 48
with Ge as cathode. Use current densities of from 1.5 to 30 A/cm2 ,
voltage up to 1,500 V. Use pulse rate of 3 pulses/s
InSb 3 HF, 5 HN0 3, 3 acetic, 11 H 2 0 (used on 211 plane) 49

have met with only limited success. However, they do give excellent spatial resolu-
tion of the variations. With the proper choice of etch and multiple-beam inter-
ferometric observation, exceedingly closely spaced striations can be observed.
Diffusion Pipes. Pipes are small unplanned diffused regions which provide ohmic
paths between transistor collectors and emitters. They are shown schematically in
Fig.7.16a. If a cross section of the device can be made which includes such a pipe,
then the staining procedures already discussed will show it. Unfortunately, only a
few per emitter can cause device failure and yet the chance of blindly stopping the
sectioning process at a point which will show one is rather remote. There are,
however, two alternate procedures that will often show collector-emitter shorts
(besides the electrical tests) and thus, by inference, pipes. One is to etch a slice
in Sirtl etch after all metal and oxide have been stripped away. If the collector and
emitter are still shorted, enhanced electrochemical etching will cause the pronounced·
change in the emitter regions shown in Fig. 7.16b.
By externally biasing the slice, stain and/or anodic oxide can be grown in the
shorted emitters. 56 The advantage of using an external voltage is that low-voltage
breakdowns and soft junctions can also be detected. If an integrated-circuit slice
is used, the p substrate is made plus. Thus the substrate-collector junction is for-
ward-biased while the collector-base junction is reverse-biased and the emitters will
all be floating unless they are shorted to the collector or unless the voltage is high
enough to break down the collector-base junction. The back and sides of the slice
must be protected by wax from the solution, which may be a 5 percent HF solution
for staining or a 10 percent NaCI0 4 solution for anodic oxidation. When oxidizing,
for a fixed current, the voltage will increase with time, or a fixed voltage will result
in a pronounced reduction in current. Accordingly some sort of manual or automatic
control must be used.
 Preparation of Samples for Microscopic Examination 213

C ~Base)
Pipe Collector

(a) (b)
Fig. 7.16. Diffusion pipes and their effect on Sirtl etching. The arrows indicate
the shorted emitters.

p-n-Jundion Decoration. 57 The stain and plating methods of displaying junctions

depend on delineating either the p or n region and assuming that the junction lies
along the boundary. It is also possible to decorate the high-field region at the
junction by a line of dielectric particles. 58 In order to sustain the necessary field,
the surface must be damage-free (e.g., not a lapped surface), and to obtain the
necessary particle mobility the particles must be finely divided and carried in a liquid
suspension. The suspending liquid must be nonconductive and have a dielectric
constant much less than that of the particles. Three to five-micrometer barium
titanate mixed with carbon tetrachloride in the proportions of I g of powder per
100 cm3 of liquid works satisfactorily for Si and Ge. The mixture can be applied
by eyedropper onto the surface.
Oxide Pinhole Decoration. Oxides grown or vapor-deposited on silicon can have
tiny holes or cracks in them which are too small to be seen without replication
electron micrography. * The holes can, however, be decorated and observed with
modest magnification. One of the earliest schemes was to put the slice with an oxide
layer in a Cl59 or HCI environment at temperatures above 900 C for I to 10 min.D

Wherever the hot gas contacts the silicon, a hole will be etched that is readily
apparent. The main disadvantage of this method is the high-temperature corro-
sive-gas requirement. The problem is eliminated by the use of either a copper-plating
or an electrophoretic solution to deposit readily visible particles about the pinhole.
Copper sulfate-water solution will produce copper plating about holes. If dielectric
liquids such as acetone, isopropyl alcohol, or methyl alcohol are used and the anode
is made of copper, nonconductive copper compounds will be formed and transported
to the pinhole site. 6o Ten to two hundred volts for a few minutes is required when
the anode is in the form of a wire screen held normal to the slice surface. 61 Elec-
trography can also be used by sandwiching a paper saturated with an aqueous

*For a discussion of the detection of these and other kinds of oxide defects, as well as an extensive
bibliography, see Werner Kern, Characterization of Localized Defects in Dielectric Films for Electron
Devices, Part I, Solid State Tech., 17:35-42 (March 1974); Part II, 17:78-84 (April 1974).
214 Semiconductor Measurements and Instrumentation

solution of benzidine chloride between the slice and an electrode and applying a
voltage across the assembly. Wherever current flows, i.e., at pinholes, the benzidine
will be oxidized to a colored state and form a map of the defect 10cations. 60
Package Opening. When examining encapsulated units, package opening is
sometimes tedious, and without care the device inside can be decimated before there
is a chance to examine it. There are many package types, but in general they can
be classified as metal, ceramic, or plastic. Metal cans can be opened by using a
micromilling machine,62 sander, file, or for very thin packages, even a knife blade.
A vise or chuck to clamp the package should be used, and great care taken to prevent
particles from the can or cutter from falling on the semiconductor surface. (A re-
markable number of "spurious particles" are found in packages which have an
analysis identical to knife blades and tweezers.) Ceramic packages usually have a
lid which can be snapped off rather easily using either a knife or diagonal cutters.
During such operations it is easy to crack the semiconductor material; so it is well
to practice on scrap units before attempting to open the one of interest. Plastic
packages (ordinarily epoxy or silicone) can in principle be dissolved, or at least
softened so that the plastic can be pulled away. For specific solvents, follow the
plastic manufacturer's suggestions. Alternately, virtually all such encapsulants can
be removed in hot sulfuric acid. It is important that the acid be dry; otherwise
aluminum metallization will be removed in the process. Boiling for several minutes
before use will provide a suitably dry acid.
After the package, or at least the package top, has been removed, there may still
be a thick layer of deposited Si0 2 over the surface which will make examination
difficult. These oxides will almost always dissolve much more rapidly in HF than
thermal oxide, and may thus be stripped away with little damage to the underlying
device unless considerable overetching is allowed. For oxides deposited over metal-
lization, an eraser, preferably electric, can be used for removal.

REFERENCES

1. Hans Elias, Three-dimensional Structure Identified from Single Sections, Science,

174:993-1000 (1971).
2. W. A. Gaunt, "Microreconstruction," Pitman Publishing Corporation, New York, 1971.
3. J. S. Hanson, Microsectioning: A Metallographic Technique for Semiconductor Devices,
IBM J. Res. Develop., 1:279-288 (1957).
4. Z. Nagy and J. McHardy, Mounting Specimens in Teflon for Electrochemical Studies,
J. Electrochem. Soc., 117:1222-1223 (1970).
5. M. C. Wong, Metallography of Semiconductors, Metals Rev., 38:(5):5-6 (1965).
6. R. H. Carter and F. P. Gagliano, The Metallographic Preparation of Microminiature
Devices, Microelectron. Reliability, 7:301-303 (1968).
7. R. D. Packard, Addendum to Notes on the Chemical Polishing of Gallium Arsenide
Surfaces, J. Electrochem. Soc., 112:871-872 (1965).
-8. Cecil V. King, Dangerous Chemicals in the Laboratory, J. Electrochem. Soc., 112:251C
( 1965).
9. S. F. Bubar and D. A. Vermilyea, Explosion of a Chemical Polishing Solution, J. Electro-
chem. Soc., 113:519 (1966).
10. M. S. Abrahams and C. J. Buiocchi, Etching of Dislocations on the Low-Index Faces
of GaAs, J. Appl. Phys., 36:2855-2863 (1965).
11. D. Navon, R. Bray, and H. Y. Fan, Lifetime of Injected Carriers in Germanium, Proc.
IRE, 40:1342-1347 (1952).
 Preparation of Samples for Microscopic Examination 215

12. W. J. Feuerstein, Etch Pit Studies on Silicon, Trans. A/ME, 212:210-212 (1958).
13. F. L. Vogel, W. G. Pfann, H. E. Corey, and E. E. Thomas, Observations of Dislocations
in Lineage Boundaries in Germanium, Phys. Rev., 90:489-490 (1953).
14. E. Billig, Some Defects in Crystals Grown from the Melt, I. Defects Caused by Thermal
Stresses, Proc. Roy. Soc. London, A235:37-55 (1956).
15. W. C. Dash, Copper Precipitation on Dislocations in Silicon, f. Appl. Phys., 27:1193-1195
(1956).
16. F. Secco d'Aragona, Dislocation Etch for (100) Planes in Silicon, f. Electrochem. Soc.,
119:948-951 (1972).
17. P. Wang, Etching of Germanium and Silicon, Sylvania Tech., 11 :50-58 (1958).
18. F. L. Vogel, Jr., and L. Clarice Lovell, Dislocation Etch Pits in Silicon Crystals, 1. Appl.
Phys., 27:1413-1415 (1956).
19. Donald H. Lyon, The X-Factor in Germanium, Western Elec. Engr., 7:3-12 (October
1963).
20. M. S. Abrahams, Dislocation Etch Pits in GaAs, 1. Appl. Phys., 35:3626-3628 (1964).
2l. V. N. Vasi1evskaya and E. G. Miselyuk, The Problem of Visualization of Dislocations
in Germanium by Etching, Soviet Phys. Solid State, 3:313-318 (1961).
22. Allegheny Electric Chemical Co., Tech. Bull. 6, June 1958.
23. H. A. Schell, Etch Figures on Gallium Arsenide Single Crystals, Z. Metallk., 48(4): 158-
161 (1957).
24. E. Sirtl and A. Adler, Chromic-Hydrofluoric Acid as a Specific System for the Develop-
ment of Etch Pits on Silicon, Z. Metallk., 52:529-531 (1961).
25. H. A. Schell, Etch Figures on Germanium Single Crystals, Z. Metallk., 47:614-620 (1956).
26. R. H. Wynne and C. Goldberg, Preferential Etch For Use in Optical Determination of
Germanium Crystal Orientation, 1. Metals, 5:436 (1955).
27. J. G. White and W. C. Roth, Polarity of Gallium Arsenide Single Crystals, f. Appl. Phys.,
30:946-947 (1959).
28. P. A. Iles and P. S. Coppen, On the Delineation of p-n Junctions in Silicon, f. Appl.
Phys., 29:1514 (1958).
29. S. J. Silverman and D. R. Benn, Junction Delineation in Silicon by Gold Chemiplating,
f. Electrochem. Soc., 105:170-172 (1958).
30. J. M. Lavine, The Behavior of p- and n-doped Contacts in a Space-Charge Depletion
Region, Solid State Electron., 1:107-122 (1960).
3l. D. Eirug Davies, The Implanted Profiles of Boron, Phosphorus and Arsenic in Silicon
from Junction Depth Measurements, Solid State Electron., 13:229-237 (1970).
32. C. S. Fuller and J. A. Ditzenberger, Diffusion of Donor and Acceptor Elements in Silicon,
f. Appl. Phys., 27:544-553 (1956).
33. Harry Robbins, Junction Delineation in Silicon, 1. Electrochem. Soc., 109:63-64 (1962).
34. P. J. Whoriskey, Two Chemical Stains for Marking p-n Junction in Silicon, 1. Appl. Phys.,
29:867-868 (1958).
35. D. R. Turner, Junction Delineation on Silicon in Electrochemical Displacement Plating
Solutions, f. Electrochem. Soc., 106:701-705 (1959).
36. John R. Edwards, Evidence of Phosphorus N-Skin on Silicon from Vapor Transport,
f. Electrochem. Soc., 116:866-868 (1969).
37. I. F. Nicolau, Junction Delineation and Dislo,cation Revealing in Silicon by the
HI0 4-HF-H 20 System, Solid State Electron., 12:446-448 (1969).
38. I. Berman, N+N Delineation in Silicon, f. Electrochem. Soc., 109:1002-1003 (1962).
39. R. W. Jackson, Simple Method of Revealing p-n Junctions in Germanium, f. Appl. Phys.,
27:309-310 (1956).
40. Reinhard GIang, Location of Diffused p-n Junctions on Germanium by Electrodeposition
of Copper, f. Electrochem. Soc., 107:356-357 (1960).
4l. J. C. Marinace, Diffused Junctions in GaAs Injection Lasers, f. Electrochem. Soc.,
110:1153-1159 (1963).
216 Semiconductor Measurements and Instrumentation

42. Robert H. Saul, The Defect Structure of GaP Crystals Grown from Gallium Solutions,
Vapor Phase and Liquid Phase Epitaxial Deposition, J. Electrochem. Soc., 115:1184-1190
(1968).
43. S. J. Silverman, Junction Delineation in GaSb by Differential Chemical Etch Rate,
J. Electrochem. Soc., 109:166-168 (1962).
44. A. F. Witt and H. C. Gatos, Impurity Heterogeneities in Semiconductor Single Crystals,
in Rolf R. Haberecht and Edward L. Kern (eds.), "Semiconductor Silicon," The Electro-
chemical Society, New York, 1969.
45. T. F. Ciszek, Solid-Liquid Interface Morphology of Float Zoned Silicon Crystals, in Rolf
R. Haberecht and Edward L. Kern (eds.), "Semiconductor Silicon," The Electrochemical
Society, New York, 1969.
46. Paul R. Camp, Resistivity Striations in Germanium Crystals, J. Appl. Phys., 25:459-463
(1954).
47. J. A. M. Dikhoff, Cross-sectional Resistivity Variations in Germanium Single Crystals,
Solid State Electron., 1:202-210 (1960).
48. Gurion Meltzer, Minute Resistivity Variations in Germanium Crystals and Their Effect
on Devices, J. Electrochem. Soc., 109:947-951 (1962).
49. F. Morizane, A. F. Witt, and H. C. Gatos, Impurity Distributions in Single Crystals,
J. Electrochem. Soc., 113:51-54 (1966).
50. B. Jansen, A Rapid and Accurate Method for Measuring the Thickness of Diffused Layers
in Silicon and Germanium, Solid State Electron., 2:14-17 (1961).
51. W. A. Pliskin and R. P. Gnall, Evidence for Oxidation Growth at the Oxide-Silicon
Interface from Controlled Etch Studies, J. Electrochem. Soc., 111 :872-873 (1964).
52. R. V. Jensen and S. M. Christian, Etch Pits and Dislocation Studies in Silicon Crystals,
RCA Industry Service, Lab. Bull. Ll3-1023, Mar. 5, 1956.
53. W. A. Hassett and W. R. Hechler, Metallographic Polishing Techniques for Semiconductor
Components, Semicond. Prod., 6:27-30 (October 1963).
54. J. J. Gajda, Evaluation of Semiconductors through Angle Sectioning and Junction
Delineation, SCP and Solid State Tech., 7:17-21 (November 1964).
55. K. Schuster, Determination of the Lifetime from the Stored Carrier Charge in Diffused
psn Rectifiers, Solid State Electron., 8:427-430 (1965).
56. Murlidhar Kulkarni, John C. Hasson, and George A. A. James, Mapping of Electrical
Leakage in Transistors by Anodic Oxidation, IEEE Trans. Electron Devices,
ED-19:1098-1102 (1972).
57. P. A. Iles and P. J. Coppen, Location of p-n and l-h junctions in Semiconductors, Brit.
J. Appl. Phys., 11:177-184 (1960).
58. H. E. Bridges, J. H. Scaff, and J. N. Shive (eds.), "Transistor Technology," vol. 1, D. Van
Nostrand Company, Inc., Princeton, N.J., 1958.
59. S. W. lng, Jr., R. E. Morrison, and J. E. Sandor, Gas Permeation Study and Imperfection
Detection of Thermally Grown and Deposited Thin Silicon Dioxide Films, J. Electro-
chem. Soc., 109:221-226 (1962).
60. P. J. Besser and J. E. Meinhard, Investigation of Methods for the Detection of Structural
Defects in Silicon Dioxide Layers, in "Symposium on Manufacturing In-Process Control
and Measuring Techniques for Semiconductors," vol. 2, 1966.
6l. W. J. Shannon, A Study of Dielectric Defect Detection by Decoration with Copper, RCA
Rev., 31 :431-438 (1970).
62. William C. Weger et al., "Reliability Handbook for Silicon Monolithic Microcircuits,"
prepared on contract NAS 8-20639, Texas Instruments, Inc., 1967.
63. W. D. Edwards, Liquid-Solid Interface Shape Observed in Silicon Crystals Grown by
the Czochralski Method, Can. J. Phys., 38:439-443 (1960).
64. K. R. Mayer, A Simplification of Klimper's Striation Etch for Silicon, J. Electrochem.
Soc., 120:1780-1782 (1973).
 8
Microscopy and Photography

One of the major methods of examining semiconductor materials and devices is

with optical magnification. This includes hand-held magnifiers, low-power binocular
stereoscopic microscopes, and low- and high-power binocular nonstereoscopic mi-
croscopes. In addition, various attachments such as interferometers and phase and
interference contrast are also useful. Polarization studies, widely used for mineral-
ogical investigations, are normally possible only with infrared-image converters
instead of conventional eyepieces, as most semiconductors are not transparent to
visible light. For storing the results of the various optical examinations, both low-
and high-magnification photography are routinely used, and most laboratory metal-
lurgical microscopes include a companion camera. When greater magnification is
required, particularly in combination with increased depth of view, scanning electron
microscopes are used. Their cost, complexity, and size preclude their being as widely
disseminated as optical microscopes, but their introduction into the semiconductor
industry has had a tremendous impact on the understanding of microcircuit inter-
connection systems.

8.1 BASIC OPTICSl-4

The simplest form of magnifier is a single planoconvex lens as in Fig. 8.la, which
will, if the object is between the focal point and the lens, present a magnified upright
virtual image. Because of spherical and chromatic aberrations, the magnification
of such lenses (which is given by I + 250/j, where fis the focal length in millime-
ters) is usually limited to lOX or less. Aberrations can be minimized by a combina-
tion oflenses such as that shown in Fig. 8.lb, but still, the practical limit ofmagnifi-
cation is 10 to 20 X.
When great~r power is required, compound microscopes can be used. The simplest
embodiment consists of an objective which projects a magnified real image, and
an eyepiece which produces a further enlarged virtual image of the real image. The
magnification is now given by the product of the magnification of the objective and
the magnification of the eyepiece. The objective magnification is approximately
given by L (Fig. 8.2a) divided by the focal length of the lens. L is the tube length
of the microscope and is usually about 200 mm. * This figure depicts both lenses

*The "standard" for biological instruments is 160 mm, but metallurgical microscopes tend to have
longer paths.

217
218 Semiconductor Measurements and Instrumentation

Magnification
Eye given by
1+ 250/F

(a)

Double lens
aeI)
Achromat Triplet
Fig. 8.1. Lens system for a simple microscope.
The shaded and clear portions in (b) are made
of different composition glass. A clear cement is
(b) used to join the surfaces.

1~
A I I

~~
--- --- --:;::..-::=:.. .:::..:::. . - - -
(a)

(b)

Partially silvered mirror

Oblique reflected (brightfield)

Inclined reflected
(dark field)

(c 1 (d 1
Fig. 8.2. Microscope optics. (a) Compound microscopes. (b) Arrangement of field
and aperture diaphragms and auxiliary condensers for vertical illumination. (c)
Relationship of various types of illumination. (d) Annular dark-field illuminator.
 Microscopy and Photography 219

as single elements, but in an actual microscope they will ordinarily be multielement

in order to minimize various distortions. Since most metallurgical specimens are
opaque, some form of lighting from the top is required. For low-power work, in
which the optics are usually quite large and several inches away from the object,
an external lamp beamed to the surface is adequate. For high-power work, the
vertical illuminator shown in Fig. 8.2b is used. A partially silvered mirror M is used
to direct light down through the objective. Figure 8.2c shows more details of the
various lighting possibilities.
In particular, it is to be noticed that if the incoming light ray has an angle of
incidence greater than can be obtained by projecting through the objective, the
reflected ray will also fall outside the objective and will thus not be collected.
Therefore, any image formed will be only from light scattered by an irregular
surface. Such an arrangement is called dark field and is particularly useful in
examining an otherwise smooth surface for small holes or protuberances. There are
several methods (depending on the manufacturer) of producing the required oblique-
ness, but Fig. 8.2d is typical. Objectives designed for dark field are larger in diameter
than those for bright field because of the extra space required for the coaxial lighting.
It is possible in some designs to shift the bright-field source from side to side as
in Fig. 8.2c to introduce shadows which can aid in interpretation. In the case of
instruments without this feature, removing the light from its housing and moving
it about sometimes helps.
For purposes of both convenience and contrast, a uniform but variable intensity
over the sample is required; and for eliminating glare, the light-spot size entering
the objective must be controlled. In the most common type of illumination an image
of the condensing lens is formed in the objective-image plane (Koehler illumination).
The lighting will then appear uniform, regardless of local variations in the source
intensity. The openings which control the intensity and area are referred to, respec-
tively, as the aperture and field diaphragms.
To ease eye fatigue and minimize the effects of small particles in the eye fluid
drifting across the eye's field of view, binocular microscopes are commonly used.
In these, the optical path splits after it leaves the objective and goes to two eyepieces
approximately in the manner shown in Fig. 8.3. Separation of the eyepieces to
accommodate different interpupil widths may change the optical path length of one
eyepiece and require it to be refocused, depending on the exact optical separation
used.
True stereoscopic vision requires that slightly different images be presented to the
two eyes. This may be accomplished by using a completely separate set of optics

Eyepieces

~ 1

_Light
source

Fig. 8.3. Optical path for binocular microscope.

220 Semiconductor Measurements and Instrumentation

for each eye and directing them both at the same object, but from slightly different
angles. Because the magnification is usually less than 150X, there is considerable
distance between the object and the objective and external indirect lighting can be
used; however, care must be taken to ensure equal illumination of both eye fields.
With the binocular optics just discussed it is possible to get some stereo effect by
inserting limiting apertures in the beams, but it is seldom used.
Objectives. Achromatic objectives are corrected spherically for one color, and
chromatically for red and blue. * By the use of fluorite positive lenses and barium-
flint negative lenses, it is possible to focus red, green, and blue rays simultaneously
as well as to correct spherically at two colors and thus considerably improve the
color correction. (These are referred to as apochromats.) The latter lenses do,
however, have to be further compensated by special eyepieces. Fluorites, sometimes
called semiapochromats, are intermediate in correction between achromats and
apochromats. If a cover glass is being used, the light will be refracted as it goes
through it and will introduce spherical aberration in an objective which is fully
corrected. Therefore, objectives designed for use with cover glasses should not be
used without them (and vice versa). Under normal circumstances metallurgical
microscopes do not use cover glasses over specimens; so biological-microscope
objectives should not be used with a metallurgical microscope.
Parfocal objectives are mounted so that as the nosepiece is rotated to bring them
sequentially into position, little focusing is required from one objective to the next.
For a set which is not exactly parfocal, they can often be corrected by putting washers
between the individual objectives and the nosepiece. Most manufacturers use
standard objective threads and eyepiece-tube diameters, but tube lengths are not
standard and care must be exercised in interchanging optics. Objectives are de-
scribed in terms of the type of correction (achromat, fluorite, etc.), magnifica~ion
(3.2X, lOX, etc.) or focal length, numerical aperture (which is defined in Sec. 8.2),
working distance, whether they are oil- or air-immersion, and whether designed for
a specific tube length (L of Fig. 8.2a) or are infinity-corrected and require an auxiliary
lens built into the tube. Depth of field and image intensity are dependent on
numerical aperture (N.A.); they vary as (l/N.A.)2 and (N.A.)2, respectively, and are
seldom specified. Typically, for an N.A. of 1.4, the depth of field will be in the
quarter-micrometer range.
Eyepieces. Despite the single-lens eyepiece shown in Fig. 8.2, high-quality eye-
pieces use a field and an eye lens combination, each of which may consist of multiple
elements in order to provide for various optical corrections. Three of the more
common kinds are the Huygens, the Kellner, and the Ramsden. The first, shown
in Fig. 8.4a, is characterized by two planoconvex lenses separated by half the sum
of their focal lengths. The real image is formed between the two lenses, and while
the combination corrects chromatic aberrations of the complete eyepiece, a reticle
(which must be placed in the plane of the real image) would be distorted since it
is between the lenses and they are not individually corrected. The Ramsden eyepiece
removes this difficulty by having the real image fall outside the lens combination
as in Fig. 8.4c. It also consists of two planoconvex lenses, in this case of equal focal
length, separated by two-thirds of a focal length. The Kellner eyepiece (Fig. 8Ab)

*Spherical aberration is caused by rays passing through the lens near its center not crossing the optical
axis at the same point as rays from farther out. Chromatic aberration is due to a single ray of white
light being broken up into a multitude of rays with slightly different angles because of dispersion in
the lens.
 Microscopy and Photography 221
H Field lens shifts image
- ~~====f----tl'""'=~~P1'~------:
, Real Ee I
rel;~d image I:ns Eye

(a)

_c>R==:~
Field Eye Eye
lens lens
(b)

Field lens
Eye lens Eye
Real image
and reticle

1.1I4f .1. Z/3f Either lens .1

(c)

Fig. 8.4. Optics for various eyepieces. (a)

Field lens Eye
Huygens. (b) Kellner. (c) Ramsden. Cd) lens
Orthoscopic. (d)

has an achromatic doublet for an eye lens, and it and the field lens are separated
by an amount which places the real image in the plane surface of the field lens.
Therefore, if a reticle is to be used, the Kellner must be slightly misadjusted to place
the image just outside the field lens. This may be done and it will still retain most
of its advantages of an achromatic correction and an exceptionally wide distortion-
free field.
For more complete correction, or to compensate for the objectives, and in some
cases to obtain longer eye relief (a particular problem with Huygens as the power
is increased much beyond 10 X), more complicated configurations are used. Com-
pensating eyepieces are designed for use with apochromatic objectives and are
over-color-corrected. For example, periplanes are made by making the eye lens of
a Huygens a doublet, and orthoscopes use the structure of Fig. 8.4d. These may
also be used with fluorite objectives and high-magnification achromats. They do
not, however, perform well with low-power achromats. Eyepieces for photographic
use are especially designed to produce a flatter field. Some varieties cannot be used
for direct viewing by eye, since they will only project a real image.

8.2 OPTICAL IMAGE QUALITY

Objects are made visible because of various combinations of the following:

1. Variation in reflectivity giving rise to reflection images (of most importance
in metallurgical examinations)
2. Variation in refractive index giving rise to refraction images (applicable only
222 Semiconductor Measurements and Instrumentation

if there are transparent particles or layers on top of the opaque reflecting

surface)
3. Diffraction patterns
4. Color variation due to absorption within the material
5. Color or intensity contrast due to interference (very useful in semiconduc-
tor-device studies)
6. Polarization effects
Successful examination depends on taking the necessary steps to enhance whichever
phenomenon is most amenable to interpretation, and to minimize any instrumental
weakness. Enhancement by operation on the sample itself, such as etching or staining
to produce differences in reflectivity, is covered in detail in Chap. 7. This section
is devoted to the instrumentation itself.
Refraction. For transparant objects, refraction at the various surfaces can be
obscured if they are illuminated from many directions simultaneously. The use of
a sector aperture illuminator or the more conventional adjustable plane-glass reflec-
tor (Fig. 8.2c) will provide for nonequallighting.
Diffraction and Resolution. Diffraction effects produce banding which limits
resolution and thus determines the maximum magnification that can be obtained.
It can be shown that the wider the beam of light accepted by a lens, the less
pronounced the diffraction effects will be. The angular aperture (AA), which is
the angle between the most divergent rays which can pass through a lens and form
an image, is a measure of this beam width. If the object and the front surface of
the lens are immersed in a liquid of refractive index n greater than 1, the effective
beam width is increased. To account for that possibility, the numerical aperture
N.A defined by

..
NA · AA.
= n X sln- (8.1)
2-

is now commonly used instead of angular aperture for describing all lenses, whether
or not they are designed for immersion. If they are used in air, n = 1, N.A reduces
to sin (AA/2) and has a maximum value of 1, since 180 is the largest possible
0

collection angle. For the case of n = 1, it is most difficult to design quality lenses
with an N.A greater than 0.95. However, by using a high-index-of-refraction oil
between the lens and the object, N.As of 1.4 are not uncommon.
The minimum distance s of two lines on an object which can just be separated
in an image is approximately given by
A
s=--- (8.2)
2N.A
where A is the wavelength of the light being used. Subsequent magnification must
then ordinarily be used to allow the eye to resolve the image. The objectives are
normally made with as high an N.A as possible, while the follow-on magnification
by eyepiece and/or camera can be with a lower N.A lens since after initial magnifi-
cation, lesser resolution is required. The optical system thus behaves very much like
a low-noise amplifier in which the first stage is carefully constructed to provide
enough gain at the lowest possible noise level to make the signal into the following
stages substantially above their noise level.
The resolving limit of the eyes of various individuals varies but is of the order
 Microscopy and Photography 223

of 250-,um line separation. On this basis, magnification of approximately 1,000 times

the numerical aperture is required for the eye to see all possible detail. That is,

_ _S-"ey<...;e,--_ = 250 250

(8.3)
Smicroscope S V(2 N.A.)
and for A of 0.5 ,urn, which is green light located approximately in the center of the
white-light spectrum,

250 = 500(N.A.) = 1,000 N.A. (8.4)

S 0.5
Actually, more magnification is often helpful, both because individual eyes vary,
and because it is sometimes more convenient and easier to study somewhat larger
images. Table 8.1 gives numerical aperture and resolution for a number of objectives
which are representative of various manufacturers. Further maximum eyepiece
magnifications based on the foregoing criterion are also included. It is true, however,
that one can with care make good useful photographs which have magnifications
considerably greater than those listed in the table.
Images of fine points will appear as points surrounded by faint concentric circles.
An edge (or other bright-line source) will have dim lines running parallel to it and
may sometimes be misinterpreted as a layered structure. Often only the first intensity
minimum on either side of the edge or point will be visible and will give rise to
a black band surrounding the bright image. Picture framing can also occur because
of a sloping region (e.g., an oxide step) reflecting light out of the optical system,
from pseudo Becke lines arising from abrupt changes in reflecting surface height, *

*True Becke lines arise when a transparent object with vertical sides is immersed in a medium of
different index of refraction and viewed in transmitted light. Some of the light from the object will
be refracted in such a manner that when the microscope is defocused, light or dark framing occurs.
Pseudo Becke lines are observed in metallurgical microscopes when there is a rather abrupt change in
the surface elevation. Because of the defocusing, some light from one elevation is superimposed on
the image from the other elevation and thus makes one side appear darker and the other brighter.

Table 8.1. Magnification and N.A. of Typical Metallurgical Microscope Objectives

Max Max usable

Resolution, * Separation, usable eyepiece
Magnification N.A. pm lines/mm magnification t magnificationt

3.2 0.06 4.0 250 60 19

5.5 0.15 1.7 590 150 27
6.5 0.2 1.3 770 200 31
8 0.2 1.3 770 200 25
16 0.30 0.8 1,250 300 19
20 0.50 0.5 2,000 500 25
32 0.65 0.4 2,500 650 20
45 0.66 0.4 2,500 660 15
80 0.95 0.26 4,000 950 12
100 1.36 0.18 5,500 1,360, oil immersion 13.6
160 0.95 0.26 4,000 950 6
160 1.40 0.18 5,500 1,400, oil immersion 8.8

*Based on Eq. (8.2).

tBased on Eq. (8.4). Actually, considerably more magnification can often be useful.
224 Semiconductor Measurements and Instrumentation

from something similar to a true Becke line caused by an abrupt change in the
thickness of a high-index transparent layer overlaying the reflecting surface, and
from interference effects in oxide and nitride slopes.
Ordinarily such banding only complicates interpretation, particularly when view-
ing in dark field when the bands are bright, but for low-contrast or extra small
objects, diffraction patterns may be required for any visibility. Ultramicroscopy
(based on the Tyndall effect) deliberately makes use of diffraction to produce visible
images of objects far smaller than can be resolved. Such images have little resem-
blance to the actual object shape but can be used to estimate numbers. Such
microscopes are normally used to study colloids, but various modifications have been
used to follow the growth of Si-O chains in silicon.
Inexpensive microscopes often have pronounced diffraction effects, which explains
why they may actually show faint height variations better than higher-quality
instruments and are sometimes preferred. Iflower resolution is desired for additional
contrast, the system N.A. can be decreased by stopping down the aperture dia-
phragm. This same reduction of the aperture diaphragm will also cause a more
pronounced pseudo Becke effect. In either case the result is increased contrast. A
good place to look for diffraction lines that can be easily identified as such is along
the sharp edges or the apex of sharply defined etch pits. When focused on them,
the effect of reduced resolution can be demonstrated by closing the aperture dia-
phragm and noting the increase in the number of lines. Figure 8.S shows the surface
of a low-temperature (100) silicon epitaxial layer taken with a quality metallurgical
microscope with the field stop nearly closed, and quite open. Viewing through an
inexpensive microscope with fixed stops gives results comparable with Fig. 8.5b and
demonstrates the earlier thesis that superior optics sometimes give poorer contrast.
Such effects do obscure fine detail and under ordinary circumstances should be
avoided. If the diaphragm can be varied, for optimum aperture, focus on an object,
remove an eyepiece, and adjust until the image of the light source which appears
at the back plane of the objective just fills the lens. For any given magnification,
an oil-immersion lens will reduce diffraction.
Color. Color filters may sometimes be used to produce better contrast of colored
objects. To lighten a particular color, choose a filter of the same color. To darken

(a) (b)
Fig. 8.5. Increased contrast from (a) to (b) accomplished by
stopping aperture diaphragm and slightly defocusing. The
subject is a low-temperature silicon epitaxial deposition on
a (100) silicon substrate. Magnification is 259 X.
 Microscopy and Photography 225

Table 8.2. Filters for Improving Contrast

Color of object Filter

Red Green
Yellow Blue
Green Red
Blue Yellow or red
Brown Blue
Purple Green

it, choose a filter which absorbs light of that color (Table 8.2). They are applicable
only if the object coloration arises from absorption and not from interference. It
might also be noted that green is useful for reducing eye fatigue. Because a single
color will reduce chromatic aberration and give better resolution, narrow-bandpass
filters are often used, with green again being recommended. Further, since the limit
of resolution is inversely dependent on wavelength, resolution and thus image quality
can in principle be increased by using the shortest possible wavelength for which
the lens is corrected.
Contrast. Dirty eyepieces or objectives can and often do degrade image quality.
In such cases they should be cleaned with a dry lint-free cloth. Lightly attached
particulate matter can be removed by blowing with a syringe or pressured, filtered
inert gas. For greasy surfaces (eyepieces are particularly susceptible to this), a liquid
cleaner may be required. Care should be taken either not to choose one which will
dissolve the cement between the lenses or else to be very careful and keep it away
from exposed joints. Xylene is usually satisfactory, but if there is any doubt, the
specific manufacturer should be consulted. Lens paper which has been touched by
fingers will transfer grease back to the lens, but if the paper is first rolled and then
torn in two, a fresh, clean surface is exposed. These and various other causes of
image degradation are summarized in Table 8.3.
Glare will reduce contrast, but even with minimum glare, if the object is highly
reflecting, and if the illumination intensity is too high, detail will be obscured. Glare
can arise because of reflections from the first surface of the back lens of the objective
(hence one reason for coated optics), from dust on various surfaces, and from
miscellaneous reflections caused by metal protuberances in the microscope. It is most
serious when looking at surfaces with little contrast, and for any given instrument
can be minimized by controlling the field diaphragm.
This diaphragm should never be open more than just enough to illuminate the
complete field of the microscope, and for critical cases, it may be reduced much
more, and thus illuminate only a small portion of the normal field. Scatter is reduced
in proportion to the area reduction, and yet the light intensity of the region covered
remains unchanged. Some lenses in a given manufacturer's series may be much
worse than others, and in such cases, a different objective is the only correction
available. The state of the observer's eyes also contributes to the amount of contrast
and detail that can be seen, and to assist them, a darkened room is often helpful.
Occasionally, when image quality suffers, it can be traced to a chipped objective.
Some instruments have spring-loaded objectives to minimize this possibility, but the
best way to prevent such disasters is to exercise care in focusing, particularly with
the higher-power, shorter-focal-length (and much more expensive) objectives. It is
good practice to examine the exposed objective surface periodically with a low-power
226 Semiconductor Measurements and Instrumentation

Table 8.3. Some Causes of Poor Image Definition

Microscope vibration Particularly noticeable at higher magnifications when

operating in multistory buildings
Poor focus Can arise during photography either from failure to focus
on screen properly or because screen and film are not
exactly in same plane
Dirty objectives Scatter of light due to small particulate matter or films
on surface
Chipped or etched objectives The first occurs fairly regularly because many semicon-
ductors are harder than glass and will almost always
damage the objective if it is inadvertently lowered onto
them. The latter is caused by viewing objects just etched
in HF bearing solutions and not properly washed
Cloudy lenses Cement holding lenses sometimes fails and allows ele-
ments to separate
Dust on internal lens. prisms, or May cause blurring or dark spots to appear in field of
mirror surfaces view
Excess glare See section on contrast
Use of objective designed for cover
glass
Use of oil· immersion lens without Most oil-immersion lenses are identified by a black band
oil, or reverse around the bottom
Use of wrong refractive index oil
Using eyepieces not properly cor· It is usually good practice to use objectives and eyepieces
rected for objective from the same manufacturer
Using objectives designed for
different tube length
Stereo-optics misaligned In addition to blurring, this problem causes severe
eyestrain. To check, see if an object in the center of
the field remains immobile as first one and then the
other eye is closed

magnifier for signs of chipping, dirt, etc. An eyepiece from the same microscope
will work quite satisfactorily for this purpose.
Contrast of surface-height variations can be considerably improved by dark field.
Figure 8.6 shows the surface of an integrated-circuit bar in normal bright-field and
in dark-field illumination. Phase contrast also is very useful for surface-variation
contrast, as are microscopes which use diffracted light only to view the object. This
can be accomplished by using an annular stop in the incoming beam and blocking

(a) (b)
Fig. 8.6. Comparison of (a) dark- and (b) light-field images. The subject is a
dielectric-isolated integrated circuit.
 Microscopy and Photography 227

entry of that direct ring of light after it passes back through the objective after
reflection (similar to the phase-contrast system except that opaque material is used
instead of a phase shifter). The diffracted beam will be attenuated only slightly
and will produce considerably more contrast than when mixed with the direct beam.
Probably the best way to obtain maximum height-variation contrast is to use either
a multiple-beam interferometer or a polarization interferometer such as the
Nomarski. In either case, sensitivities of a small fraction of a wavelength are
possible. The polarization varieties show height changes as color differences and
give a direct display of the surface, whereas the multiple-beam instruments produce
displacements in fringes as they traverse steps. Because of these differences, the
polarization interferometers usually give a more interpretable image, but the multi-
ple-beam better allows for quantitative step-height measurements.
Focusing. Focusing with parfocal objectives should always start with the lowest-
power objective, since this will give the greatest working distance and will minimize
the chance of jamming the objective into the object. When rotating parfocal objec-
tives while in focus, care must be taken if the surface being viewed is in a depression,
e.g., an integrated-circuit bar in a delidded package, since high-power objectives
may not clear the depression walls. If a fuzzy view of the light-source filament
becomes visible, the objective is too close to the object and should be slowly backed
away. For lenses that are not parfocal, the objective may be lowered to just above
the surface (as observed by placing the eye at object level and watching the spacing)
and focused by moving the objective away from the object. For instruments with
Koehler illumination, the field-diaphragm leaves (Fig. 8.2b) will be in simultaneous
focus with the object. It may therefore be stopped down and focusing done on the
edge of one of its leaves. This procedure is particularly useful when the object is
highly reflecting and difficult to focus on. When all else fails, dust particles may
have to be added to the surface to help find it. Small x-y motion of the object while
moving the focus control will also sometimes help. When long working distance
is required, objectives of low magnification and long focal length must be used.
The overall magnification can be maintained by using a higher-power eyepiece, but
resolution may be lost (see Table 8.1).
When oil immersion is used, the average slice is so light that oil surface tension
will pull it to the lens and prevent focusing unless it has been firmly attached to
the stage. Further, the oil itself is better put on the lens than on the edge of a slice,
since it will usually run off the latter before the lens can be positioned. Remember
also that lenses for oil immersion are especially designed for oil of a given index
and should not be used in air or with oils of other indexes. Similarly, dry (air)
objectives should not be used with oil, since resolution will suffer.
Binocular and multiple-viewing microscopes have provisions for focusing the
remainder of the eyepieces after one eyepiece-objective combination has been
focused. This provision is necessary because most eyes are slightly different and
individual focusing will minimize eyestrain. The eye will accommodate some degree
of misfocusing but will tire easily; so when using the microscope for extended times,
the following procedure should be used.
1. Relax eyes.
2. Focus fixed eyepiece-objective combination.
3. Focus the variable eyepiece by moving it all the way out (plus, if it has a
scale), then slowly moving it in. When the eyepiece is changed in this
direction, the image comes into view from infinity. If the eyepiece is moved
228 Semiconductor Measurements and Instrumentation

in too far and the image blurs, do not attempt to focus by moving it slowly
back out, while viewing, but rather start the procedure all over. Otherwise,
"pulling" of the eye may occur.

8.3 SPECIALIZED OPTICAL EQUIPMENT

In addition to the basic microscope, there are a number of specialized instruments

and attachments that are quite useful to the semiconductor viewer. By using addi-
tional beam splitters, for example, one can add more than one set of eyepieces to
a microscope so that two people can simultaneously view and discuss the same
object. Projection screens are sometimes used, but with the reflected light used in
most metallurgical microscopes, the image is quite dim, and resolution suffers
because of screen grain. If a rotating screen composed of lenticular mirrors is used,
resolution is considerably improved,* but at the expense of increased complexity.
A television pickup and monitor can also be used for multiple viewing, but if it
is in black and white, much information is lost, since color is an important identifica-
tion feature in most microscopic examinations.
For comparing two similar objects, e.g., masks, microscopes with two separate
objectives and provision for combining their images in a common binocular head
are available. The combined view may be either a split field, i.e., the input from
one objective occupies one half of the field and that from the other objective the
other half; or the two images can be superimposed. For very high magnification
work, metallographs are sometimes used. They differ from other microscopes in
being much more rigid as well as more versatile, since they have a wide assortment
of attachments which can be precisely located because of the optical bench used
for mounting the optics.
Toolmaker's microscopes have x-y specimen stage travel as well as the vertical
position controlled by precision micrometers and are monitored by dial indicators
so that distances between surface features can be easily measured. When very small
crystals are studied, the angles between various exposed planes can be determined
by using a microscope (micro goniometer) with both a calibrated rotating stage and
calibrated inclinable optical axis. 6 By inclining both the light source and the micro-
scope at angles of 45 to the viewing surface as shown in Fig. 8.7, a light-section
0

microscope is formed which enables step heights to be measured. 7 It does not have
as fine a resolution as a microinterferometer but is more applicable to production
measurements.
The equipment just described is all derived from modifications of the basic optics
of Fig. 8.2. There is, however, other optical equipment dependent on additional
phenomena which are also of use in examining semiconductor materials and devices.
Examples of these are phase contrast, interference contrast, and polarizers.
Polarization Microscopy. In materials which are not optically isotropic there are
three kinds of polarization effects that may occur in transmitted light. The most
common is double refraction (the index of refraction is dependent on the direction
of the E vector). Some materials are optically active; i.e., the direction is rotated
as it traverses the material. Finally, some materials have absorption coefficients
which vary with the direction of the E vector (pleochroism).
In order to study these effects, polarizers are used. These are optical elements

*Aerial Image Projection System, Vision Engineering, Ltd.

 Microscopy and Photography 229

Eye

):r t7 Ret""

~~
/ V~"~
90"

,, ",
1L-lI----- "
, ,- - - -- - '-----------------'
(0 )

( b)
Fig. 8.7. (a) Optical path for a light-section microscope. (b) An example of line
displacement.

which resolve randomly polarized light into two perpendicular components and then
transmit only one of them. The plane of polarization bears a fixed relation to the
physical construction of the polarizer and can be changed with respect to a given
set of coordinates by rotating the polarizer about its optical axis. If a second polarizer
(analyzer) is placed in a linear polarized beam and rotated until the plane of
polarization of the light it transmits is 90 to that transmitted by the polarizer, little
0

light will pass, and the combination is referred to as crossed polarizers.

Polarization microscopes have two extra optical elements: a rotatable polarizer
which is inserted between the light source and objective, and the analyzer, which
may be placed anywhere in the optical path between the object and the eye. Usually,
230 Semiconductor Measurements and Instrumentation

Polarizer
/Analyzer
Filter \

W~ ~
Fig. 8.8. An infrared conoscope for
observing strain in silicon. The infrared
Infrared image
converter converter has image-forming optics
incorporated into it. For l.l-J-tm oper-
Converging Sample
ation, a silicon filter and Polaroid HR6
lens polarizing sheet may be used.

however, it is placed between the objective and the eyepiece and is fixed in angular
position with respect to the microscope frame. Objectives used with polarizing
microscopes must be strain-free and are usually specially manufactured. For that
reason, ordinary objectives are not recommended for use in polarization microscopes.
When an isotropic object is viewed between crossed polarizers, the field will remain
dark regardless of its orientation. Uni- or biaxial specimens will appear bright in
each quadrant as they are rotated unless viewing is along one of the optical axes.
To determine quickly whether a sample is isotropic or not, instead of a polarizing
microscope, a conoscope may be used. In it the light is converging when it passes
through the crystal and gives rise to very distinctive interference patterns. Figure
8.8 is a schematic of a low-power conoscope for large samples, and Fig. 8.9 shows
the kind of patterns to be expected. Figure 8.10 shows a conoscopic picture taken
from an infrared-image converter of a uniformly strained silicon slice and illustrates
the strain conversion of the normally isotropic cubic silicon to uniaxial behavior.
If reflected polarized light is used, i.e., a microscope with an opaque illuminator,
anisotropic reflection coefficients are observed for all noncubic crystals and can aid
in separating various material phases. Conoscopic observations of isotropic materials
by reflected light will give cross configurations similar to those observed on uniaxial
materials in transmitted light.s Polarization microscopy as just described is seldom
used in semiconductor studies except to search for strained regions.
Interference Microscopy. Interferometry can be combined with various lens
systems to give microinterferometry and is very useful in obtaining the contrast
necessary to study small-scale surface steps. In some forms, the conventional dis-
placed fringes associated with interferometers are observed. 9 In others, interference
is used to enhance the image contrast. 10, 11 Figure 8.11 a and b shows two versions
of the first type. The simple arrangement of Fig. 8.11a is widely used in conjunction
with angle-lap and stain techniques (see Chap. 7). If the reference surface has a
low reflectivity and high transmission, two-beam Fizeau interference fringes are
observed. The reference may be a thin piece of glass (e.g., a cover glass) or an
attachment designed to fit over the end of the microscope objective. The more
sophisticated dual-beam instrument of Fig. 8.11b has the advantage of not requiring
a reference surface in close contact with the surface being observed. It can be used

Fig. 8.9. Conoscopic interference patterns ob-

served by transmitted light. (a) The optical axis is
perpendicular to the surface. (b) The optical axes
lie in a plane perpendicular to the surface and lying
(a) (b) along a line connecting the apexes of the hyper-
Uniaxial Biaxia I bolas.
 Microscopy and Photography 231

Fig. 8.10. Transmission conoscopic picture

of a strained silicon slice.

at relatively low power to study deviation from planarity of slice surfaces. 12,13
Two-beam instrumentation is useful for detecting deviations from planarity down
to perhaps one-tenth wavelength. When the reference and the surface to be ex-
amined are lightly aluminized to increase reflectivity,9 multiple reflections occur, the
lines are sharpened, and with considerable care the sensitivity can be increased to
5 to 10 A.
There are also methods of obtaining image contrast by interference. The simplest
one is the conventional phase contrast described below. However, more elaborate
techniques based on polarization colors are more pleasing to use and usually give
a higher-intensity image.

A
.b
?I
I
I
I I
%----~--
I I
E
I
I
I

Object
Y I Reference
surface

(a)

A.
c:b
9I
I
a, I

~-~ffi~-+-0++~- L
Fig. 8.11. (a) A partially reflecting transparent reference
surface placed over the object yields interference fringes.
'Reference
surface
rI
(b) The reference surface is widely separated from the ob- +
'5? 02
ject through the use of a micro-Michelson interferometer. Object .d;;"
The optics 01 and 02 are matched microscope objectives. (b)
232 Semiconductor Measurements and Instrumentation

Phase Contrast. One method for increasing contrast is to introduce phase shift
in a portion of the beam as shown in Fig. 8.12. The source-light beam has a stop
so that only an annular ring of light is transmitted. In the plane between the
objective and eyepiece where that ring is imaged, a phase plate ring is placed which
shifts the phase of the light going through it by a quarter wavelength. This shift
affects all the direct beam, but most of the light reflected or diffracted from the ob-
ject will not pass through the phase plate and from that point on will be of different
phase from the background light. The phase shifter is usually placed on the end
of the objective housing, and a phase-contrast objective can be recognized by the
plate, as well as by manufacturer's designations on the objective. The annular stop
in the incident beam must be changed in size to accommodate each objective; this
may be accomplished by rotating a disk with a number of apertures matched to
specific objectives. Further contrast can be obtained by simultaneously reducing
the intensity of the background by placing a filter in series with the phase ring.
In order to provide for a continuous transition from phase to bright field, the source
ring can be moved with respect to the objective. If it is far away (Fig. 8.12b), the
light will pass unimpeded through the center of the phase plate, there will be no
phase change, and the illumination is bright-field. Moved closer, it will pass through
the phase-shifting region and there will be the phase contrast just described. Closer
still, it will be imaged outside the retarding region and a bright field will again be
seen. Further movement will begin to shift the light path over to the edge where
it will be blocked by the microscope body and give dark field. Phase contrast was
originally conceived for improving contrast of colorless specimens in transparent
fluids through differences in index of refraction, but when applied some years later
to opaque samples, its greatest usefulness proved to be making small variations in
height visible. It will also aid in detecting any variations in refractive index of
transparent surface films as well as defining regions which produce differing amounts
of phase shift when the incident light is reflected from them.
Interference Contrast.lO Rather than using a flat plate as a reference surface

Source
ring
stop

--_t--I
I
~~Ou~c'~9ht I

1iT~~- Ring image and groove coincide

+1+ for phose controst
r:::::::~=::::J<E--- Source ring images in plane of phase'
plate. The plate is sufficiently
different in thickness in that region
Objective to shiftthephase by A12.

Opaque surf.::.;ac::;.e_ _ _-L-_ _ __

(a)

r¥J=::n
t t
I
Image of source
Phase contrast Bright field Bright field
as described in
(a) above Fig.S.12. Phase-contrast op-
( b) tics.
 Microscopy and Photography 233

J- ( b)

~ (c)

Analyzer

Polarizer

Biprism
'-'='----.,----'
II
Fig. 8.13. Interference contrast. The light is 1\
1\
resolved into two perpendicular components I \
which emerge from the biprism with slight path <¢::»
deviations. The biprism is oriented at a 45 0 I I
\ I
\ I
angle with the polarizer. The analyzer and
6
polarizer are crossed. Thus, any phase differ- II
ence due to a path difference of the two rays \ \ Object

will appear as a polarization color. (a)

for obtaining interference as was done in the dual-beam instrument, or shifting the
phase of the scattered and diffracted light with respect to the direct beam reflection
as in phase contrast, it is possible to separate the incident white light into light with
two perpendicular planes of polarization and laterally displace one beam slightly
with respect to the other as shown in Fig. 8.l3a. If the two beams strike a flat surface,
they will be reflected in phase and upon recombination will yield a normally colored
image. However, if there is an incline as in Fig. 8.13b, the two will be out of phase,
and upon recombination, will give a polarization color as previously discussed. The
color then is a measure of the slope of the incline. Were the step to be abrupt as
in Fig. 8.l3e, the two levels would be of uniform but different color. In order that
the beam displacement will not produce a banding effect, it is limited by optical
design to less than the limit of resolution of the optics. There are several designs
differing in detail, but the one which has been most accepted for semiconductor
work is that of Nomarski. It is an exceedingly useful technique for studying slices
at various stages of processing. Figure 8.14 is comprised of two photographs of
approximately the same area of a silicon slice which had been lightly etched. Figure
8.14a is an ordinary photograph taken through a conventional microscope and shows
little detail. Figure 8.14b was taken using the same microscope with a Nomarski
interference attachment and shows much additional detail. It is also possible to
provide a form of interference contrast built entirely into an eyepiece, which can
then be used with any microscope. 10 Such eyepieces, however, are relatively rare
and seldom used.
234 Semiconductor Measurements and ~nstrumentation

(0) (b)
Fig. 8.14. Thc cnhanced contrast from (a) to (b), available through the use of a
Nomarski interference-contrast attachment. Magnification 224 X in each case. The
subject is a silicon slice etched with Dow etch.

Infrared Microscopy. Infrared imaging is useful for examining semiconductors

which are not transparent to visible light. An ordinary microscope can be equipped
with a camera and infrared film, e.g., Kodak 1M, or have an infrared-image converter
substituted for the eyepiece and used out to the cutoff of the converters, which is
at about 1.2 p.m. When observing silicon, which will transmit only past 1.1 p.m, the
light converted is reasonably monochromatic because only wavelengths longer than
1.1 p.m will reach the converter, and only light with wavelengths less than 1.2 p.m
will be converted. Since the light has a rather narrow wavelength spread, lack of
chromatic corrections is not serious, and spherical aberration can be corrected by
adjusting the spacing between front and rear lenses of the objective in the same
manner that cover-glass thickness variations were accounted for around the turn
of the century. Reasonable image quality is thus possible, although the converter
lens systems have severe barrel distortion.
More sophisticated systems can be constructed using either infrared vidicons and
electronic scanning or a single-element detector and mechanical scanning. Consid-
erable additional freedom is afforded with the mechanical scan, since lenses or
mirrors and detectors can be chosen for optimum performance over any desired
wavelength range. 14 - 16 Longer wavelengths, for example, are sometimes helpful in
delineating impurity-concentration variations, since free-carrier absorption increases
with increasing wavelength. Infrared microscopes can also be used in the reflection
mode, like a conventional metallurgical microscope, when looking for doping varia-
tions since reflectivity, as well as transmissivity, is a function of carrier concentration.
When applicable, reflected light is much simpler, since the back of the slice need
not be polished. Thin films of opaque semiconductors can be viewed without
infrared, and in particular, silicon-on-sapphire from its very nature (thin, on a
transparant backing) can be studied directlyY
The temperature variations over a transistor or integrated circuit can also be used
to give a "picture" by using a suitable scan system and detector and the thermal
emission of the object itself as the source. Such pictures or thermal contours are
most helpful in locating hot spots and current crowding in new designs. 18 ,19
 Microscopy and Photography 235
8.4 PHOTOGRAPHy20-26

The photography most likely to be encountered is photomicrography, i.e., the taking

of high-magnification pictures with the aid of a compound microscope. However,
unity magnification to perhaps 50 X is very useful for studying slices, small crystals,
and packages. Techniques for this magnification range are similar to those of
conventional close-up photography and give rise to photomacrography. The latter
does not use a compound microscope for image formation but rather relies on a
single lens, just as in conventional photography.
Photomicrography is most conveniently combined with a microscope having a
separate tube for camera attachment, though conversion kits to slip over an eyepiece
are available. There is no requirement for a lens in the camera; however, if it has
one, it may be used by focusing the microscope in the normal manner, setting the
camera focus to infinity, and placing its lens close to the eyepiece. Some cameras
are fixed-length and are designed to be in focus with the microscope, but the most
versatile employ a ground glass so that the image can be viewed directly. Photo-
macrography may use a camera with a specially designed close-up lens or, in some
cases, standard lenses with provisions for moving them farther from the film in order
to increase magnification. For example, either rings or bellows attachments are
available for many 35-mm cameras. Sixteen-millimeter movie-camera lenses are
particularly recommended for close-up work. 20 They, as well as conventional lenses,
will usually work better used backward because of their basic optical design.
Exposure. The matter of proper exposure is most easily handled by using an
exposure meter. They are available commercially or can be made in the case of
photomicrography by taping a CdS cell over a spare eyepiece and using it in
conjunction with a suitable resistance-measuring circuit. As long as the eyepiece
used with the camera is of the same power as the one to which the photocell is
attached, meter readings are independent of objective. Calibrations can then be
made involving whichever of the variables, time or meter reading, is most conven-
ient. For very low light levels, film speed is often slower than the published index
number (failure of the reciprocity law); so appropriate corrections may be required.
Table 8.4 indicates the severity of the problem as exposure times exceed I s. Some-
times it is tempting to vary the light-source intensity in order to bring the light level
at the eyepiece to a standard level to match a fixed film speed and shutter time.
However, since this method changes the filament temperature and hence spectral

Table 8.4. Effect of Nonreciprocity on Film Exposure*

Normalized time-light intensity

Exposure time, s product for same density on film

0.001
0.01
0.1
1.0 1.3
10 2
100 4
1,000 16

"Typical values. Manufacturer's recommendations for specific film used

should be followed.
236 Semiconductor Measurements and Instrumentation

distribution of light, it is not recommended for color photography. When a print

is relatively dark but detail can be seen, it is usually necessary to quadruple the
exposure time or intensity in order to get a usable picture. If the picture is just
slightly on the dark side and lacks a little detail by being a slight gray, doubling
the time should be adequate. The latitude of various films will vary, and in the
interest of film conservation, it is recommended that a chart similar to that of Fig.
8.15 be made for each film type being used. It can then serve as a guide in correcting
for improper exposures. Thus, even without an exposure meter or regular use of
a given camera-light combination, the proper exposure can be quickly found. Notice
that if a completely dark, or a completely washed-out film results, the light or time
could be changed by at least a factor of 16 without shifting to the other extreme.
When using macrophotographic lenses with j-stop adjustments, remember that each
full stop (f/l.4, fl2, f/2.8, f/4, f/5.6, f/8, f/ll, f/16, f/22, fl32, and fl45) changes
the light intensity by a factor of 2. The larger the number, the less the intensity.
If rings are used between the lens and camera body to increase magnification, the
f number is decreased and may be calculated from
Vf
feff = F
where V is the distance from the lens to the film surface and F is the focal length
of the lens. The exposure time T will then be
V2
Tnew = Torig F2
Focusing. Accurate focusing can be troublesome, even with a ground-glass screen.
The grain of the glass will often be so large that visual resolution is lost. To minimize
this effect, a small portion of the screen should be clear. For example, a ~-in­
diameter plug of ground glass can be removed by cavitroning or core drilling and
a clear one substituted, or a cross can be drawn on the ground surface and a small
piece of glass cemented to it. The cement will reduce the effect of the grinding and
make the glass in that region appear practically clear. The image is then focused
on the clear surface and can even be viewed with a low-power hand magnifier for
better definition. This procedure is particularly helpful when the image is very dim,

Fig. 8.15. Test photograph to show film latitude and assist in estimating
exposure times. Each step doubles the time.
 Microscopy and Photography 237

(a) (b)

Fig. S.16. Picture framing which occurs when the aperture diaphragm
is nearly closed and the microscope is slightly defocused. This provides
a quick method of determining which side of a microscopic discontinuity
is raised since (a) if defocusing is by moving the objective toward the
surface, the bright line will be over the raised region. (b) Moving it away
causes the bright line to lie on the low side of the boundary.

but it does require accurate alignment of the eye to the light rays passing through
the clear region. Under high magnification it can be extremely difficult on a screen
to tell when the system is exactly focused, even with a clear-glass screen. There
will appear to be a range of focusing where the image appears no clearer. However,
should there be framing of the image by black or white pseudo Becke lines, they
can be used as a guide. As the focus is changed, the framing can be seen to change
from white to black, to black to white (or vice versa). Proper focus has been reached
when the transition occurs and the lines appear neither black nor white. Figure
8.16 shows the two extremes of framing. If the photograph is to be used for subse-
quent measurements, it is imperative that the proper focus be used; otherwise the
framing as illustrated in Fig. 8.16 can cause large errors. When a very exacting
focus is required, or if the film plane does not exactly coincide with the glass plane,
it may be necessary to take a sequence of pictures with the fine-focus control set
at different positions.
At high magnification, the edges of the field may show distortion or fuzziness no
matter how careful the focus. This may be because the face under observation is
not absolutely perpendicular to the optical axis, and that is therefore the first thing
that should be checked. An unmatched eyepiece and objective can cause similar
results, as can poor-quality optics. The only choice in such cases is either to accept
the quality or to upgrade the optics.
Depth of Field and Detail. In photomicrography, the depth of field is determined
by the microscope objective N.A. For instruments without aperture control, the
depth is thus controlled exclusively by the objective choice. If the aperture is
variable, it can be stopped down to decrease N.A. and increase depth of field.
However, resolution may suffer. When high power, maximum resolution, and great
depth of field are all required at once, a scanning electron microscope may be the
only solution, but sometimes a composite photograph can be made either by multiple
exposures on the same film as the point of focus is changed or by taking a series
of pictures with different regions focused, cutting the different sections from the
photograph, and making a composite. If the height contours are linear, e.g., viewing
down a slope, the latter is quite practical. Attempting multiple exposures on the
same film will give a washed-out appearance and overexposure if many steps are
used.
In photomacrography, the fstop of the lens and the magnification can be varied
238 Semiconductor Measurements and Instrumentation
11

10

7
E
.:. 6 \
:E
~ 5 \
'+-
o
:::c. 4
Q)
\
o 3

2
\
~/22 Fig. 8.17. This curve relates the depth of detail at-
fl16
fill Va tainable at optimum camera aperture as the final mag-
5 8 10 12.5 15 20 nification at the print is varied. (Reproduced with
Mag nif i cation permission from copyrighted Kodak Publication N-12B.)·

to change the depth. However, as magnification and f number increase, depth of

detail may become more important than depth of field. In principle, depth of field
should continue to increase as thefnumber increases, but when the point is reached
where diffraction effects are predominant, depth of detail suffers. Figure 8.17 shows
a curve which relates depth of detail to total photograph magnification, and gives
the f number required at various magnifications. 20 Total magnification is the product
of that of the camera and any subsequent enlargements. However, enlargement
magnification should probably not exceed 3 X.
Film Resolution. The eye can resolve the order of 5 lines/mm; so for no subsequent
enlargement, the film should have at least that capability. Table 8.5 summarizes
typical film resolution. However, if the total magnification, objective X
eyepiece X enlargement, exceeds the magnification shown in Table 8.1, empty
magnification will still result, regardless of the resolution. The choice of magnifica-
tion might depend on aesthetics or on the desire to provide visible separation of
some special features of the subject. In the latter case, remember that the limit of
resolution of the eye should be the guide for minimum magnification.
Color Rendition. It is important when photographing objects such as oxide colors
or colors on specific devices that color contrast be maintained on the film. In general,
when photographed in daylight flash or fluorescent light, greens, reds, and blues

Table 8.5. Resolution of More Common Film Types

Type Film speed (ASA) Manufacturer Resolution, lines/mm'

52 400 Polaroid 22-28

51 125 Polaroid 22-28
57 3,000 Polaroid 22-28
55/P/N 64 Polaroid 14-17 (positive)
150-165 (negative)
Pan X 32 Eastman Kodak 136-225 (negative)
Plus X 120 Eastman Kodak 96-135 (negative)
TriX 160 Eastman Kodak 69-95 (negative)

'Based on manufacturer's specifications.

 Microscopy and Photography 239

appear dark gray and magenta, cyan, and yellow appear light gray or white.
Sometimes contrast can be enhanced by using light filters (not applicable to inter-
ference colors such as in oxide layers), sometimes by changing the background
(applicable to photographing large objects where the background color can be
changed), and sometimes by the proper choice of film. Table 8.2 summarized the
color of filters or lighting to be used. Filters should also be used as necessary to
provide color balance during color photography. It may also be desirable to use
neutral filters to reduce microscope light intensity, since decreasing filament temper-
ature will shift the spectral distribution. As an aid in maintaining the proper color
temperature, some transformers have the approximate color temperature marked
on their controls. Tables and nomographs are available to assist in the proper filter
choice. 24,25 For the more common film and light sources, Table 8.6 gives suggested
filters.
Lighting. When using macroscopic techniques for photographing objects with
highly specular surfaces, for example, a polished silicon slice, oblique lighting will
usually result in a photograph giving a dark-colored surface. In order to have the
surface appear light in color so that minute markings and fine surface detail can
be readily seen, a lighting system similar to that used in the metallurgical microscope
can be used. For small objects such as dice and headers, a cover glass glued to
some support as shown in Fig. 8.18 will suffice. For larger areas such as 2- or
3-in-diameter slices, commensurately larger reflectors are required. In the latter case
a large-area light source will also be necessary and may be made of a close-spaced
array oflow-wattage bulbs with a diffuser of Mylar sheet. The whole area can then
be photographed at one time, and all surface markings will show without any
reflections from the camera provided it has been adequately dulled or shielded to
eliminate any bright reflective metal from its surface. In either case, image quality
will be degraded if the reflector and camera optical axis are not carefully aligned 23
as indicated in Fig. 8.18.
Other choices of lighting are diffused and oblique. Simple oblique lighting from
a single source will cause a profusion of highlights from rough reflecting surfaces
which may obscure detail. In such cases diffused lighting may be required. As an
example, Fig. 8.19 shows the difference between using two diametrically opposed
lights (to reduce shadows) and diffused light from a writing-paper cylinder sur-
rounding the object and lighted from the outside by one of the lights. However,
for other types of subjects where there is a dearth of specularly reflecting surfaces,

Table 8.6. Filters to Correct Light Sources to Color Film*

Wratten filter type or equivalent

Approximate Kodak Kodak Kodak Polaroid

Light source color temp type B type A daylight type color

6-V tungsten ribbon filament 3000K 82A 82C 80A + 82A 80B + CC30B
6-V tungsten coil filament 3100K 82 83B 80A + 82
Zirconium arc, 300-750-W 3200K None 82A gOA 80B + CC20B
tungsten coil filament
Carbon arc 3700K 8lC 8lA 80C 80B
Xenon arc 6500K 85B 85 None None

*From data in Refs. 24 and 25.

240 Semiconductor Measurements and Instrumentation

Fig. 8.18. Vertical illuminator for photomacrography.

a single small bare bulb may produce greater detail. For large subjects and trouble-
some reflections, spray-on films are available to produce a dull surface.
Single lights can be moved from position to position and multiple exposures
made, or a combination of diffuse lighting and a single bulb to produce some
particular highlight may be helpful. If the total exposure time is long enough and
if the camera is in a dark room, the shutter can be placed on "time" and the light
moved slowly from one position to another, leaving it on those preferred areas for
longer periods of time. With color photography different-colored lights beamed from
different directions may help accentuate, and yet keep separate, many different
highlights.
Stereophotographs. 26 It may sometimes be desirable to take stereoscopic-pair
photographs either with a camera or through the microscope. Dual cameras with
the lenses separated a few centimeters are available which have been used for several
years, and stereo aerial photography is accomplished by moving the camera over
the terrain and sequentially photographing with a single lens. Neither of these
approaches is particularly applicable for photomacrography, but by taking a photo-
graph, rotating the subject approximately 8 and rephotographing, satisfactory
0
,

stereo pairs can be generated. Either diffused lighting or rotation of the lights with
the sample may be required in order not to change the highlighting between the
two photographs radically. Ordinarily two conventional photographs and a standard
viewer would be used, but for special applications, one photograph might be taken
through a red filter and the other through green, and both then viewed with a red
filter over one eye and a blue one over the other.

(0) (b)
Fig. 8.19. Photographs of a %-in-diameter rod of polycrystalline silicon showing the
effect of lighting. (a) Taken with two high-intensity reading lamps arranged to
minimize shadows. Notice that various reflections dominate the picture. (b) Taken
by surrounding the section with a tube of writing paper and shining one of the lights
previously used on the outside of the tube. Now considerable detail of the individual
spherulites is visible.
 Microscopy and Photography 241

REFERENCES

1. Emile Monnin Chamot and Clyde Walter Mason, "Handbook of Chemical Microscopy,"
vol. 1, John Wiley & Sons, Inc., New York, 1954.
2. L. C. Martin and B. K. Johnson, "Practical Microscopy," Chemical Publishing Company,
Inc., New York, 1951.
3. Harold Schaeffer, "Microscopy for Chemistry," D. Van Nostrand Company, Inc., New
York, 1953.
4. Bureau of Naval Personnel, "Basic Optics and Optical Instruments," Dover Publications,
Inc., New York, 1969.
5. George L. Clark (ed.), "The Encyclopedia of Microscopy," Reinhold Publishing Corpo-
ration, New York, 1961.
6. Tadami Taoka, Eiichi Furubayashi, and Shin Takeuchi: Gonio-microscope and Its
Metallurgical Applications, Japan. J. Appl. Phys., 4:120-128 (1965).
7. W. E. Degenhard, Light-Section Microscope Measures Thin-Film Thickness, Electron.
Prod., May 1965.
8. Eugene N. Cameron, The Study of Opaque Minerals in Reflected Light, in "Symposium
on Microscopy," Spec. Tech. Pub. 257, American Society for Testing and Materials,
Philadelphia, 1959.
9.S. Tolansky, "Multiple-Beam Interferometry of Surfaces and Films," Dover Publications,
Inc., New York, 1970.
10. M. Fran~on, "Progress in Microscopy," Row, Peterson & Company, New York, 1961.
11. B. W. Mott, Metallurgical Aspects of Microscopy, in A. E. J. Vickers (ed.), "Modern
Methods of Microscopy," Butterworths Scientific Publications, London, 1956.
12. Walter Kinder, The Interference Flatness Tester and Interference Instruments for Surface
Testing, Zeiss Inform., 58:136-140 (1965).
13. A. E. Feuersanger, Interference Microscopy of Thin Films and Semiconductor Structures,
Solid State Des., 4:29-32 (October 1963).
14. J. F. Black, B. Sherman, and V. Fowler, Examination of Semiconductor Wafers with
a Scanned Laser Infrared Microscope, in RolfR. Haberecht and Edward L. Kern (eds.),
"Semiconductor Silicon," The Electrochemical Society, New York, 1969.
15. D. C. Gupta, B. Sherman, Ed Jungbluth, and J. F. Black, Non-destructor SIC Testing
Using Scanned Laser Techniques, Solid State Tech., 14:44-50 (March 1971).
16. Richard A. Sunshine and Norman Goldsmith, Infrared Transmission Microscopy Utiliz-
ing a High-Resolution Video Display, RCA Rev., 33:383-392 (1972).
17. Richard A. Sunshine, Optical Techniques for Detecting Defects in Silicon-on-Insulator
Devices, RCA Rev., 32:263-278 (1971).
18. David Peterman and Wilton Workman, Infrared Radiometry of Semiconductor Devices,
Microelectron. Reliability, 6:307-315 (1967).
19. Anon., IR Scanner Detects Flaws in Microcircuit, Electronics, 43:99-100 (Nov. 23, 1970).
20. "Photomacrography," Kodak Scientific Publication N-12B, 1969.
21. "Basic Scientific Photography," Kodak Scientific Data Book, 1970.
22. "Photomicrography of Metals," Kodak Scientific Publication, P-39, 1971.
23. "Photography through the Microscope," Kodak Scientific Publication P-2, 1970.
24. "Kodak Filters for Scientific and Technical Uses," Kodak Publication B-3, 1972.
25. "How to Use Polaroid Polacolor Land Film for Technical and Industrial Purposes,"
Polaroid Corp., 1970.
26. William C. Hyzer, Taking Stereo Photos in the Laboratory, Res./Develop., 23:51-56
(December 1972).
 9
The Electron Microscope
and Other Analytical Instruments

Unlike other chapters which have dealt extensively with one instrument or type
of measurement, this one discusses a variety of instrumentation, but in much less
detail. The rationale is that the other measurements will probably be widely used
by many individuals, whereas the equipment described here usually requires spe-
cialists to operate and interpret results. Thus the intent of this chapter is not to
give full details but rather to provide insight into what the various techniques have
to offer and to mention problems peculiar to semiconductor measurements.

9.1 ELECTRON MICROSCOPY, GENERAL

Optical microscopy has an upper limit of magnification of about 1,200 X and,

at that magnification, a very small depth of field. These two limitations, coupled
with the fact that most microcircuits have spacings between diffusions, metallization,
etc., that are comparable with the wavelength of light used by the microscope, have
led to the increased popularity of electron microscopy. These instruments use
electrons accelerated by tens of kilovolts to produce the image and resolve much
smaller objects. The increased resolution arises from the much shorter wavelength
Ae of electrons, given approximately by

Ae(A) = jl~O
where V is the electron-acceleration voltage. There are two basic types of electron
microscopes: transmission (TEM), which is analogous to a light microscope, and
scanning (SEM), which sweeps the surface. The TEM is capable of very high
resolution (3 to 5 A), the SEM to only 100 to 200 A. However, the first can be used
only with objects thin enough to allow appreciable transmission of the electron
beam. The actual thickness that can be tolerated depends on the material and the
electron-accelerating voltage used, but in general is less than 2,000 A. Thus most
of the thin films used in microelectronics are too thick for viewing even if they were
not on much thicker substrates. Bulk materials and thicker films must then be
thinned or, if only surface texture is of interest, replicated by a film thin enough
to be used.
The SEM depends on a different set of phenomena for contrast, and all measuring
243
244 Semiconductor Measurements and Instrumentation

v,

Electron
beam
Electron
beam Fig. 9.1. Simple electron-beam lenses.

can be done from one surface. For basic material studies such as looking for
precipitates and studying grain structure and dislocations, the TEM is most appro-
priate. For device process control and failure analysis, the SEM is far more helpful
and is used both as an extension of optical microscopy and for detecting defects
not readily discernible any other way.

9.2 TRANSMISSION MICROSCOPyl,2

The transmission electron microscope is based on the fact that it is possible to

focus electrons. That is, it is possible to produce an electrostatic or magnetic field
of such shape that electrons leaving one point in somewhat different directions can
be brought back together again at another point. The main requirement for such
a field (or lens) is that it have axial symmetry. Figure 9.1 shows a simple example
of both a magnetic and an electrostatic lens. In practice they will be much more
complex, just as the simple optical lenses described in Chap. 8 are seldom used in
actual equipment.
With a family of lenses and a source of electrons a microscope can be built which
may appear as in Fig. 9.2. Such a microscope has three features not found in optical
microscopes. One is the electron source, which is usually a heated tungsten filament
(and must be replaced quite frequently) and the high-voltage power supply. Second,
the whole beam path must be evacuated, since the mean free path of the relatively
low energy electrons is quite short in air. Third, because the eye cannot see the
electrons directly, a fluorescent screen must be used for viewing. By substituting
film for the screen, the image can be photographed. In order to extend the contrast
range, and also to provide for group viewing, the fluorescent screen can be coupled
to a TV camera. The brightness and contrast can then be independently varied and
electronic signal processing used if desired. 3
The stage for holding the sample is an insert machined to fit into the objective
pole-piece assembly. Actual support is usually by a removable piece of wire mesh
(typically 200 per inch) covering the end of the insert. To provide for photo stereo
pairs, some stages can be tilted. Others have been designed to operate at high
temperatures, at low temperatures, and to provide stress on the sample during
observation. These various additions, of course, have to be done without appreciably
altering the magnetic field of the lenses and thus degrading performance.
Since most samples are not thin enough in their normal state to be studied directly,
an important TEM experimental procedure is sample thinning. If a single thin layer
which is part of a thicker composite is to he studied, stripping rather than thinning
may he required. For example, if the structure of a 20o-A-thick NijCr resistor of
an integrated circuit is to be studied, the silicon and oxide can be sequentially
 The Electron Microscope and Other Analytical Instruments 245

removed from the back in one small area and the protective coating stripped from
the front. The resistor film will then be supported by the unremoved Si, and the
whole assembly may be mounted for examination. Surface replication should be
used only if very high resolution of surface features is required. Otherwise the SEM
is more convenient.
Transmission Sample Thinning. Numerous techniques have been developed for
metal thinning. 4 Many of these can be adapted to semiconductors if account is taken
of their brittle nature and if the appropriate etchant is chosen. Unlike metals, if
the thinning is done near room temperature, stress relief during thinning should
not cause migration or loss of dislocations. Usually the sample is etched completely
away in some places and is too thick in others, but the proper thickness can usually
be found in the transition region. Table 9.1 summarizes thinning procedures reported
for various semiconductors. One pitfall which can cause misinterpretation is the
tendency for some etches to give rough surfaces or to leave debris on the surface,
either of which may be interpreted as a precipitate. 9 Also, native oxides can grow
quite rapidly in air after the thinning operations; so interpretation should consider
the possibility of features associated with the oxide.
Replication. 4 The simplest form of replication is shown in Fig. 9.3. The surface

- Anode

~--~
Condenser lens
IIiIa ____
Condenser aperture

Object

Objective lens

Intermediate image

--
Pro j ector lens

Fig. 9.2. Diagram of an electron microscope. The

magnetic lenses are more complex than the one
shown in Fig. 9.l. The gap forms two cylindrical
magnetic poles. Their exact shape is carefully cal- :::;;;;;;;;;;;;;;;;;t;;;;;;;;;;;;;;~ Final image
- Final viewing screen or
culated and precision-machined.
.
photographic plate
246 Semiconductor Measurements and Instrumentation

Table 9.1. Etchants for Sample Thinning

Material Etchant* Mode Reference

Si 95 HN0 3, 5 HF, with sample attached to Chemical 5,6

Teflon holder and rotated

9 HN0 3, 1 HF Jet 7

4 g NaOH, 96 ml H 20, plus sodium Float specimen 8

hypochlorite to suppress hydrogen evolution on etch

Ge 9 HN0 3 , 1 HF Jet 7

Warm dilute sodium hypochlorite Float specimen 8

on etch

GaAs 40 HCI, 4 H 20 2 , I H 20, at 20'C Jet 9

25% perchloric acid, 75% glacial acetic Electrolytic 10

acid, gently flowing from an orifice above
sample at 42 V

GaP CI in methanol Jet 11

PbSe 50 ml 45% KOH, 50 ml ethylene glycol, Electrolytic 12

10 ml H 20 2 • H 20 2 may be added during
etching to maintain rate. Surface stains
may be removed with 10 ml acetic acid,
10 ml water

PbTe 20 g KOH, 45 ml H 2 0, 35 ml glycerol, 20 ml Electrolytic 13

ethenol 4-6 V, 0.2 A/cm 2
* See Sec. 7.2 for safety precautions.

to be examined is coated with a film of a material such as collodion or carbon thin

enough for the electron beam to penetrate easily. Then, in order to provide contrast,
shadowing is introduced by evaporating some heavy metal onto the film from a
low angle. Without it, the uniform thickness of the film would appear nearly
featureless. The replica used in the microscope may be made in a one-step process
(as in Fig. 9.3) or in two or more steps by making an intermediate replica and then
using it to generate the one actually examined. The first is preferred, but there are
a limited number of materials to be used in the microscope, and if they and the
object are not compatible, intermediate steps become necessary. The final film is
almost always Formvar, collodion, or evaporated SiO, Si0 2, or carbon. The shadow-
ing material is chosen for its electron-stopping power, ability to be deposited with
very small grains, and resistance to growing larger grains during the electron-beam
heating which occurs during observation. Carbon with platinum shadowing has been
used to study initial nucleation of Si when being grown epitaxially onto various
substrates such as Si14 and sapphire. Replication is also widely used in grain-size
studies of the various metallization system such as AI, Au, and Ni/Cr which are
found in semiconductor devices.

9.3 THE SCANNING MICROSCOPE15

Figure 9.4 is a diagram of an SEM. The purpose of the series of lenses is not
to provide magnification as was done on the TEM but rather to reduce the diameter
 The Electron Microscope and Other Analytical Instruments 247

Thick object

(0 )

Replicating film

Thick object

( b)

Fig. 9.3. Surface replication and shadowing

for TEM. After shadowing, the film is
stripped from the object and viewed directly. (c)

of the electron beam so that it is only 200 or 300 A in diameter when it hits the
sample. Further, there must be a means of deflecting the beam over the surface
in a raster fashion. This can be done either with electrostatic plates or by magnetic
coils. When the beam strikes the sample, there is the possibility of extracting several
different kinds of signals as shown in Fig. 9.5. Some of the incident electrons will
be backscattered with no appreciable energy loss and may be detected by a sur-

'1---0 - 40 to -100 kV
,,,:..~_Filament
Crossover
...c-- - Shield
"'-Anode

'ggg:- -:ggg'

-=--
~
-~
.-I

~ -~
~-
~
Fig. 9.4. Diagram of an SEM. For detector details
see Fig. 9.5. Sample
248 Semiconductor Measurements and Instrumentation

Lens

00 0 0 o 0 0 0
00 0 0 o 0 0 0
o 0 0 0 o 000
PIN detector for
reflected electrons
Fig. 9.5. SEM signals. The cath-
odoluminescence detector is not
shown. It must be optically coupled
Amplifier by lens or light pipe to the point
of electron-beam impact.

face-barrier PIN diode. Low-energy secondary electrons will be generated and can
be collected by biasing a wire mesh a few hundred volts positive. They are then
accelerated by several thousand volts before striking a scintillator crystal. The light
emitted as they strike is coupled to a photomultiplier tube whose output is propor-
tional to the number of secondary electrons collected. Should the material being
studied exhibit cathodoluminescence, the emitted light can be coupled to a detector
via a light pipe or a lens system. Finally, the currents and voltages generated in
the sample owing to the incident electron beam can be measured. This may be
by inserting a low-impedance current amplifier in the sample-ground connection
or by monitoring various leads of finished devices.
The chosen signal, which actually may be a composite from two or more of the
phenomena just described, can then be used for several sorts of display. Generally
a cathode-ray tube (CRT) will be used and one beam scan across its face will be
synchronized with one sweep across the sample surface. For two-dimensional cover-
age of the surface a succession of sweeps like a TV raster is used. Magnification
is determined by the ratio of the beam movement on the surface to the spot move-
ment across the face of the CRT. If Z-axis modulation is used, the conventional
TV-type picture results. Y-axis modulation of the CRT beam makes the display
take on a three-dimensional-like appearance. 16 -iS It produces considerable distortion,
however, since the coordinates on the screen are a function not only of the position
of the electron beam on the sample surface but also of the signal amplitude.
Contrast Mechanisms. Work function and atomic number affect the yield of both
secondary electrons and the backscattered beam, but the most important feature
from the standpoint of displaying surface topography is the variation of yield with
the angle of incidence () of the impinging electron beam. 19 Over an appreciable
range of (), the number of secondary electrons is proportional to sec (). For most
instruments this transforms into a sensitivity for angular change of from I to 4 0
•

For the case of reflected electrons, behavior is similar. However, since the detector
can receive only line-of-sight electrons, whereas the secondary-electron collector does
not have that limitation, reflected electron displays tend to show greater shadowing.
The potential of the object surface can have considerable effect on the number
of secondary electrons collected but will depend somewhat on the actual placement
and geometry of the electron collector. 19 Such voltage contrast can be used to
delineate p-n junctions and to locate breaks in metallization. 20 A major disadvantage
is that charge buildup on insulators will cause loss of detail. Because of this, devices
with insulating-layer overcoatings for leads protection usually have it removed before
SEM analysis; although if the insulating material is oflow atomic number, e.g., Si0 2,
 The Electron Microscope and Other Analytical Instruments 249

-
Electron beam scan

11 1 1 1 1

I /
f
Si0 2
y";""~
Surface leakage

Al V'10,000 AO

Si02

Si 1/w « Leakage
time constant

Fig. 9.6. Use of lead modulation to obtain voltage contrast

through an insulating overcoat. (From Crosthwait. 22)

the backscattered high-ene.gy electrons can be used to form an image of underlying

metal. 21 An alternate approach that can be used in combination with voltage contrast
to show which leads have voltage applied to them, even with overcoating, is shown
in Fig. 9.6. If the voltage on the lead is modulated at a frequency high compared
with the time for charge deposited on the insulator surface to leak away, there will
be a modulation of the surface voltage above the lead because of capacitive coupling.
This modulation is enough when operating a conventional TTL circuit at its rated
voltages to enable lead breaks and other malfunctions to be observed even with
a 1O,ooo-A overcoat of Si0 2 • When insulating surfaces are to be examined for their
own sake, they should first be coated very lightly with a metal film which can then
be grounded.

--
Incident beam
...--

r----c~r---------------~~--,
1 -1 r- Hole diffusion length

o-l-~-Signal

Fig. 9.7. Use of a p-n junction to produce an SEM signal. If

the incident electron produces a hole-electron pair in the shaded
region, current will flow.
250 Semiconductor Measurements and Instrumentation

(01 {bl

(el
Fig. 9.8. Examples of SEM photographs. (a) Silicon needles
several mils high growing up from a silicon substrate. (b)
Ti: W / Au metallization contacting an integrated-circuit emitter.
(c) A plated lead crossing mesas anisotropically etched into a
silicon surface. (Photographs courtesy of K. E. Bean, A. N. Akridge,
and Farris D. Malone, Texas Instruments Incorporated.)

A beam impinging close to a p-n junction will induce carriers which will contribute
to a current flow if they reach the junction before recombining. 15 Thus, in Fig. 9.7,
if the carriers are generated anywhere within the shaded region, they will produce
a current which can be detected as was shown in Fig. 9.5. In materials without
junctions, the beam can be used to modulate the conductivity and make conductivity
profiles.
The mixing of signals alluded to earlier can sometimes be used to considerable
advantage. For example, by combining the secondary electron signal with that from
the p-njunctions, the junctions can be clearly defined, whereas otherwise some other
contrast mechanism might only vaguely show them. Likewise the cathodolumines-
cence signal could be mixed with secondary emission. 15 There are also a variety
of electronic manipulations that can be used to vary contrast. For example, the time
derivative of the secondary electron signal can be used, either alone or mixed. To
increase the dynamic range that can be recorded on the phosphor, fixed amounts
of direct current can be removed in steps and a series of contours mapped out, each
of which will have the full range of contrast allowed by the phosphor. 24
 The Electron Microscope and Other Analytical Instruments 2S 1

SEM Applications. By far the greatest application of the SEM is in the inspection
of structures and devices with high magnification and great depth of field. As an
example, Fig. 9.8, which shows three representative SEM photographs, includes a
photograph of some silicon crystallites growing up from a substrate that would have
been impossible to produce any other way. Integrated-circuit metal coverage over
oxide steps has been widely studied. 25 - 28 Some care must be exercised in looking
at steps, since excess intensity and a shadowing can both occur because of the angles
used. Large angles favor showing good detail when viewing a step in position B
of Fig. 9.9, but in position A there is little difference between structures a and b.
Therefore, whenever there is a question of interpretation, the surface should be
viewed from several angles. * The fact that the beam does not hit normal to the
surface will produce distortion which sometimes makes it difficult to visualize accu-
rately the shape of the object being viewed and also makes it difficult to estimate
dimensions even though the system magnification is approximately known. If the
dimensions of some feature, e.g., an oxide thickness, are known, they can be used
as a guide. If no features are known, polystyrene latex spheres are available in
several sizes in the 0.1- to l-,um range and can be added to the surface for a
comparative calibration.
By using p-n-junction current as the signal, making charge collection maps, and
combining with the outline of diffusions in planar structures, inversion layers can
be located. 29 - 34 The electron beam can induce enough charge in the oxide to remove
the inversion layer; so one should start with low enough intensity to prevent anneal-
ing before the opportunity to observe it. Should such premature annealing occur,
however, it would be reflected in reduced leakage current, and this would not go
unnoticed.
Electron-Beam Device Testing. Electron-beam probing can be used for some
specialized electrical testing of semiconductor components and in principle has the
advantage over mechanical probes because mechanical damage is minimized and
the probe size can be made very smalL Disadvantages are that the electron beam
may crack the pump oil in the ambient above the sample and deposit a thin carbon
layer over the semiconductor surface, that the interpretation of electron-beam signals

"Rather standard SEM microcircuit-viewing specifications (e.g., NASA) are available which when
followed will allow reasonable correlation among different sets of observers.

~ A
\- B
(0 )

Fig. 9.9. Effect of angle on SEM detail. (a) The

signal increases near the ledge because more
secondary electrons can escape the solid. (b)
Because of the viewing angle, the trench at A' A'
is not seen. (b)
252 Semiconductor Measurements and Instrumentation

may be difficult, and that it may be impossible to get enough numerical data to
characterize the component completely.
Two modes of operation can be used. In one, the component under test is biased
through the normal contacts and interconnects, and secondary emission at any
selected point on the surface is used to estimate the relative voltage at that point.
In the second mode, only one external connection is made to the component and
the electron beam is used as the other one. Current from the fixed contact is then
measured. The first method is particularly attractive when very complex circuitry
is examined because it allows the point of failure to be seen as voltage contrast. 35- 39

9.4 ELECTRON DIFFRACTION4o-42

An electron beam will be diffracted by the periodic lattice of any crystal it tra-
verses, and if the optics of the TEM are slightly changed, a diffraction pattern rather
than an image of the surface topography can be projected onto the screen. If the
crystal is large with respect to the beam area, spots will be produced and can be
interpreted in terms of crystal structure. For near perfect crystals, lines (Kikuchi
lines) will also be seen; they are sometimes used to determine orientation. Samples
with multiple crystallites considerably smaller than the beam size and randomly
oriented will show rings. To a first approximation the ring diameter D (unless there
is a stage of magnification between the sample and screen) is given by

D = 2AeL
d
where Ae is the electron wavelength, L the distance from sample to screen, and d
the lattice spacing of the planes causing diffraction.
The arrangement as shown in Fig. 9.lOa is well suited to studying small areas,
and indeed the procedure often is to first examine the sample in the normal TEM
mode and then change optics and look at the diffraction of the same region (se-
lected-area electron diffraction). However, transmission electron diffraction (TED)
suffers from the same disadvantage as the TEM in that a very thin sample is
required. The diffracted beam and the normal transmitted beam can also be com-
bined to give transmission electron diffraction contrast microscopy. In this case
crystallographic defects in the thin section become visible and single dislocations,
stacking faults, etc., can all be studied. * For pertinent references see Chap. 2.
Diffraction patterns can also be produced from backscattered electrons using the
geometry of Fig. 9.l0b. Now a sample of any reasonable thickness can be used,
but the problem becomes one of signal strength. The backscattered signal goes down
as the electron energy goes up; so operation is restricted to electron energies of tens
or hundreds of electron volts rather than the tens or hundreds of kilo electron volts
of a TED. This sort of instrument gives low-energy electron diffraction, or LEED.
Because the energies are low, the beam penetration is very shallow and diffraction
is from the first few atomic layers next to the surface. Such equipment is thus capable
of studying surface contamination and/or surface reorientation effects.
Higher-energy beams can be used for reflection diffraction (RHEED) (Fig. 9.lOc)
by having a small grazing angle and depending on forward-scattered electrons, whose

*TED is almost always done with a conventional transmission electron microscope. The other methods
described usually involve equipment built especially for the purpose.
 The Electron Microscope and Other Analytical Instruments 253

(a)

( b)

(c)

Fig. 9.10. Various electron-diffraction configurations. (a) TED.

(b) LEED. (c) RHEED. (d) RHEED. (d)

yield does not go down as energy increases. If the surface is reasonably rough as
in Fig. 9.lOd, the beam can penetrate the asperities and the system is basically the
same as TED. However, if the surface is atomically quite smooth, at shallow angles,
penetration is quite low, and RHEED will respond to essentially the same few surface
layers as LEED. One point to remember is that even though the beam-spot size
may be small, the low grazing angles will allow contribution from a ribbon of
appreciable length, and localized measurements become difficult. RHEED is not
as widely used as LEED for studying surfaces but has one advantage in that small
local areas of differing crystal structure are more easily observed. 43
Display of the diffracted beam may be by photographic film, direct viewing on
a fluorescent screen, or collecting the electrons in a Faraday cup. In any case grids
can be used to reject lower-energy electrons not associated with the elastically
scattered beam. The Faraday cup can be used with electronic-scanning systems to
produce a CRT display similar to that obtained from a densitometer profile of the
film and is useful in observing time-dependent phenomena such as those which may
develop during evaporation. 44 This application presupposes that the diffraction
system is combined with other equipment and used in conjunction with it. If
provisions are made only for heating the sample, annealing and surface contami-
nation studies* can be made, but with evaporation or molecular-beam45 sources,
epitaxy and polycrystalline growth can be monitored in situ. Various gases can be
admitted to the vacuum chamber and surface interactions studied.

* Surface contamination devoid of structure is more often studied by electron spectroscopy (e.g., Auger),
discussed later. Diffraction is used if the contamination reacts with the surface and produces a change
in structure or, occasionally, by observing an overall reduction in diffraction intensity because of masking
by a disordered layer of contaminant. 46
254 Semiconductor Measurements and Instrumentation

Table 9.2. X-Ray Testing Methods

Method Parameter measured End use

Diffractometer Lattice spacing Thermal-expansion coefficient, lattice

strain, composition
Linewidth Crystal perfection
Line intensity Polarity through structure factor
Double-crystal Linewidth Crystal perfection
spectrometer
Laue reflection Lattice spacing Orientation, estimate of amount of
misorientation
Topography Display of dislocations, Same as parameters measured
stacking faults, twins
X-ray microprobe Characteristic line energy Composition analysis

When really clean surfaces are to be studied, great care is necessary to prevent
the instrument itself from contaminating the surface; so a vacuum of 10-9 torr or
better is required and the clean surface is produced by cleaving the sample in the
diffraction chamber or by extended heating at elevated temperatures.
One of the more interesting aspects of the LEED clean-surface studies on semi-
conductors has been the observation of a superlattice with spacing much larger than
the normal d values, but always an integral number of d values. For example on
(111) silicon surfaces a 7 X 7 spacing, as well as several others, may be found,
depending on prior surface and heat treatments. 41

9.5 X-RAYS

X-rays are generated when high-energy electrons strike some other material.
Several sharp peaks will be superimposed on a background whose shape is similar
to that of blackbody optical radiation. The wavelength ofthe peaks is characteristic
of the target material, while the minimum wavelength and general shape of the
continuous spectrum are primarily functions ofthe energy of the impinging electrons
(applied accelerating voltage). For electron-acceleration voltages corresponding to
minimum wavelengths longer than those of the characteristic peaks (lines), no lines
will occur. For most purposes, the x-rays are first generated and then used in a
variety of equipment. However, the procedure can be reversed; i.e., an unknown
material can be bombarded with a beam of electrons and the wavelengths of the
characteristic radiation measured. From this a composition analysis is possible, and
because of the small spot size possible with an electron beam, very small regions
can be examined. This procedure is usually referred to as x-ray microprobe analysis.
Table 9.2 summarizes the more common applications of x-ray technology to
semiconductor measurements. Diffraction is the phenomenon most used. A simple
diffractometer schematic is shown in Fig. 9.11. Constructive interference, i.e., a peak
in x-ray intensity, will occur when
n"A = 2dsin8
where n is the order, "A the x-ray wavelength, and d the spacing between two con-
secutive scattering planes. This is Bragg's law and is the basis for crystal .diffracto-
meters. Provisions are made to allow the 8 and 28 angles to be quite precisely set,
and for many applications, a gear train is provided to rotate simultaneously the
 The Electron Microscope and Other Analytical Instruments 255

Fig. 9.11. Diffractometer schematic. Meas- Incident x-roy beam

ured from the incident beam, the reflecting
plane must be rotated to () and the detector
to 2() for maximum intensity.

crystal by B and the detector arm by 2B. Beam-width control is by slits, and wave-
length control is by using a combination of a characteristic line of the chosen target
material and the absorption edge of a specific filter material. Perhaps the most
obvious use of a diffractometer is to determine d from a measurement of B. The
value for d can then be used in a number of way:,;. If a material with known lattice
spacings is being examined, the orientation can be determined by matching the d
with previously calculated spacings for various orientations (see Chap. 1). If provi-
sions can be made for observing the material from many directions and measuring
the spacings for several orientations (as, for example, if a powder sample were used),
they can be compared with tables of known spacings and the sample composition
determined.
Double-Crystal Spectrometer. The primary purpose ofthis instrument is to provide
as nearly a monochromatic and parallel beam as possible so that the line width
observed is dependent on the sample and not on the instrument. One way of
accomplishing this is by using the diffracted beam from one crystal as the x-ray

Detector

Parallel position

(0 )

Fig. 9.12. Two geometries for

double-crystal spectrometers. The
conditions of the spectrometer are
described by first listing the radiation Anti para Ilel position
used and then the reflection order for
each crystal. Kal (11) means the
first-order reflection is to be used on
both crystals, and by convention, the
fact that the second number is positive
means the crystals are arranged in
antiparallel geometry. (b)
256 Semiconductor Measurements and Instrumentation

source for a second crystal as shown in Fig. 9.12. The first diffracted beam will
still be somewhat divergent, because the crystal is not perfect and because slightly
different x-ray wavelengths will be diffracted at different angles, but in general the
beam is far more parallel than one defined only by slits. The deviation from
parallelism is minimized by obtaining the most perfect first crystal possible, and
by using as nearly monochromatic radiation as possible. Since less of the total energy
is reflected as the beam width is narrowed, the intensity continually decreases so
that even with a very intense source, the second diffracted beam will be quite weak,
and some care must be exercised in the detection system. Alignment is also very
important and, if not carefully done, will distort the line shape and shift the position
of the peak. 47 - 49
X-Ray Topography. The diffractometers just mentioned are not the only methods
by which diffraction effects can be observed. For example, by the proper choice
of x-ray, sample, and film geometry, the additional diffraction effects resulting from
crystal defects such as dislocations and stacking faults will produce a photographic
image of the defect (x-ray topography). The photograph is a 1: 1 reproduction of
the sample and all dislocations in it which have a component of their Burger's vector
perpendicular to the diffracting plane. Any magnification must be achieved by
subsequent enlargement of the film and is restricted to a few hundred X because
of film grain. However, in semiconductor work magnifications of less than 100 are
usually used. Because of the low magnification, and hence poor resolution when
compared with electron-microscope observation, the method is most appropriate
when the dislocation density is relatively low. Topography is widely used to study
damage induced as a function of device-processing steps and has an advantage over
other methods of being nondestructive.
Figures 9.13 and 9.14 show some of the geometries used. 50- 60 Figure 9.13a is
that of transmission Berg-Barrett and requires the absorption coefficient-thickness
product pi of the sample to be less than 1 for good contrast. A disadvantage of
this equipment is that it requires a well-collimated beam and the area of the crystal
covered is quite small. Figure 9.13b shows the projection-topography procedure in
which the crystal and film, but not the shield, are slowly moved perpendicular to
the diffracted beam. This works well as long as the crystal lattice is quite flat
(unstrained) over the whole sample area. However, if there is any bending or
warping, only a portion of the crystal will satisfy diffraction conditions and a spotty
photograph will result.
To improve contrast, it is usually desirable to keep the film as close to the crystal
face as possible. However, as can be seen in Fig. 9.13b, proximity and large-distance
scanning are not very compatible; so an alternate arrangement with the film and
translation parallel to the crystal as in Fig. 9.13c is often used. The scan system
of Fig. 9.13b creates considerable distortion between the vertical and horizontal
scales. Figure 9.13c corrects that deficiency, but if it is desired to keep the original
Lang geometry, individual scan controls for sample and film can be used and each
allowed to move parallel to its face.
To minimize warping effects, scanning combined with oscillation (SOT), Fig. 9.13d
can be used, and topographs of complete silicon slices after processing (which usually
tends to produce considerable bowing) can be made.
Film contrast is dependent on having a very monochromatic x-ray source; so for
some studies, e.g., stacking faults, a double-crystal spectrometer geometry as in Fig.
9.13e may be helpful.
 The Electron Microscope and Other Analytical Instruments 257

Sample
Narrow
x-ray beam
(a) - -'-----A~---I~stoP

(b)
- ~
7.
/Directionof
translation

Direction of/'
translation
(c)

Direction of
translation

Fig. 9.13. Lang x-ray topography with varia-

tions. (a) Original (narrow x-ray beam). (b) With
(d)
~L-J
scanning capability (film and sample are moved
in unison perpendicular to the diffracted beam).
(c) Film parallel to sample surface (film and
sample are moved in unison parallel to the sam- Direction of
ple face). (d) Scan combined with oscillation to translation
observe warped surfaces (film and sample are /
moved in unison parallel to the sample face as (e)
well as rocked about the beam direction). (e)
Combined with double-crystal monochrometer.

Fig. 9.14. By adjusting the stop as shown, only

the diffraction contributions between planes Y- Y'
and Z-Z' are recorded. (Adapted from Lang. 50 )
258 Semiconductor Measurements and Instrumentation

If it is desired to look at an interior portion of the crystal, stops can be arranged

so that only the contribution from the desired region is allowed to hit the film, as
is shown in Fig. 9.14.50 Two-layered structures with different lattice spacings (e.g.,
GaAs epitaxially grown on Ge) will give two topographs which can then be examined
to see which defects originated in which layer without using any additional stops. 51
In examining wedge-shaped samples of high-perfection crystals, e.g., the rounded
edge of a silicon chemically polished slice, banding may be observed which is due
not to lattice strain but rather to interference effects.61 However, distortion of these
"Pendell6sung" fringes can be used to estimate strain nonuniformities such as occur
near dislocations. 62 .
For a thick crystal, i.e., one in which ILt ~ 1, little x-ray transmission would
normally be expected, but by careful alignment of the crystal for Bragg reflection,
enhanced transmission will occur if the crystal is highly ordered but not where there
is a lattice defect. 63-65 This method has been used more often for Ge and GaAs
than has Lang, since their higher atomic number gives higher absorption coefficients
and makes the Lang method (ILt ~ 1) less attractive because of the thinner samples
or harder x-rays required.
Reflection geometry is also applicable to topography and is most appropriate if
the surface or thin layers such as an epitaxial layer are to be examined. Modifications
similar to some of those used for transmission, e.g., double-crystal monochrometer,
and the use of selective stops to define interior sections, have been used. 6o,66
Topographs can also be made using white radiation and a large-cross-section x-ray
beam. 67 In this manner the spots will also be large and will show crystallographic
detail. An application for which it is particularly suited is the rapid mapping of
slices which may contain polycrystalline regions. 68
Different diffraction planes can be used to generate the topographs, and by
considering which ones show a particular dislocation, that dislocation can be charac-
terized as to direction and Burger's vector. 69
A variety of special-purpose cameras have been constructed. For example, a
vidicon has been substituted for the film so that viewing can be in real time. 70 By
providing a high-temperature sample chamber, dislocation motion can be detected,
and in fact, the deleterious effects of high-temperature processing can be examined
in si(u. 71 - 73 Further details relating to equipment, precautions, interpretation, etc.,
are to be found in Refs. 74 to 81.
Microprobe Analysis. * By irradiating a material with a high-energy beam of
electrons, it can be made to emit x-rays just as does the target of a conventional
x-ray tube. The presence or absence of characteristic emission peaks of the various
elements can then be used as a basis for compositional analysis. 82 Figure 9.15 is
a schematic of such equipment. Since a controlled electron beam is an important
part of this equipment, it is often combined with a scanning electron microscope.
By scanning the incident electron beam across the surface, a map ofthe concentration
of chosen elements can be prepared. As is normal with x-ray analysis, the sensitivity
is rather poor; however, it is relatively nondestructivet and has good surface resolu-
tion. It has been used for semiconductor impurity analysis83 ,84 but is much more

*For more extensive information relating to x-ray microprobing see, for example, the series "Advances
in X-Ray Analysis," published by Plenum Press, and Ref. 87.
t Excluding radiation damage and the possibility of the deposition of pump-oil compounds on the
surface.
 The Electron Microscope and Other Analytical Instruments 259
Electron beam

Deflection plates
Crystal monochrometer

",droo ~':::::~::::i!~
Display

SEM display
Display

Pulse- height
analyzer

Fig. 9.15. X-ray microprobe. The surface to be studied can

be scanned by deflecting the electron beam. A crystal detector
combined with a pulse-height analyzer may be used or a
monochrometer and conventional detector. For correlation
purposes most equipment has one or more varieties of electron
detectors so that it can be operated in a scanning-electron-
microscope mode. Depending on the instrument, beam deflec-
tion may be either electrostatic, as shown, or magnetic.

useful in examining the metallization and dielectric systems used in semiconductor-

device manufacture. 85 In order to assist in interpretation of the data if quantitative
results are desired, various computer-based computations can be used. 86,87 With care
a microprobe can be used for light-element analysis, but performance is considerably
better for atomic weights above 12 to 15. By using charged particles rather than
electrons to generate x-rays, the general techniques can be extended to much lighter
elements. 88 However, the requirement for a particle accelerator is introduced, and
lateral resolution becomes very poor.

9.6 ELECTRON SPECTROSCOPy89-93

Electron spectroscopy concerns itself with the energy spectrum of electrons emitted
from atoms of the material being studied. Depending on the method of excitation,
the electrons can come either from the valence shell or from an inner one, and may
be either a one-step or a two-step process as shown in Fig. 9.16. They will have
an energy characteristic of the kind of atom and the particular electron levels
involved in the transition. Therefore, by determining the energy of the ejected
electron, the element from which it came can be deduced. The electrons generally
have a very low energy and are absorbed before reaching the surface if they are
generated at depths of greaterthan perhaps 20 A. This restricts electron spectroscopy
to a study of the top few atomic layers of a material, but it also allows the surface
layers to be studied independently of the remainder.
There are several kinds of spectroscopy (Table 9.3) based on the particular emission
process used. Photoelectron emission is a one-step process in which an electron is
directly emitted if the energy of the incident photon is high enough. If the electron
is removed from one of the inner shells (either by photoionization or by an electron
beam), the hole can be filled by either a valence electron falling into it, coupled
by x-ray fluorescence, or by ejection of another (Auger) electron. The relative
260 Semiconductor Measurements and Instrumentation

'Q. _e
e

VOlenCeshe¥
~'
Inner shells
PESOS Auger
(0) ( b)

Fig. 9.16. Origin of electrons

Innershells
measured in electron spectros-
copy. Auger electrons are the
PESIS ones most used in semiconduc-
(c) tor studies.

number of each is determined by the incident energy. Below 10 keY the Auger
process is favored. Above it x-ray fluorescence is more probable. Auger spectroscopy
(AES) is the one which has found most application in semiconductor studies and,
when combined with sputter etching, can be used for depth profiling as well as
surface investigations.
Figure 9.17 a shows the general character of the electron energy spectrum produced
by incident electrons. Those which leave with the same energy as the incident
electrons were elastically scattered and are the ones used for electron diffraction.
The peak near zero energy is from secondary electrons generated by multiple

Table 9.3. Electron-Beam Instrumentation Acronyms

ESCA Electron spectroscopy for chemical analysis. Sometimes used as synonym for
PES IS, often used to cover whole area of photoelectron spectroscopy
PESIS Photoelectron spectroscopy of inner-shell electrons
PESOS Photoelectron spectroscopy of outer-shell electrons
UPS Ultraviolet photoelectron spectroscopy
XPS X-ray photoelectron spectroscopy
INS Ion-neutralization spectroscopy
FES Field-emission spectroscopy
AES Auger electron spectroscopy
SEM Scanning electron microscopy
TEM Transmission electron microscopy
TEDCM Transmission electron diffraction contrast microscopy
TED Transmission electron diffraction
RHEED Reflected high-energy electron diffraction
RED Same as RHEED
lED Incident electron diffraction, same as RHEED
LEED Low-energy electron diffraction
 The Electron Microscope and Other Analytical Instruments 261

Secondary electrons

W Elastic
(a 1 Auger
z electrons
scattering
~
0

W
-0
'-
( b) w
z
-0

(c)
(f)

Fig. 9. 17. Electronenergyspectrum. o Electron energy, E -

collisions within the material being examined. Between the secondary and the elastic
peaks there is fine structure due to Auger transitions. The peaks are small; so the
derivative dN(E)/ dE is used to enhance their detectability, and appears as in Fig.
9.17h. Experimentally, two kinds of energy analyzers are commonly used. One, with
a retarding field, shields the actual detector by a grid or series of grids whose potential

Synchronous
detector

Strip chart
recorder

Ref signal from chopper

Thermocouple

Rotating Reference
Attenuator
sector beam

Sampling
area

I
Sample
beam

Fig. 9.18. Infrared spectrometer. (Adapted from Perkin-Elmer Model 621 Instruction
Manual.)
262 Semiconductor Measurements and Instrumentation

can be varied. In that manner, only electrons above a given energy can penetrate
to the detector. The signal S for a given setting is proportional to the total number
of electrons above that energy E, or

S = LX> N(E) dE
Ex

S(E) appears as in Fig. 9.17c. When this sort of detector is used, two differentiations
(both done electronically) are required to give the dN/dE energy spectrum of Fig.
9.17 b that is normally cataloged. The other type of analyzer uses an electrostatic-lens
system and allows only electrons in a small energy window of E to E + dE to reach
the detector. Its signal is then N(E), or that of Fig. 9.17a.
A number of transitions will be probable for each element, so that the spectra
can become quite complicated if there are many species on the surface. While
calculations of the expected energies have been made, experimental spectra obtained
from known materials are usually used. 93 To facilitate identification, the major peaks
vs. elements are tabulated and can be used for initial screening. Fortunately there
is little overlap between elements, and further, because of the extreme purities
required.in semiconductor operations, few species are to be observed on any given
sample. Sensitivity is very good; approximately 10 12 atoms per square centimeter
can be detected. 92 This corresponds to 10 18 to 10 19 per cubic centimeter in the
bulk, or to a few hundredths of a monolayer.
In common with LEED systems, Auger spectroscopy must be used in very high
vacuums, i.e., _10- 10 torr; otherwise surface contamination from the system may
build up too rapidly for measurements to be made. Since the vacuum and e1ectron-
beam requirements are similar for LEED and AES, the two are often combined
into one multipurpose instrument. In order to extend the capability to depth profil-
ing, an ion sputter gun can also be combined with the other elements to erode away
the surface. 94.95 The vertical depth scale is established from the sputter etch rate.
By making sure that the area removed by sputtering is much larger than the electron
beam, any chance of contribution from the sidewalls of the depression is eliminated.
AES can be used both for studying contaminants left on presumably clean surfaces
and for the analysis of thin films, both metallic and dielectric. It has been used,
for example, to look for metallic impurities such as Ni, Fe, and Au which might
participate in the formation of the superlattices discussed earlier.96.97 Diffusion data
in very thin layers, e.g., Si into thin evaporated Au layers98.99 and NijCr thin-film
resistor91 interdiffusion, can be obtained more easily than from other types of
measurements. Auger signals are generated for light elements from atomic weight
3 on and thus can provide more information than x-ray microprobe analysis. In
particular, organic surface contaminants as a function of surface treatments such
as vapor etching, aqueous etches and rinses, and asher photoresist removal have
all been studied with AES.I00-I06 Light-element dielectrics such as Si0 2 , silicon
nitride, and silicon oxynitride can also be analyzed in this manner.107

9.7 OPTICAL SPECTROSCOPY

Optical spectroscopy, which involves measuring the relative intensity of light as

a function of wavelength, is categorized by both the wavelength of interest (infrared,
visible, ultraviolet) and whether the light is being emitted, absorbed, or reflected
by the sample.
 The Electron Microscope and Other Analytical Instruments 263

Emission Spectroscopy. The sample to be analyzed is subjected to a high temper-

ature such as an arc, flame, or spark which volatilizes it and breaks molecular bonds.
The atoms will then absorb energy and re-emit with a line spectrum characteristic
of each individual atomic species. In the uv and visible regions gratings are com-
monly used as dispersive elements, and the lines are recorded on film. Because of
the extraordinarily low impurity levels required in semiconductors, it is not as helpful
as some other methods in determining doping levels. However, for raw materials
and the myriads of chemical supplies used in the semiconductor industry it probably
is the most widely used of analytical toolS. 108,109
Absorption Spectroscopy. A high-intensity light source containing emission lines
of the specific element to be analyzed for is passed through a flame of a gas burner
into which the material to be analyzed has been injected. In this case, if any of
the specific element is indeed present, it will absorb at the same frequency as the
light-source emission and cause a reduction in the intensity. Such equipment has
the disadvantage of requiring a separate light source for each element of interest
and either a gaseous or liquid source, but for the routine analysis of one element
it is very fast and inexpensive.
Flame Photometry. Flame photometry is really emission spectroscopy in which
the sample is injected into a flame much as in absorption spectroscopy. Indeed,
the burners are the same and commercial equipment usually combines both modes
of operation. Unlike conventional emission spectroscopy, this one has extreme
sensitivity (parts per billion to parts per trillion) for certain elements and can -Je
used to study semiconductor wash-solution contamination by alkali metals such as
potassium and sodiumpo-112
Infrared-Absorption Spectroscopy. The high temperatures used to produce the
emission bands used in the previously discussed methods break all molecular bonds
and hence will give no information concerning molecular structure or bonding
configurations. By keeping the sample near room temperature and measuring the
infrared absorption, spectra are obtained which are dependent on particular bonds.
Infrared spectroscopy is most used for analyzing organic compounds but is applicable
to semiconductor analysis. For example,113 the 9-llm band due to Si-O bonding
will allow oxygen incorporated into the Si lattice to be determined down to about
10 17 atoms per cubic centimeter. Similarly, the Si-C bond produces a 16-llm
absorption band used for carbon analysis. 114 Other applications relating to the
semiconductor industry involve the examination of surface films such as doped
oxides 115 and the stains that sometimes are found on Si surfaces after etchingP6
Infrared instruments may use either gratings or alkali-halide prisms for dispersion.
The prisms are water-soluble; so they must be protected from high-moisture envi-
ronments (many prisms are lost because nitrogen purges are inadvertently shut
of!). Photographic film is not sensitive for wavelengths much beyond 111m; so
infrared spectrometers use detectors such as thermopiles or semiconductor photo-
conductive cells. The wavelength is then scanned by rotating the grating or prism,
and the detector output is recorded on a strip chart. Figure 9.18 shows a typical
spectrometer schematic.
In order to afford greater sensitivity and to minimize the effects of atmospheric
attenuation, a double-beam instrument is ordinarily used. That is, the beam splits
and goes through two similar paths, except that one of them has provisions for
inserting the sample. The light is chopped (usually mechanically) so that signal
processing can be ac. For high absorption, the signal-to-noise ratio may be very
poor; so some variety of phase-sensitive detection is almost always used.
264 Semiconductor Measurements and Instrumentation

Most qualitative analyses will use only a strip-chart recording of relative transmit-
tance vs. wavelength. However, for quantitative analysis (such as for a and C in
Si and Ge) the actual absorption coefficient a must be determined for one or more
of the bands. This is done through the equation
1 e-aiL"(l - R)2
= (9.1)

where 10 is the intensity of the incident beam, 1 the intensity of the light transmitted,
R the reflection coefficient, and x the sample thickness. This equation assumes
normal incidence, parallel sides on the sample, and a surface finish adequate to
prevent scattering (which usually means an optical finish). The solution ofEq. (9.1)
is (from ASTM F 45-64T)

(9.2)

1+ VI + 4C2R2
where B = loge 2C

T
C = (1 _ R)2

and T=L
10
The reflection coefficient R can be measured separately, or for well-characterized
materials, the known value at the wavelength of interest may be inserted into the
equation. n will ordinarily be the number found in tables, and for a small,

R = (nl - n2)2 (9.3)

n1 + n2
where n 1 is the index for the semiconductor and n 2 equals 1 for operation in air
or vacuum. If the complex dielectric constant N = n - ik is used for optical charac-
terization, * the absorption coefficient is given by

a = nwk (9.4)
A
Emittance Spectroscopy.1l7,1l8 Instead of measuring the absorption coefficient
directly as in absorption spectroscopy, in regions where ax ~ 1, the thermal emission
may be measured. It is proportioned to ax and, because of the difficulty of deter-
mining a for the case of ax ~ 1, may be easier to measure.
Reflectance Spectroscopy. The reflectance spectrum will also contain information
similar to that of the other methods and is sometimes used to study the effect of
adsorbed layers on surfaces. A more unusual semiconductor application is that of
electroreflectance, in which the reflectance from a space-charge region generated
either by immersion in a suitably biased electrolyte or by depositing a thin semi-
transparent metal (Schottky diode) over the surface is measured. From such meas-
urements band-structure information and doping levels can sometimes be de-
duced.1l9-121

*For instance, an ellipsometer might be used to determine N at the wavelength of interest.

 The Electron Microscope and Other Analytical Instruments 265

9.8 MASS SPECTROSCOPY

Mass analyzers convert a portion of the sample to be analyzed into ions and then,
by a combination of curved condenser plates and a magnetic field, bring all ions
with the same charge-to-mass ratio to a common focal point. These instruments
in general have greater sensitivity than optical-emission spectroscopes and for that
reason are very useful in semiconductor analysis.
Solid-source mass analyzers are most applicable and ordinarily make use of a
high-frequency, high-voltage spark between two electrodes cut from the material
to be examined. However, if the material is available only in powder form, it can
be pressed into electrodes with a binder, although sensitivity is lost because a portion
of the beam will come from the binder. If only thin layers are available, a counter-
electrode of some other material can be used, but again, sensitivity suffers. 108,109
lon-Microprobe Mass Analyzer. 122 ,123 The mass spectrograph has adequate sensi-
tivity for many useful semiconductor measurements but does lack in spatial resolu-
tion. In order to correct that deficiency, a beam of ions such as argon can be focused
onto a small area on the surface to be analyzed and used to sputter it away locally.
The secondary ions from the surface can then be collected and analyzed by a mass
spectrometer. A schematic of such an instrument is shown in Fig. 9.19. By moving
the sputtering ions across the surface in raster fashion and setting the spectrometer
to detect a particular elm value, topographic scans of a given element's concentration
can be made. By stopping the beam and sputtering a hole into the surface, an
impurity profile normal to the surface can be generated, although calibration is very
difficult because of problems associated with determining and maintaining given
sputtering rates. A further difficulty is that the walls of the sputtered hole will not
be exactly perpendicular, so that at all times there will be some sputtered contribution

'--_. . . .f.-

_..L..._-' Sample

Fig. 9.19. Schematic of an ion-probe mass analyzer. A is the

primary ion source. The magnetic and electrostatic optics of Bare
used to focus the beam. C is a mass spectrometer which analyzes
the secondary ions which are ejected from the material studied.
The secondary ions generate electrons at D which are detected by
a scintillator-photomultiplier combination. Display can then be by
a variety of methods.
266 Semiconductor Measurements and Instrumentation

over the whole depth of the hole. The measured profile will thus not be correct
and furthermore will vary from instrument to instrument (particularly those of
different manufacturers). In many instances the error is negligible, but it is also
possible to change the character of the profile completely. Accordingly considerable
care must be exercised in evaluating and interpreting such data.

9.9 ION BACKSCATTERING

Figure 9.20a is a schematic of the procedure used in ion-scattering experiments.

A high-energy ion beam (up to several million electron volts) capable of penetrating
into the material to be used is allowed to impinge on its surface, and the scattered
beam energy is analyzed. 124 The scattered energy will depend both on the relative
masses of the colliding particles (beam and sample constituents) and on the depth
at which the collisions take place. A typical idealized spectrum will appear as the
solid line in Fig. 9.20b. Should the sample be single-crystal and carefully aligned
along a crystallographic axis, the beam can penetrate much more deeply by "chan-
neling" between rows of atoms before a collision occurs. Thus the energy of the
scattered beam will be substantially reduced, as indicated by the dotted line.
If there are misplaced atoms in the channel, i.e., interstitials, there will be addi-
tional scattering. For example, if the surface is damaged by ion bombardment so
that interstitials of the sample are formed, an energy peak will occur as in Fig. 9.21a.
Should the interstitials be foreign atoms, a peak will still occur, and if the mass
of the foreign interstitial is different from the host, the energy of the scattered ions
will be different and will be displaced. Figure 9.21b shows the appearance if the
interstitial has a mass greater than that of the host atoms.
Sensitivity can be very good, and the technique can be used for analyzing films
and contamination layers on the surface of semiconductors. Examples include
composition of silicon nitride and aluminum oxide films deposited on Si;125,126 the

~ector
/
// Scaitered beam

Collimated ion beam

Sample
(a)

Random orientation

Ul
Q)
u
ta
c.
4-
o
6
z

Energy of scaitered beam

(b) Fig. 9.20. Ion backscattering.
 The Electron Microscope and Other Analytical Instruments 267

--- Random orientation

Q)
E
:;:::
:!:
c
:J
"-
V>
C
oS
,", " , :J\
spectrum \
Host interstitial

(a)

Scattered ion energy

Q)
Foreign
E
:;::: interstitial
:!:
c
:J
"-
V>
C
oS

Fig. 9.21. Use of ion scattering to detect inter- ( b)

stitials. Scaltered ion energy

density of amorphous Si films;127 the growth of secondary films, e.g., an Si0 2 layer
over gold deposited on Si; 128 and miscellaneous surface contamination. 129,130

9.10 RADIOACTIVE METHODS

Neutron-Activation Analysis. los Analysis is performed by irradiating the

sample with neutrons, which converts a portion of the impurities into some radioac-
tive species, and then monitoring the decay time of the activity. The activity A will
be given by
A = cp(JN(l - e- At )
where cP is the integrated neutron flux, (J the absorption cross section of a given
species, N their number, A the decay constant of the newly generated radioactive
species, and t the time after irradiation. In general, all the impurities as well as
the matrix will become radioactive; so means of separating signals must be devised.
The choice of detecting y- or /3-rays will remove some conflict. The short-lifetime
components can often be allowed to decay so that only those with longer lifetimes
are observed. Finally, some chemical separation may be required.
Because of the sensitivity required, the matrix activity can be of particular trouble,
and indeed for most III-Vs is bad enough to virtually preclude its use. However,
for Si and germanium it is a very useful and widely used method.
Charged-Particle-Activation Analysis. 13l Rather than neutron activation, a number
of charged-particle reactions can be used. Some of these will allow greater sensitivity
to elements such as boron, carbon, nitrogen, and oxygen.
Radioactive-Tracer Analysis. If a radioactive isotope of a particular element is
used, its movement as a function of processing can be followed by detecting the
radiation. The element whose motion is to be studied can be totally radioactive,
but more likely will be considerably diluted with normal atoms. It is assumed that
268 Semiconductor Measurements and Instrumentation

the radioactive atoms will be uniformly distributed among the others and will behave
identically with them except for the radioactivity. Radiotracer studies have limited
application but can be very useful in tracking the introduction of impurities if
suitable radioactive elements are available in a form that can be used. Such studies
are most commonly applied to diffusion l32 and segregation-coefficient determi-
nations. 133 They have proved very helpful in establishing a direct correlation be-
tween etch-defined striations in melt-grown crystals and actual impurity-concentra-
tion nonuniformities. 134 Through autoradiograms, local variations of surface buildup
of impurities can be studied, and in particular, redistributions after various washes
and swabbing procedures can be noted. I08
There are several ways of applying tracer data to diffusion-coefficient determi-
nation. They all depend on interpretations based on a combination of the diffusion-
boundary conditions and properties of the emitted radiation. Such studies should
always consider both facets of interpretation before conclusions are drawn. Probably
the easiest method is to remove thin layers sequentially from the diffused surface
(mechanically, by etching, or by oxidation and subsequent removal of the oxide)
and count the activity of each layer. Alternately the activity remaining can be
counted. In such cases the possibility of absorption of radioactivity originating well
below the surface must be taken into account. One major source of error occurs
in either case ifthere are unexpected pile-ups of the tracer. For example, if diffusion
through a thick Si0 2 layer were being studied, pinholes could let the diffusant reach
the silicon, diffuse into it, and remain despite innumerable oxide-etch cycles.
If the absorption coefficient of the radiation in the semiconductor material being
studied is known, a measure of its intensity before and after diffusion combined
with an assumed profile will allow the diffusion coefficient to be calculated. Should
the diffusion be quite deep, a perpendicular section can be taken and the intensity
profiled in a manner such as that described in Ref. 132. If it is suspected that a
portion of a normally ionized impurity is not ionized and therefore not contributing
to electrical conductivity (e.g., phosphorus in high concentrations in silicon), a
heavy-concentration diffusion can be made using a radioactive source. Layers can
then be sequentially stripped away and simultaneous counting and electri-
cal-resistivity readings made. The impurity concentration as determined by radio-
activity and the electrical concentration as determined by resistivity can then be
compared.

REFERENCES

1. V. K. Zworykin et aI., "Electron Optics and the Electron Microscope," John Wiley &
Sons, Inc., New York, 1945.
2. Cecil E. Hall, "Introduction to Electron Microscopy," McGraw-Hill Book Company,
New York, 1953.
3. Anon., TV Display Systems and Image Intensifier for Electron Microscopes, Norelco
Rep!r., 20:18-23 (April 1973).
4. Desmond H. Kay (ed.): "Techniques for Electron Microscopy," F. A. Davis Company,
Philadelphia, 1965.
5. R. J. Jaccodine, Interaction of Diffusion and Stacking Faults in Si Epitaxial Material,
J. Appl. Phys., 36:2811-2814 (1965).
6. M. V. Sullivan and R. M. Finne, Meeting of Electrochemical Society, Houston, October
1960.
7. G. R. Booker and R. Stickler, Method of Preparing Si and Ge Specimens for Examina-
 The Electron Microscope and Other Analytical Instruments 269

tion by Transmission Electron Microscopy, Brit. J. Appl. Phys., 13:446-448 (1962);

G. Das and N. A. O'Neil, Preparation of Large-Area Electron-Transparent Samples
From Silicon Devices, Solid-State Tech., 17:29-31 (August 1974).
8. B. A. Irving, The Preparation of Thin Films of Germanium and Silicon, Brit. J. Appl.
Phys., 12:92-93 (1961).
9. E. Biedermann and K. Brack, Preparation of GaAs Specimens for Transmission Electron
Microscopy, J. Electrochem. Soc., 113: 1088 (1966).
10. Eugene S. Meieran, Transmission Electron Microscope Study of Gallium Arsenide,
J. Appl. Phys., 36:2544-2549 (1965).
11. B. D. Chase, D. B. Holt, and B. A. Unvala: Jet Polishing of Semiconductors, J. Electro-
chern. Soc., 119:310-313 (1972).
12. H. Abrams and R. N. Tauber, Transmission Electron Microscopy of As-grown PbSe
Single Crystals, J. Electrochem. Soc., 116: 103-104 (1969).
13. E. Levine and R. N. Tauber, The Preparation and Examination ofPbTe by Transmission
Electron Microscopy, J. Electrochem. Soc., 115:107-108 (1968).
14. T. G. R. Rawlins and L. E. Bresselard, Electron Microscope Replica Study of Epitaxial
Silicon Nucleation on Silicon, Trans. Met. Soc. AIME, 236:280-284 (1966).
15. P. R. Thornton, "Scanning Electron Microscopy," Chapman & Hall, Ltd., London, 1968;
Oliver C. Wells (ed.), "Scanning Electron Microscopy," McGraw-Hill Book Company,
New York, 1974.
16. Thomas E. Everhart, Deflection-Modulation CRT Display, Proc. IEEE, 54:1480-1482
(1966).
17. Norman A. Foss, Deflection-Modulation Display of Depletion Movement in Epitaxial
and Metal-Semiconductor Junctions, J. Appl. Phys., 41 :823-825 (1970).
18. G. Y. Robinson, Scanning Electron Microscopy Study of the Avalanche Multiplication
Factor, Proc. IEEE, 57:2169-2170 (1969).
19. T. E. Everhart, O. C. Wells, and C. W. Oatley, Factors Affecting Contrast and Resolution
in the Scanning Electron Microscope. J. Electron. Control, 7:97-111 (1959).
20. R. P. Beaulieu, C. D. Cox, and T. M. Black, "An SEM Surface Voltage Measurement
Technique," 10th Annual Proceedings Reliability PhysiCS, pp. 32-35, 1972 (and references
contained therein).
21. A. J. Gonzales, "Factors Involved in the Scanning Electron Microscope Analysis of Glass
Passivated Devices," 9th Annual Proceedings Reliability PhYSics, pp. 142-148, 1971.
22. D. L. Crosthwait, Jr., "Synchronous Biasing of Integrated Circuits in the SEM," Pro-
ceedings 6th Annual Stereoscan Colloquium, Kent Cambridge Scientific, Chicago, 1973.
23. Kurt F. J. Heinrich, Charles Fiori, and Harvey Yakowitz, Image-Formation Technique
for Scanning Electron Microscopy and Electron Probe Microanalysis, Science,
167:1129-1131 (1970).
24. P. R. Thornton, D. V. Sulway, and D. A. Shaw, Scanning Electron Microscopy in Device
Diagnostics and Reliability Physics, IEEE Trans. Electron. Devices, ED-16:360-371
(1969).
25. T. E. Everhart, O. C. Wells, and R. K. Matta, Evaluation of Passivated Integrated Circuits
Using the Scanning Electron Microscope, J. Electrochem. Soc., 111 :929-936 (1964).
26. M. J. Alter and B. A. McDonald, The SEM as a Defect Analysis Tool for Semiconductor
Memories, 9th Annual Proceedings Reliability Physics, pp. 149-154, 1971.
27. John W. Adolphsen and Robert J. Anstead, Use a SEM on a Production Line?!! 8th
Annual Proceedings Reliability Physics, pp. 238-243, 1970.
28. Robert J. Anstead, Failure Analysis Using a Scanning Electron Microscope, Sixth
Annual Reliability Physics Symposium Proceedings, pp. 127-137, 1967.
29. P. R. Thornton et aI., Failure Analysis of Microcircuitry by Scanning Electron Micros-
copy, Microelectron. Reliability, 6:9-16 (1967).
30. P. R. Thornton et aI., Device Failure Analysis by Scanning Electron Microscopy,
Microelectron. Reliability, 8:33-53 (1969).
270 Semiconductor Measurements and Instrumentation

31. I. G. Davies et aI., The Direct Observation of Electrical Leakage Paths due to Crystal
Defects by Use of the Scanning Electron Microscope, Solid State Electron., 9:275-279
(1966).
32. P. R. Thornton et aI., Quantitative Measurements by Scanning Electron Microscopy,
I. The Use of Conductivity Maps, Microelectron. Reliability, 5:291-298 (1966).
33. J. W. Thornhill and I. M. Mackintosh, Application of the Scanning Electron Microscope
to Semiconductor Device Structures, Microelectron. Reliability, 4:97-100 (1965).
34. R. K. Matta, Application of the Scanning Electron Microscope to Semiconductors, Solid
State Tech., 12:34-42 (1969).
35. G. S. Plows and W. C. Nixon, Operational Testing of LSI Arrays by Stroboscopic
Scanning Electron Microscopy, J. Sci. Instr., 1:595-600 (1968).
36. G. V. Lukianoff andR. C. Mullaney, "Electrical Continuity Testing of Passivated
Metallization by Scanning Electron Microscopy," 8th Annual Proceedings Reliability
PhYSics, pp. 244-246, 1970.
37. S. K. Behera and D. P. Speer, "A Procedure for the Evaluation of Failure Analysis
ofMOS Memory Circuits Using the Scanning Electron Microscope in Potential Contrast
Mode," 10th Annual Proceedings Reliability Physics, 1972.
38. J. P. Fleming, Electron Beam Testing, Gentle and Fast, Electronics, 42:92-94 (1969).
39. J. F. Norton and H. L. Lester, "Integrated Circuit Diagnostics Using Electron Beam
Probes," presented at the National Electronics Conference, Chicago, 1969.
40. P. B. Hirsch, R. B. Nicholson, A. Howie, and D. W. Pashley, "Electron Microscopy
of Thin Crystals," Butterworth & Co. (Publishers), Ltd., Washington, 1965.
41. P. J. Estrup and E. G. McRae, Surface Studies by Electron Diffraction, Surface Sci.,
25:1-52 (1971).
42. E. Bauer, Reflection Electron Diffraction, chap. 15; and Low Energy Electron Diffrac-
tion, chap. 16, in R. F. Bunshah (ed.), "Techniques of Metals Research," Interscience
Publishers, Inc., New York, 1969.
43. R. C. Henderson, W. J. Polito, and J. Simpson, Observation of SiC with Si(111)-7 Surface
Structure Using High-Energy Electron Diffraction, Appl. Phys. Lett., 16:15-17 (1970).
44. C. W. B. Grigson, Improved Scanning Electron Diffraction System, Rev. Sci. Instr.,
36:1587-1593 (1965).
45. A. Y. Cho, GaAs Epitaxy by a Molecular Beam Method: Observations of Surface
Structure on the (001) Face, J. Appl. Phys., 42:2074-2081 (1971).
46. G. J. Russell and D. Haneman, Oxygen Adsorption on Vacuum Cleaved GaAs at
Liquid Nitrogen Temperature by LEED, Surface Sci., 27:362-366 (1971).
47. Herbert W. Schnopper, Spectral Measurements with Aligned and Misaligned Two-
Crystal Spectrometers, I, Theory of the Geometrical Window, J. Appl. Phys.,
36:1415-1423 (1965).
48. Herbert W. Schnopper, Spectral Measurements with Aligned and Misaligned Two-
Crystal Spectrometers, II, Alignment, J. Appl. Phys., 36:1423-1430 (1965).
49. Herbert W. Schnopper, Erratum, J. Appl. Phys., 36:3692 (1965).
50. A. R. Lang, Crystal Growth and Crystal Perfection: X-Ray Topographic Studies,
Discussions Faraday Soc., (38) 292-297 (1964).
51. Eugene S. Meieran, Reflection X-Ray Topography of GaAs Deposited on Ge,
J. Electrochem. Soc., 114:292-295 (1967).
52. A. R. Lang, A Method for the Examination of Crystal Sections Using Penetrating
Characteristic X-Radiation, Acta Met., 5:358-364 (1957).
53. A. R. Lang, Direct Observation ofIndividual Dislocations by X-Ray Diffraction, J. Appl.
Phys., 29:597-598 (1958).
54. A. R. Lang, The Projection Topograph: A New Method in X-Ray Diffraction Micro-
radiography, Acta Cryst., 12:249-250 (1959).
55. A. R. Lang, Studies oflndividual Dislocations in Crystals by X-Ray Diffraction Micro-
radiography, J. Appl. Phys., 30:1748-1755 (1959).
 The Electron Microscope and Other Analytical Instruments 271

56. G. H. Schwuttke, X-Ray Diffraction Microscopy Study ofImperfections in Silicon Single

Crystals, J. Electrochem. Soc., 109:27-32 (1962).
57. A. E. Jenkinson and A. R. Lang, X-Ray Diffraction Topographic Studies of Dislocations
in Floating-Zone Grown Silicon, in J. B. Newkirk and J. H. Wernick (eds.), "Direct
Observations of Imperfections in Crystals," Interscience Publishers, Inc., New York,
1962.
58. G. H. Schwuttke, New X-Ray Diffraction Microscopy Technique for the Study of
Imperfections in Semiconductor Crystals, 1. Appl. Phys., 36:2712-2721 (1965).
59. Kazutake Kohra, Mitsuru Yoshimatsu, and Ikuzo Shimizu, X-Ray Observation of Lattice
Defects Using a Crystal Monochrometer, in J. B. Newkirk and J. H. Wernick (eds.),
"Direct Observations of Imperfections in Crystals," Interscience Publishers, Inc., New
York, 1962.
60. Mitsuru Yoshimatsu, Atsushi Shibata, and Kazutake Kohra, A Modification of the
Scanning X-ray Topographic Camera (Lang's Method), in Gavin R. Mallett, Marie Fay,
and William M. Mueller (eds.), "Advances in X-Ray Analysis," vol. 9, Plenum Press,
Plenum Publishing Corporation, New York, 1966.
61. N. Kato and A. R. Lang, A Study of Pendellosung Fringes in X-Ray Diffraction, Acta
Cryst., 12:787-794 (1959).
62. N. Kato, Dynamical Diffraction Theory of Waves in Distorted Crystals, II, Perturbation
Theory, Acta Cryst., 16:282-290 (1963).
63. W. W. Webb, X-Ray Diffraction Topography, in J. B. Newkirk and J. H. Wernick (eds.),
"Direct Observations of Imperfections in Crystals," Interscience Publishers, Inc., New
York, 1962.
64. Volkmar Gerald, X-Ray Methods for Detection of Lattice Imperfections in Crystals,
in William M. Mueller (ed.), "Advances in X-Ray Analysis," vol. 3, Plenum Press,
Plenum Publishing Corporation, New York, 1960.
65. G. H. Schwuttke, Direct Observation of Imperfections in Semiconductor Crystals by
Anomalous Transmission of X-Rays, 1. Appl. Phys., 33:2760-2767 (1962).
66. J. K. Howard and R. D. Dobrott, Compositional X-Ray Topography, 1. Electrochem.
Soc., 113:567-573 (1966).
67. L. G. Schulz, Method of Using a Fine-Focus X-Ray Tube for Examining the Surface
of Single Crystals, 1. Metals, 6: 1082-1083 (1954).
68. Laurence N. Swink and Maurice J. Brau, Rapid Non-destructive Evaluation of Macro-
scopic Defects in Crystalline Materials: The Laue Topography of (Hg, Cd) Te, Met.
Trans., 1:629-634 (1970).
69. Junji Matsui and Tsutomu Kawamura, Spotty Defects in Oxidized Floating-zoned
Dislocation-free Silicon Crystals, Japan. J. Appl. Phys., 11: 197-205 (1972).
70. Jun-ichi Chikawa, Isao Fujimoto, Sigeaki Endo, and Kiyoshi Mase, X-Ray Television
Topography for Quick Inspection of Si Crystals, in Howard R. Huff and Ronald R.
Burgess (eds.), "Semiconductor Silicon," The Electrochemical Society, Princeton, 1973.
71. Heinrich Grienauer, High Temperature X-Ray Topography of Silicon in Howard R.
Huff and Ronald R. Burgess (eds.), "Semiconductor Silicon," The Electrochemical
Society, Princeton, 1973.
72. I. Blech, J. Guyaux, and G. Cooper, High Temperature Camera for X-Ray Topography,
Rev. Sci. [nstr., 38:638-641 (1967).
73. Jun-ichi Chikawa, Isao Fujimoto, and Takao Abe, X-Ray Topography Observation of
Moving Dislocations in Silicon Crystals, Appl. Phys. Lett., 21 :295-298 (1972).
74. U. K. Bonse, M. Hart, and J. B. Newkirk, X-Ray Diffraction Topography, in J. B.
Newkirk and G. R. Mallett (eds.), "Advances in X-Ray Analysis," vol. 10, pp. 1-8,
Plenum Press, Plenum Publishing Corporation, New York, 1967.
75. E. M. Juleff, A. G. Lapierre III, and R. G. Wolfson, The Analysis of Berg-Barrett Skew
Reflections and Their Applications in the Observation of Process-induced Imperfections
in (111) Silicon Wafers, in J. B. Newkirk and G. R. Mallett (eds.), "Advances in X-Ray
272 Semiconductor Measurements and Instrumentation

Analysis," vol. 10, pp. 173-184, Plenum Press, Plenum Publishing Corporation, New
York, 1967.
76. A. Authier, Contrast of Dislocation Images in X-Ray Transmission Topography, in J. B.
Newkirk and G. R. Mallett (eds.), "Advances in X-Ray Analysis," vol. 10, pp. 9-31;
Plenum Press, Plenum Publishing Corporation, New York, 1967.
77. S. B. Austerman and J. B. Newkirk, Experimental Procedures in X-Ray Diffraction
Topography, in J. B. Newkirk and G. R. Mallett (eds.), "Advances in X-Ray Analysis,"
vol. 10, pp. 134-152, Plenum Press, Plenum Publishing Corporation, New York, 1967.
78. H. P. Layer and R. D. Deslattes, A Simple Nonscanning Camera for X-Ray Diffraction
Contrast Topography, J. Appl. Phys., 37:3631-3632 (1966).
79. J. S. Makris and C. H. Ma, A Modified X-Ray Diffraction Microscope Technique for
Study of Dislocations in Crystals, Trans. Met. Soc. AIME, 230:1110-1112 (1964).
80. G. Dionne, High-Resolution X-Ray-Diffraction Topography Using K,8 Radiation,
J. Appl. Phys., 38:4094-4096 (1967).
81. G. J. Carron, X-Ray Topographic Camera, Rev. Sci. Instr., 38:628-631 (1967).
82. Wilhad Reuter, Electron Probe Microanalysis, Suiface Sci., 25:80-119 (1971).
83. D. B. Wittry, J. M. Axelrod, and J. O. McCaldin, Use of the Electron Probe X-Ray
Microanalyzer in the Study of Semiconductor Alloys, in Harry C. Gatos (ed.), "Prop-
erties of Elemental and Compound Semiconductors," Interscience Publishers, Inc., New
York, 1960.
84. M. I. Nathan and S. H. Moll, Electron Beam Micro Analysis of Germanium Tunnel
Diodes, IBM J. Res. Develop., 6:375-377 (1962).
85. Frank J. Cocca and Kenneth G. Carroll, Electron Microprobe Analysis of Impurity
Heterogeneities in Thermally Grown Silicon Oxide, IEEE Trans. Electron. Devices,
ED-15: 962-966 (1968).
86. S. S. So and H. R. Potts, Computer Programs for Quantitative and Semiquantitative
Analysis with the Electron MIcroprobe Analyzer, J. Electrochem. Soc., 115:64-70
(1968).
87. Rolf Woldseth, "X-Ray Energy Spectrometry," Kevex Corp., Burlingame, Calif., 1973.
88. Wendland Beezhold, Ion-induced Characteristic X-Ray Micro-Analysis, in Howard R.
Huff and Ronald R. Burgess (eds.), "Semiconductor Silicon," The Electrochemical
Society, Princeton, 1973.
89. Thomas A. Carlson, Electron Spectroscopy for Chemical Analysis, Physics Today,
25:30-39 (January 1972).
90. Homer D. Hagstrum, Electronic Characterization of Solid Surfaces, Science,
178:275-282 (1972).
91. Roland E. Weber, Auger Electron Spectroscopy for Thin Film Analysis, Re-
search/Development, 23:22-28 (October 1972).
92. Chuan C. Chang, Auger Electron Spectroscopy, SUiface Sci., 25:53-79 (1971).
93. Paul W. Palmberg et aI., "Handbook of Auger Spectroscopy," Physical Electronic
Industries, Edina, Minn., 1972.
94. J. M. Morabito and J. C. Tsai, In-Depth Profiles of Phosphorus Ion-implanted Silicon
by Auger Spectroscopy and Secondary Ion Emission, Surface Sci., 33:422-426 (1972).
95. P. W. Palmberg, Use of Auger Electron Spectroscopy and Inert Gas Sputtering for
Obtaining Chemical Profiles, J. Vacuum Sci. Tech., 9:160-163 (1972).
96. J. T. Grant and T. W. Haas, Auger Electron Spectroscopy of Si, Surface Sci., 23:347-362
(1970).
97. Norman J. Taylor, Thin Reaction Layers and the Surface Structure of Silicon (111),
Surface Sci., 15:169-174 (1969).
98. Tadoshi Narusawa, Auger Electron Emission from Gold Deposited on Silicon (111)
Surface, Japan. J. Appl. Phys., 10:280-281 (1971).
99. T. Narusawa, S. Komiya, and A. Hiraki, Auger Spectroscopic Observation of Si-Au
Mixed Phase Formation at Low Temperatures, Appl. Phys. Lett., 21 :272-273 (1972).
 The Electron Microscope and Other Analytical Instruments 273

100. R. L. Moon and L. W. James, Auger Spectra of Hc1 Vapor-etched n+ GaAs 100
Substrates, J. Electrochern. Soc., 120:581-583 (1973).
101. John J. Uebbing and Norman J. Taylor, Auger Electron Spectroscopy of Clean Gallium
Arsenide, J. Appl. Phys., 41 :804-808 (1970).
102. B. A. Joyce and J. H. Neave, An Investigation of Silicon-Oxygen Interactions Using
Auger Electron Spectroscopy, Surface Sci., 27:499-515 (1971).
103. R. C. Henderson, Silicon Cleaning with Hydrogen Peroxide Solutions: A High Energy
Electron Diffraction and Auger Electron Spectroscopy Study, J. Electrochern. Soc.,
119:772-775 (1972).
104. Chuan C. Chang, Contaminants on Chemically Etched Silicon Surfaces: LEED-Auger
Method, Surface Sci., 23:283-298 (1970).
105. J. H. Affleck, Auger Spectroscopy and Silicon Surfaces, in Charles P. Marsden (ed.),
"Silicon Device Processing," National Bureau of Standards, Spec. Pub. 337, 1970.
106. John J. Uebbing, Use of Auger Electron Spectroscopy in Determining the Effect of
Carbon and Other Surface Contaminants on GaAs-Cs-O Photocathodes, J. Appl. Phys.,
41 :802-804 (1970).
107. H. G. Maguire and P. D. Augustus, The Detection of Silicon-Oxynitride Layers on the
Surfaces of Silicon-Nitride Films by Auger Electron Emission, J. Electrochern. Soc.,
119:791-793 (1972).
108. Philip F. Kane and Graydon B. Larrabee, "Characterization of Semiconductor Mate-
rials," McGraw-Hill Book Company, New York, 1970.
109. J. Paul Cali (ed.), "Trace Analysis of Semiconductor Materials," The Macmillan Com-
pany, New York, 1964.
110. William R. Knolle, Flame Emission Analysis of Potassium Contamination in Silicon
Slice Processing, J. Electrochern. Soc., 120:987-991 (1973).
Ill. J. E. Barry, H. M. Donega, and T. E. Burgess, Flame Emission Analysis for Sodium
in Silicon Oxide Films and on Silicon Surfaces, J. Electrochern. Soc., 116:257-259 (1969).
112. William R. Knolle, and Theodore F. Retajczyk, Jr., Monitoring Sodium Coptamination
in Silicon Devices and Processing Materials by Flame Emission Spectrometry,
J. Electrochern. Soc., 120:1106-1111 (1973).
113. W. Kaiser and P. H. Keck, Oxygen Content of Silicon Single Crystals, J. Appl. Phys.,
28:882-887 (1957). .
114. A. R. Bean and R. C. Newman, The Solubility of Carbon in Pulled Silicon Crystals,
J. Phys. Chern. Solids, 32:1211-1219 (1971).
115. W. A. Pliskin, Use of Infrared Spectroscopy for the Characterization of Dielectric Films
on Silicon, in Howard R. Huff and Ronald R. Burgess (eds.), "Semiconductor Silicon,"
The Electrochemical Society, Princeton, 1973.
116. K. H. Beckmann, Investigation of the Chemical Properties of Stain Films on Silicon
by Means of Infrared Spectroscopy, Surface Sci., 3:314-332 (1965).
117. M. Blatte, Emittance Spectroscopy as a Diagnostic Tool for Semiconductors, in Rolf R.
Haberecht and Edward L. Kern (eds.), "Semiconductor Silicon," The Electrochemical
Society, New York, 1969.
118. D. L. Stierwalt and R. F. Potter, Lattice Absorption Bands Observed in Silicon by Means
of Spectral Emissivity Measurements, J. Phys. Chern. Solids, 23:99-102 (1962).
119. R. Sittig and W. Zimmerman, Doping Inhomogeneities in Semiconductors Measured
by Electrorefiectance, in Howard R. Huff and Ronald R. Burgess (eds.), "Semiconductor
Silicon," The Electrochemical Society, Princeton, 1973.
120. Richard A. Forman, David E. Aspnes, and Manuel Cardona, Transverse Electrore-
fiectance in Semi-insulating Silicon and Gallium Arsenide, J. Phys. Chern. Solids,
31 :227-246 (1970).
121. Manuel Cardona, Kerry L. Shaklee, and Fred H. Pollak, Electrorefiectance at a Semi-
conductor-Electrolyte Interface, Phys. Rev., 154:696-720 (1967).
122. Helmut Liebl, Ion Microprobe Mass Analyzer, J. Appl. Phys., 38:5277-5283 (1967).
274 Semiconductor Measurements and Instrumentation

123. A. J. Socha, Analysis of Surfaces Utilizing Sputter Ion Source Instruments, Surface Sci.,
25:147-170 (1971).
124. J. W. Mayer, L. Eriksson, and J. A. Davies, "Ion Implantation in Semiconductors,"
Academic Press, Inc., New York, 1970.
125. J. Gyulai et al., Analysis of Silicon Nitride Layers on Silicon by Backscattering and
Channeling Effect Measurements, Appl. Phys. Lett., 16:232-234 (1970).
126. M. Kamoshida and J. W. Mayer, Backscattering Studies of Anodization of Aluminum
Oxide and Silicon Nitride on Silicon, J. Electrochem. Soc., 119:1084-1090 (1972).
127. M. H. Brodsky, D. Kaplan, and J. F. Ziegler, Densities of Amorphous Si Films by
Nuclear Backscattering, Appl. Phys. Lett., 21:305-307 (1972).
128. Akio Hiraki, Eriabu Lugujjo, and J. W. Mayer, Formation of Silicon Oxide over Gold
Layers on Silicon Substrates, J. Appl. Phys., 43:3643-3649 (1973).
129. W. K. Chu, J. W. Mayer, M-A. Nicolet, T. M. Buck, G. Amse1, and F. Eisen, Micro-
analysis of Surface, Thin Films, and Layers Structures by Nuclear Backscattering and
Reactions, in Howard R. Huff and Ronald R. Burgess (eds.), "Semiconductor Silicon,"
The Electrochemical Society, Princeton, 1973.
130. D. A. Thompson, H. D. Barber, and W. D. Mackintosh, The Determination of Surface
Contamination on Silicon by Large Angle Ion Scattering, Appl. Phys. Lett., 14: 102-103
(1969).
13l. E. A. Schweikert and R. E. Wainerdi, Ultratrace Analysis of Light Elements Using
Charged Particle Activation, Application to the Determination of Oxygen in Silicon,
J. Electrochem. Soc., 115:249C (1968).
132. B. I. Boltaks, "Diffusion in Semiconductors," Academic Press, Inc., New York, 1963.
133. S. Nakanuma, Radiotracer Studies on the Incorporation of Phosphorus in Epitaxially
Grown Silicon, J. Electrochem. Soc., 111: 1199-1200 (1964).
134. G. R. Cronin, G. B. Larrabee, and J. F. Osborne, Annular Facets and Impurity
Striations in Tellurium Doped Gallium Arsenide, J. Electrochem. Soc., 113:293-294
(1966).
 Index

A-B etch, 35, 199 Cold probe, 146

Absorption spectroscopy, 263 Color charts, 173
Achromats, 220 Complexes, 23
AES (Auger electron spectroscopy), 253, 260 Conductivity mobility, 131
Air gages, 155 Conductivity type, 144
A1Sb polarity determination, 16 Conoscope, 230
Amorphous layers, 22 Contrast, 225
Angle lapping (see Beveling; Sectioning; Staining) Copper decoration, 23, 34, 35, 52
Angles: Copper displacement plating, 200, 211
between planes, 3, 4 Copper etch, 33, 199
trace, 6 Corbino effect, 144
Anodic oxide, 212 CP-4 etch, 32, 33,41,42, 199
Anomalous dispersion, 14 CP-4a etch, 36, 41, 199
Antistructure, 22 Crystal orientation, I
Apochromats, 220 Crystallographic defects, 21
ASTM etch, 33, 199 Cyanide etch, 33, 199
ASTM F43, 67
ASTM F47, 33, 42
ASTM F76, 137, 138 d values for cubic crystals, 17
ASTM F81, 68 Damage:
ASTM F95-71, 169 neutron, 53
ASTM FI2I, 25 oxidation-induced, 38, 52
ASTM FI43-71T, 182 radiation, 53
Auger spectroscopy, 253, 260 surface, 29, 49, 210
Dark field, 219, 226
Dash etch, 32, 33, 39, 199
Bardeen-Herring source, 36 Debye-Scherrer pattern, 35
Becke lines, 223 Decoration:
pseudo-,31 by anodic oxidation, 211, 213
Bell No.2 etch, 199 copper, 23, 34, 35, 52
Beveling, 50, 175, 188 by etching (see Delineation)
double, 92 by selective deposition, 43
Birefringence, 22, 45, 52 by staining (see Staining)
(See also Polarization microscopy) Defects:
Borrmann's topography, 35 antistructure, 23
Bragg angle, 17, 46 complex multiple, 23
Brewster angle, 165 dislocations, 22, 25
foreign atoms, 23
Frenkel,23
C-V (capacitance-voltage) plot, 88 inclusions, 43
Capacitance-voltage (C-V) measurements, 88 interstitials, 22, 53, 266
Carbon in silicon 25, 267 lattice, 22
Carrier concentration, 65 lineage, 22, 41, 42
(See also Resistivity) point, 21, 53
Cathodoluminescence, 43, 108 radiation, 22, 52
CdS: Schottky, 21
inclusions in, 45 stacking faults, 36
polarity determination, 16 strain, 22
CdTe polarity determination, 16 surface, 52
Charged-particle-activation analysis, 24, 267 surface damage, 22, 49, 210
Chemical safety, 196 twins, 22, 40
Chromatic aberration, 225 de Haas-van Alphen effect, 134
Cleavage planes, II Delineation:
Cleaving, II, 193 damaged regions, 210
Climb,26 dislocations, 29

275
276 Index
Delineation (ConI.) Etchants (ConI.)
epitaxial layer, 209 cyanide, 199
general, 200 Dash, 32, 199
grain boundaries, 42 Dow,33,199
junction, 201 ferricyanide, 42, 199
resistivity striations, 211 GaAs dislocations, 35
stacking faults, 39 Ge dislocations, 33
twin boundaries, 40 grain boundaries, 42
Delta four-point probe, 73 InSb dislocation, 36
Depth of detail, 237 iodine, 199
Depth of field, 237 Mercury, 33, 199
Diamond: optical refiectogram, 15
cleavage, 11 p-etch, 199
dislocation detection, 35 planar, 199
inclusions in, 45 polarity determination, 16
twin planes, 11 polish, 199
Differential resistance in avalanche, 52, 66 Purdue, 199
Diffraction effects, 222, 252 Richards-Crockers, 35, 199
Diffractometer, 46, 254 Russian, 33, 199
Diffusion-coefficient measurements, 268 Sailor, 39, 199
Diffusion-length measurements, 118 Schell, 199
Diffusion pipes, 212 Secco, 33, 199
Diode breakdown voltage, 85 Si dislocation, 33
Direction cosines, 6 Sirt!, 32, 33, 39, 42, 200, 204, 209, 210
Direction indices, 3 stain, 207
Dislocatious, 22, 25 stains and, 200
counting procedures for, 29, 33 Superoxol, 33, 41, 199
decoration of, 23, 34, 52 twin definition, 41
diffusion induced, 32 W-R, 35,199
etchants for, 33 white, 41, 199
loops, 23, 27, 28 Ettingshausen voltage, 137
misfit, 28, 32 Extrinsic stacking faults, 36
partial,33 Eyepieces, 220
stair rod, 39
Double beveling, 92
FES (field-emission spectroscopy), 21, 260
Double-crystal spectrometry, 34, 255
Field-emission spectroscopy (FES), 21, 260
Dow etch, 33, 199
Film resolution, 238
Drift mobility, 131
Film speed, 235
Dunlap ellipse, 135
Flame photometry, 263
Fluorites, 220
Edge dislocation, 25
Foreign atoms, 23
Electroluminescence, 108, 121
Four-point probe, 66
Electron backscattering, 183
errors in using, 79
Electron-beam device testing, 251 Fourier-transform spectrophotometer, 170
Electron diffraction, 40, 252 Fracture patterns, II
Electron microscopy, 243 Frenkel defect, 23
etchants for thinning, 246
Fringe lines, 176
replication, 245 Fused-salt etch, 39
resolution, 243
sample thinning, 244
scanning (see Scanning electron microscope) GaAs:
transmission, 244 antistructure, 23
Electron paramagnetic resonance (EPR), 23, 50, 52, 53 Bragg angles, 17
Electron spectroscopy, 259 cleavage, 11
Electronic gage, 155 crystallographic defects, 21
Ellipsometers, 88, 158 d values, 17
Emission spectroscopy, 24, 263 dislocation detection, 35
Emittance spectroscopy, 264 growth planes, 9
Epitaxial layer: inclusions in, 45
delineation of, 204, 209 junction delineation, 206
resistivity, 75, 83, 86 misfit dislocations, 28
thickness, 155, 156, 166, 169, 170, 181 orientation of, 8
EPR (see Electron paramagnetic resonance) polarity determination, 16
Etch pits, II, 29 stacking-fault etchants, 39
fiat-bottomed, 29 x-ray diffraction by, 35
orientation of, 12, 31 GaP dislocation detection, 35, 36
Etchants: GaSb polarity determination, 16
A-B etch, 35, 199 Germanium:
ASTM,199 Bragg angles, 17
Bell No.2, 199 cleavage, II
composition of, 198, 199 crows feet, 52
CP-4, 33, 41, 199 crystallographic defects, 21
CP-4a, 199 d values, 17
 Index 277
Germanium (Cont.) Interference effects, 165
dislocation etches, 33 Interference fringes, 175, 179
dislocations in, 25 Interference microscopy, 230
epitaxial layers (see Epitaxial layer) Interferometry, 159, 175
etch-pit orientation, 12 multiple-beam, 179
grain-boundary etchant, 42 Internal friction, 24
growth fiats, 9 Interstitials, 22, 23, 266
growth planes, 9 Intrinsic stacking faults, 36
helices in, 28 Inversion layers, 1,65, 131
inclusions in, 45 Iodine etch, 199
junction delineation, 200, 205 Ion backscattering, 50, 266
lineage in, 41 Ion mass analyzer, 24, 265
misfit dislocations, 28 Ion microprobe, 89
orientation of, 8, 13 Ion-neutralization spectroscopy (INS), 260
oxygen in, 25
stacking-fault etchants, 39
stacking-fault orientation, 12 Junction delineation, 201, 213, 250
temperature coefficient of resistivity, 81
twin planes, 11, 40
vacancy density, 21 Kellner eyepiece, 220
x-ray diffraction by, 35 Koehler illumination, 219
Glare, 225
Glide direction, 25
Glide planes, 26 Lang x-ray topography, 257
Grain boundaries, 42 Lateral profiling, 93
Growth planes, 9 Lattice defects, 22
Lattice stress and strain, 22, 44
Laue method, 8, 18
Hall angles, 140 LEED (low-energy electron diffraction), 252, 260
Hall effect, 133 Lifetime(s):
AC measurements, 137 boundary effects, III
ASTM measurement procedure, 138 carrier injection, 110, 113
behavior with temperature, 134 charge-collection efficiency, 121
calculations, 136 definition of, 105
for concentration measurements, 66, 85, 133 diffusion-length measurements, 118
by Corbino effect, 144 drift, 120
Dauphinee and Mooser, 143 high resistivity material, 121
errors in measurements, 135, 140 light sources, 110
four-point probe measurements, 141 literature guide, 108
high resistivity samples, 144 microwave, 109
in inhomogeneous samples, 139 minimum sample thickness, 112
by magnetoresistance, 144 noise, 121
measuring equipment, 142 PEM,I17
in melts, 144 photoconductive decay, 107
mixed conduction, 134 photoconductivity, 114
for typing, 146 range of measurements, 109
units, 136 surface photovoltage, 115
van der Pauw method, 141 Light-section microscope, 181
Hall mobility, 131, 144 Lineage, 22, 41, 42
Hardness, 32 Loops, dislocation, 23, 27, 28
Helices, 28 Low-energy electron diffraction (LEED), 252, 260
HgCdTe dislocation etch, 35
HgSe polarity determination, 16
HgTe polarity determination, 16 Magnetoresistance, 144
Hot probe, 145 Mass spectroscopy, 265
Huygens eyepiece, 220 solid,24
Mechanical damage, 2, 22, 28, 49, 154,210
Mechanical damping, 24
lED (incident electron diffraction), 260 Mechanical surface damage, 2, 22, 38, 45, 49, 210
Impurity striations, 211 Mercury etch, 33, 199
lnAs polarity determination, 16 Metal discontinuities, 248
Inclusions, 22, 43 Michelson interferometer, 170
Infrared-absorption spectroscopy, 53, 263 Microgoniometer, II, 228
Infrared microscopy, 34, 234 Micrometer, 154
InP polarity determination, 16 Microprobe analysis, 258
INS (ion-neutralization spectroscopy), 260 Microscope eyepieces, 220
InSb: Microscopes:
cleavage, 11 binocular, 219
dislocation etch pits, 30, 36 diffraction in, 222
growth planes, 9 electron, 243
orientation of, 8 eyepieces, 220
polarity determination, 16 image contrast, 221, 225, 234, 248
Interference contrast, 13, 22, 39, 231 image degradation, 226
278 Index
Microscopes (Cont.) Photography (Cont.)
infrared, 234 light meter, 235
interference, 230 lighting, 239
metallurgical, 228 reciprocity law, 235
objectives, 220 stereophotography, 240
polarization, 228 Photomagnetoelectric effect, 50, 108, 117
resolution of, 222, 243 Photometry, flame, 263
scanning electron, 246 Photomicrography, 235
split-field, 228 Pinholes, oxide, 213
stereoscopic, 219 Pipes, diffusion, 212
toolmakers, 228 Planar etch, 199
ultra, 224 Planar Hall voltage, 133
Microwave measurements, 84, 109 Planes, crystallographic: angles between, 3
Mobility: directions of, 3
conductivity, 131 indices, I
drift, 131 models for, 4
errors in measurement, 132 relative positions of, 3
Hall, 131, 144 Plasma resonance, 87
majority carrier, 131 Plastic flow, 44, 82
minority carrier, 132 Plating, selective, 20 I
Models, crystal, 4 Point defects, 21
Monsanto evaluation standards, 179 Poisson's ratio, 47
MOS (metal-oxide-semiconductor) capacitance, 90, Polarity determination, 14
106-108, 131, 146 Polarization microscopy, 228
Multiple-beam interferometry, 179 Polarizers, 161
Polycrystal regions, 43
Polygonization, 26, 27
Nemst voltage, 137 Potting, 194
Neutron-activation analysis, 24, 267 Prismatic loops, 28
Newton-ring interferometer, 48 Probes, resistivity, 78
Nicol polarizer, 161 Profiling:
Nomarski interference, 233 lateral resistivity, 93
Numerical aperture, 232 surface height, 181
vertical resistivity, 88
Profilometer, 181
Objectives, microscope, 220 Pseudo-Becke line, 31, 223
Optical absorption spectroscopy, 24, 262 Purdue etch, 199
Optical gage, 155
Optical reflectograms, 13
Orientation: Q-meters, 84
crystal, I
sawing to, 18
Oxide damage, 213 Rad (rd), 53
Oxide thickness, 173, 179 Radiation damage, 52
Oxygen: Radioactive-tracer analysis, 24, 267
in Ge, 25 Ramsden eyepiece, 220
in Si, 25, 211, 263, 267 Reciprocity law (photographic), 235
swirls, 211 Recombination centers, 106
RED (see Reflected high-energy electron diffraction)
Reflectance spectroscopy, 264
p etch, 199 Reflected high-energy electron diffraction (RHEED),
p-n-junction delineation, 201, 213, 250 252,260
Package opening, 214 Reflectograms, optical, 13
Partial dislocations, 28 Refractive index by ellipsometry, 160
Pattern shift, 52 Resistivity, 65
PbS, 23 AC meters, 76
PbSe, dislocation etch, 36 attenuated total reflection, 87
PbSeTe, dislocation etch, 36 C-V measurements, 88
PbSnTe, inclusions in, 45 cylindrical samples, 71
PESIS (photoelectron spectroscopy of inner-shell delta four-point probes, 73
electrons), 260 epitaxial layers, 75, 83, 86
PESOS (photoelectron spectroscopy of outer-shell errors in measurement, 79
electrons), 260 four-point probe: linear, 69
Phase contrast, 226, 232 square, 72
Phase-shift corrections, 169 four-point probe correction factors, 70
Photoconductive decay, 107 instrumentation, 75
Photoconductivity, 114 microwave measurements, 84
Photography: optical absorption, 87
depth of detail, 237 plasma resonance, 87
depth of field, 237 probes: liquid, 78
exposure, 235 metal,78
film resolution, 238 profiling, 88
focusing, 236 Q-meter,84
 Index 279
Resistivity (Cont.) Silicon (Cont.)
radial variation, 68 lineage in, 41
single-point probe, 68 misfit dislocations, 28, 32
spreading resistance, 66, 82 nitrogen in, 267
square-array corrections, 74 orientation of, 8
temperature coefficient of, 81 oxygen in, 25, 211, 263, 267
test structures, 67 oxygen swirls in, 211
thermal rebalance, 85 polygonization, 26
three-layered structures, 72 Si0 2 precipitation, 28, 211
three-point probe, 85 SiP in, 43
two-layered structures, 71, 75, 83, 86 slip in, 26
two-point probe, 67 stacking-fault etchants, 39
van der Pauw, 72 stacking-fault orientation, 12
Resolution: stacking-fault swirls in, 211
electron microscope, 243 strain in, 45
optical microscope, 222 surface damage in, 29, 38, 51, 210
photographic, 238 temperature coefficient of resistivity, 81
Resolving limit (optical), 222 twin planes, 11, 40
RHEED (refiected high-energy electron diffraction), vacancy density, 21
252,260 x-ray diffraction by, 35
Richards-Crockers etch, 199 Si02 in Si, 28
Righi-Leduc voltage, 137 SiP in silicon, 43
Roentgen, 53 Sirt! etch, 32, 33, 39, 42, 199, 200, 204, 209, 210
Russian etch, 33, 199 Slip, 42
Slip directions, 25
Slip lines, 27
Safety, chemical, 196 Slip planes, 25
Sailor's etch, 33, 39, 199 Solid mass spectroscopy, 24
Scanning electron microscope (SEM), 32, 246, 260 Spectrometer, double-crystal, 255
viewing specifications, 251 Spectrophotometer, 167
Schell etch, 199 Spectroscopy:
Schottky defects, 21 absorption, 263
Screw dislocations, 28 electron, 259
Secco etch, Dow, 33, 199 emission, 263
Sectioning, 50, 187 emittance, 264
by cleaving, 193 infrared-absorption, 263
delineation stains, 200 mass, 265
diffusion pipes, 200, 212 solid, 24
experimental, 188 optical, 262
interpretation, 175, 187 reflectance, 264
perpendicular, 192 Spreading resistance, 66, 82
safety precautions, 196 Stacking faults, 22, 28, 36, 182
transistors, 194 etchants for, 39
very small angle, 192 geometry of, 12, 183
Seebeck coefficient, 44 orientation of, 12, 37
Selective plating, 20 I Staining, 146, 200, 207
Selectively staining, 201 effect of space-charge region, 201
SEM (scanning electron microscopy), 32, 246, 260 (See also Sectioning)
SiC, 43 Stains and etchants, 200
dislocation etch pits, 36 Step-height measurements, 181, 226
polarity determination, 16 Stereographic-projection charts, 4
stacking-fault etchant, 39 Stereophotographs, 240
Silicon: Strain, lattice, 22, 52
boron in, 267 azimuthal variations in, 48
Bragg angles, 17 from diffUSion, 45
carbon in, 25, 211, 263 measurement of, 46
cleavage, II from oxide overgrowth, 45
copper decoration of, 23, 33, 52 in vapor deposited layers, 45
crystallographic defects, 21 Substitutional impurities, 23
d values, 17 Suhl effect, 108
diffusion pipes in, 212 Superoxol etch, 33, 41, 199
dislocation etches, 33 Surface contamination, 262-264, 267, 268
dislocations in, 25 Surface damage, 2, 29, 38, 45, 52, 210
electron diffraction by, 35 Surface defects, 52
epitaxial layer (see Epitaxial layers) Surface photovoltage, 108, 115
etch-pit orientation, 12 Surface recombination velocity, 105, 135
grain-boundary etchant, 42 Surface roughness, 52, 181
growth fiats, 9
growth planes, 9
helices in, 28 TED (transmission electron diffraction), 260
impurity striations, 211 TEDCM (transmission electron diffraction contrast
inclusions in, 45 microscopy), 260
junction delineation, 200, 204 TEM (transmission electron microscopy), 260
280 Index
Temperature coefficient of resistivity, 81 Twins (Cont.)
Temperature profiling, 234 etchants for, 41
Tensor properties, I higher-order, 40
Tesla, 136 planes, II
Thermal emf, 145 Two-point probe, 67
Thermal rebalance, 85 Tyndall scattering, 44, 224
Thermoelectric probe, 85 Type checking, 144
Thickness measurements, 153
absorption methods, 157
air gages, 155 Ultramicroscopy, 44, 224
by beveling, 175 UPS (ultraviolet photoelectron spectroscopy), 260
color charts, 173
conversion factors, 155
dielectric films, 168 Vacancies, 21, 22
diffused layers, 175 VAMFO (variable-angle monochrometer fringe
electron backscattering, 183 observation), 173
ellipsometry, 158 van der Pauw method, 66, 72
epitaxial layer, 155, 156, 166, 169, 170, 181
Fourier-transform spectrophotometer, 170
interferometry, 165 W-R etch, 199
Michelson interferometer, 170 WAg etch, 33, 39,42, 199
Ni/Cr films, 183 White etch, 41, 199
phase-shift corrections, 169
silicon nitride on Si, 173
Si0 2 on Si, 173, 179 X-ray diffractometer, 46, 254
slices, 156, 168 X-ray double-crystal spectrometer, 50
from stacking faults, 182 X-ray fluorescence, 183
of steps, 181 X-ray goniometer, 15
summary of methods, 154, 155 X-ray microprobe, 24, 90, 183, 254
VAMFO,I72 X-ray photoelectron spectroscopy (XPS), 260
by weight differential, 81 X-ray topography, 39, 40, 44, 46, 50, 51, 256
x-ray microprobe, 183
Three-point probe, 66, 85
Tolansky multiple-beam interferometry, 179 Young's modulus, 47, 48
Topography, 34, 44, 256
Trace angles, 6
Traces, 6 (ZnCd)S,29
Transmission electron diffraction (TED), 252, 260 ZnS:
Transmission electron microscopy (TEM), 244, 260 etch pits, 36
Trapping, 106 inclusions in, 45
Twins: polarity determination, 16
detection, 22, 41 ZnTe polarity determination, 16