Introduction

• William Roentgen discovered X-

rays in 1895 and determined they
had the following properties
1. Unlike ordinary light, they are
invisible
2. Travel in straight lines
3. Darken photographic plates
4. Make shadows of absorbing
material on photosensitive paper
5. Much more penetrating than light
and can easily pass through the
human body, wood, quite thick
pieces of metal, and other
objects.

1. Roentgen was awarded the Nobel Prize in 1901.

2. The phenomenon of x-ray diffraction was
discovered in 1912 and this discovery proved the
wave nature of x-rays.
 Introduction
X-rays were discovered by W.C. Röentgen in 1895, and led to
three major uses:

• X-ray radiography , used for creating images of light-opaque

materials, relies on the relationship between density of
materials and absorption of x-rays. Applications include a
variety of medical and industrial applications.

• X-ray fluorescence spectrometry relies on characteristic

secondary radiation emitted by materials when excited by a
high-energy x-ray source and is used primarily to determine
amounts of particular elements in materials.

• X-ray crystallography relies on the dual wave/particle nature of

x-rays to discover information about the structure of crystalline
materials.
The Electromagnetic Spectrum

Cu-Kα
 z
y

H
E

x 
E  A sin 2   t 
 
Production of X-Rays
 Continuous Spectrum

X-Rays are produced at the point of

impact and radiate in all directions.
If e is the charge of the electron
(1.60x10-19 coulomb) and V the
voltage across the electrodes,
then the kinetic energy (in joules)
of the electrons on impact is given
by the equation

m = mass of the electron (9.11x10-31 kg)

v = velocity in m/sec just before the
impact. At 30,000 V velocity is about
SWL one-third that of light.

Most of the kinetic energy of the

electrons striking the target is
converted into heat, less than one
Heterochromatic, continuous or white radiation percent is transformed into X-Rays
White radiation is also called bremsstrahlung
 Continuous Spectrum

Icont. Spectrum = AiZVm

Where, A = proportionality constant, m
= constant (nearly equal to 2), i = tube
current (number of electrons per
second striking the target), Z = atomic
number of the target

SWL
 Generating characteristic radiation
– An incoming high-energy
photoelectron dislodges a
k-shell electron in the
target, leaving a vacancy in
the shell
– An outer shell electron then
“jumps” to fill the vacancy
– A characteristic x-ray
(equivalent to the energy
change in the “jump”) is
generated

L-shell to K-shell jump produces a

K x-ray
M-shell to K-shell jump produces a
K x-ray
 Characteristic Spectrum

B = proportionality constant
VK = K excitation voltage
i = tube current
n = constant (about 1.5)

SWL
Mosley’s Law

  C (Z   )
 Absorption
Ix = I0 e-mx
Ix = intensity of transmitted beam
I0 = intensity of incident beam
m = linear absorption coefficient (dependent on the
substance considered, its density, and wavelength
of x-rays
X = distance traversed

Ix = I0 e (-m/r)rx
m/r  mass absorption coefficient (constant of the
material and independent of its physical state)
 Absorption

(m/r)  w1(m/r)1+ w2(m/r)2 + w3(m/r)3 + ……..

Where, w1, w2, w3, etc., are the weight fractions of

elements 1,2,3. etc., in the substance
and
(m/r)1, (m/r)2, (m/r)3 etc., are the mass absorption
coefficients of elements 1,2,3. etc., in the substance
Mass Absorption coefficients m/r (cm2/gm) and densities r
Variation with wavelength of the energy per x-ray quantum and
of the mass absorption coefficient of nickel
Absorption coefficients of lead, showing k and L absorption edges
Atomic energy levels (schematic). Excitation and emission
processes indicated by arrows. The insert at top right shows
the fine structure of the L state.
The emission of the K1 line is due to a K to LIII transition. The
frequency  K1 is given by the equation

Subscripts K and LIII refer to

absorption edges and the
subscript K1 to the emission line
Comparison of the spectra of copper radiation (a) before and
(b) after passage through a nickel filter (schematic). The
dashed line is the mass absorption coefficient of nickel.
Filters for suppression of K radiation
Mass Absorption coefficients m/r (cm2/gm) and densities r
Crystallography
Miller indices of lattice planes
 Planes of a form are sets of equivalent lattice
planes related by symmetry. In general, planes
of a form have the same spacing but different
Miller indices.

Faces of a cube,
(100), (010), (001), (100), (0 10), and (00 1)
are planes of the form 100
 Planes of a zone
Planes of a zone are
planes which are all
parallel to one line,
called the zone axis.

hu + kv + lw = 0

u = k1l2 – k2l1
v = l1h2 – l2h1
w = h1k2 – h2k1
All shaded planes in the cubic lattice
shown are planes of the zone [001]
Cesium chloride (CsCl)
 Sodium chloride (NaCl)

4 Na+ at 0 0 0, ½ ½ 0, ½ 0 ½ and 0 ½ ½
4 Cl- at ½ ½ ½ , 0 0 ½, 0 ½ 0 and ½ 0 0
 Diamond

000 + face-centering translation (0 0 0, ½ ½ 0, ½ 0 ½ and 0 ½ ½

¼ ¼ ¼ + face centering translation (¼ ¼ ¼ , ¾ ¾ ¼ , ¾ ¼ ¾ and ¼ ¾ ¾)
 Zinc blende

S: 000 + face-centering translation (0 0 0, ½ ½ 0, ½ 0 ½ and 0 ½ ½

Zn: ¼ ¼ ¼ + face centering translation (¼ ¼ ¼ , ¾ ¾ ¼ , ¾ ¼ ¾ and ¼ ¾ ¾)
Plane spacings
Interplanar angles
Diffraction I: Directions of
Diffracted Beams
Effect of path difference on relative phase

A wave front is a surface

perpendicular to the direction
of propogation
Conclusions from the previous slide

1. Differences in the length of the path

traveled lead to differences in phase

2. The introduction of phase differences

produces a change in amplitude

3. Two rays are completely in phase

whenever their path lengths differ either
by zero or by a whole number of
wavelengths.
 Bragg’s Law

QK – PR
= PK cosq - PK cosq
=0

ML + LN = d' sinq +
d' sinq  2d' sinq

Diffraction of x-rays by a crystal

n = order of reflection (it may take on
any integral value consistent with sin q
n  2d' sinq not exceeding unity and is equal to the
number of wavelengths in the path
difference between rays scattered by
adjacent values
Note: shift is actually not a problem!  Why is ‘systematic’ shift not a problem?

n   AY + YB AY  XY Cos[180  ( + q )]   XY Cos( + q )
YB  XY Cos(  q )
n   AY + YB  XY [Cos( q )  Cos( + q )]  XY [2 Sin Sinq ]
d
n  [2 Sin Sinq ]  2 d Sinq n   2 d Sinq d
 Sin( )
Sin XY
 Scattering modes
1. By atoms arranged randomly in space, as in a monatomic
gas. This scattering occurs in all directions and is weak.
Intensities add.

2. By atoms arranged periodically in space, as in a perfect

crystal:
(a)In a very few directions, those satisfying the Bragg law,
the scattering is strong and is called diffraction.
Amplitudes add.
(b) In most directions, those not satisfying the Bragg law,
there is no scattering because the scattered rays cancel
one another.
 Order of reflection

Equivalence of (a) a second-order 100 reflection and (b) a first order 200 reflection

A reflection of any order can be

considered as a first order
reflection from planes, real or
fictitious, spaced at a distance
1/n of the previous spacing.
 Diffraction directions

  2dSinq
Cubic Tetragonal

d a 1 h2 + k 2 l 2
( + 2)
h2 + k 2 + l 2 d2 a2 c
2 2 2
sin 2 q  ( h + k + l 2
)  2 h2 + k 2 l2
4a 2
sin 2 q  ( + 2)
4 a2 c
2
sin 2 q110 
2a 2

Diffraction directions are determined solely

by the shape and size of the unit cell
 Diffraction Methods

 q
Laue method Variable Fixed

Rotating-crystal method Fixed Variable (in part)

Powder method Fixed Variable

(a) Transmission and (b) back-reflection Laue methods

(a) Transmission and (b) back-reflection Laue patterns of an

aluminum crystal (cubic). Tungsten radiation.
Location of Laue spots (a) on ellipses in transmission method
and (b) on hyperbolas in back-reflection method
Rotating-crystal pattern of a quartz crystal rotated about its c axis
Formation of a diffracted cone of radiation
in the powder method
Debye-Scherrer powder method: (a) relation of film to specimen
and incident beam; (b) appearance of film when laid out flat.
POWDER METHOD
Diffraction cones and the Debye-Scherrer geometry
Different cones for different reflections

Film may be replaced with detector

Debye-Scherrer powder patterns of copper (FCC), tungsten
(BCC), and zinc (HCP).
 Diffraction Under Nonideal Conditions

Effect of crystal size on diffraction

By subtraction we find

and

Therefore

A more exact treatment of the problem gives

 Scherrer formula

0.9
t
B cos q B

Effect of fine particle size on diffraction curves

XRD Line Broadening

Instrumental  Unresolved 1 , 2 peaks

 Non-monochromaticity of the source (finite width of  peak)
Bi
 Imperfect focusing

Crystallite size
Bc

Strain  ‘Residual Strain’ arising from dislocations, coherent precipitates

Bs etc. leading to broadening

Stacking fault
In principle every defect contributes to some broadening
Other defects

B ( FWHM )  Bi + Bc + Bs + BSF + ...

B ( FWHM )  Bi + Bc + Bs + BSF + ...
 Subtracting Instrumental Broadening

 Instrumental broadening has to be subtracted to get the broadening effects due to

the sample

1
 Mix specimen with known coarse-grained (~ 10mm), well annealed (strain free)
 does not give any broadening due to strain or crystallite size (the only
broadening is instrumental). A brittle material which can be ground
into powder form without leading to much stored strain is good.
 If the pattern of the test sample (standard) is recorded separately then the
experimental conditions should be identical (it is preferable that one or more peaks
of the standard lies close to the specimen’s peaks)

2
 Use the same material as the standard as the specimen to be X-rayed but with large
grain size and well annealed
B ( FWHM )  Bi + Bc + Bs + BSF + ...

For a peak with a Lorentzian profile B  Bi  Bc + Bs  Br

Hendrik Antoon Lorentz

Longer tail On the theory of reflection and refraction of light

For a peak with a Gaussian profile Br2  B 2  Bi2

A geometric mean can also used Br2  ( B  Bi ) B 2  Bi2

Johann Carl Friedrich Gauss (1777-1855),
painted by Christian Albrecht Jensen
http://en.wikipedia.org/wiki/Carl_Friedrich_Gauss University of Göttingen
Scherrer’s formula For Gaussian line profiles and cubic crystals

  → Wavelength
k
Bc   L → Average crystallite size ( to surface of specimen)
tCos(q B )
 k → 0.94 [k  (0.89, 1.39)]
~ 1 (the accuracy of the method is only 10%)
Strain broadening

Bs   Tan(q B )
  → Strain in the material
Separating crystallite size broadening and strain broadening

Br  Bc + Bs k
Bc  Bs   Tan(q )
t Cos(q )

k
Br  +  Tan(q )
t Cos(q ) Plot of [Br Cosq] vs [Sinq]

k
Br Cos(q )  +  Sin(q )
t

K/t
Comparative x-ray scattering by
crystalline solids, amorphous
solids, liquids and monatomic
gases.
Plane spacings
Cell volumes
Interplanar angles
 Numerical problems
1. Determine, and list in order of increasing angle, the values of 2θ and (hkl)
for the first three lines (those of lowest 2θ values) on the powder patterns
of substances with the following structures, the incident radiation being
CuKα.
a) simple cubic structure (a = 3.00 A),
b) Simple tetragonal (a = 2.00 A, c = 3.00 A),
c) Simple tetragonal (a = 3.00 A, c = 2.00 A),
d) Simple rhombohedral (a = 3.00 A,  = 800).

2. Calculate the breadth B (in degrees of 2q), due to the small crystal effect
alone, of the powder pattern lines of particles of diameter 1000, 750, 500, and
250 A. Assume q = 450 and  = 1.5 A. For particles 250 A in diameter,
calculate the breadth B for q = 10, 45, and 800
Diffraction II: Intensities of
Diffracted Beams
Diffraction from the (001) planes of (a) base-centered and (b) body-centered
orthorhombic lattices
 A Scattering by an Electron

The intensity I of the beam scattered by a single electron of charge e coulombs

(C) and mass m kg, at a distance r meters from the electron, is given by

 m0   e  2
2
4
K
I P  I0   2 2  sin   I 0 2 sin 
2

 4   m r  r

Where, I0 = intensity of the incident beam

m0  4 x 10-7 m kg C-2
K = constant
  angle between the scattering direction and the direction
of acceleration of electron
 A Scattering by an Electron

I0 = Intensity of the incident beam

m0  4 x 10-7 m kg C-2
K = constant
  angle between the scattering direction and the
direction of acceleration of the electron

On the average, Ey will be equal to Ez , since

the direction of E is perfectly random

Coherent scattering of x-rays by a single electron

The y component of the incident beam accelerates the electron in
the direction Oy. It therefore gives rise to a scattered intensity at P
The total scattered intensity at P is obtained by summing
the intensities of these two scattered components:

The intensity of the scattered z component is

 A Scattering by an Electron

Coherent scattering of x-rays by a single electron

K 
I P  I0 2 
(1 + Cos 2
2q ) 

K = 7.94 x 10-30 m2
IP/ I0 = 7.94 x 10-26 in the forward
r  2  direction at 1 cm from the electron
 
Incoherent Scattering (Compton modified) From loosely bound charges
 Here the particle picture of the electron & photon comes in handy

E1  h 1 (1 , 1 ) Electron knocked aside

2q

E2  h 2 (2 , 2 )
  2  1  0.0243(1  Cos2q )

No fixed phase relation between the incident and scattered waves

Incoherent  does not contribute to diffraction
(Darkens the background of the diffraction patterns)
 Incoherent Scattering (Compton modified) From loosely bound charges
 Here the particle picture of the electron & photon comes in handy

Elastic collision of photon and electron (Compton effect)

No fixed phase relation between the incident and scattered waves

Incoherent  does not contribute to diffraction
(Darkens the background of the diffraction patterns)
 B Scattering by an Atom

 Angle of scattering leads to path differences

 In the forward direction all scattered waves are in phase
 f  Atomic Scattering Factor
Amplitude of wave scattered by an atom

Amplitude of wave scattered by an electron

Scattering by an atom  [Z, (q, )]

Sin(q )


 f  Q  (for fixed )
- f    (for fixed q)

The atomic scattering factor of copper

The atomic scattering factors
 Incident X-rays

SPECIMEN Heat

Fluorescent X-rays

Scattered X-rays Electrons

Coherent Compton recoil Photoelectrons

From bound charges
Auger electrons
Incoherent (Compton modified)
From loosely bound charges

Transmitted beam
Effects produced by the passage of x-rays through matter
 Structure Factor
The resultant wave scattered by all the atoms of the unit cell is called structure
factor. The structure factor, designated by the symbol F, is obtained by simply
adding together all the waves scattered by the individual atoms.

If a unit cell contains atoms 1,2,3,….N, with fractional coordinates u1v1w1,

u2v2w2, u3v3w3, … and atomic scattering factors f1, f2, f3, …., then the structure
factor for the hkl reflection is given by

2 i ( hu1 + kv1 + lw1) 2 i ( hu2 + kv2 + lw2) 2 i ( hu3 + kv3 + lw3)

F  f1e + f 2e + f 3e + 

N
Fhkl   f n e 2 i ( hun + kvn +lwn )

1
 Amplitude of wave scattered by all atoms in uc
F  Structure Factor 
Amplitude of wave scattered by an electron

I F
2

Structure factor is independent of

the shape and size of the unit cell
 Structure factor calculations
Simple Cubic
e ni  (1) n
A Atom at (0,0,0) and equivalent positions
e(odd n) i  1
e(even n) i  +1
eni  eni
eiq + e iq
 Cos(q )
2

i[2 ( h 0 + k  0 + l  0)]
F f e  fe  f
0

F2  f 2  F is independent of the scattering plane (h k l)

 B Atom at (0,0,0) & (½, ½, 0) and equivalent positions Base centered cell

1 1
[2 i ( h  + k  + l  0)]
F  f e[2 i ( h 0+ k  0+l  0)] + f e 2 2

h +k
[2 i ( )]
i ( h + k )
 fe +fe 0 2
 f [1 + e ]

F 2f F2  4 f 2
i ( h + k )
F  f [1 + e
e.g. (001), (110), (112); (021), (022), (023)
]
F 0 F2  0
e.g. (100), (101), (102); (031), (032), (033)

 F is independent of the ‘l’ index

 C Atom at (0,0,0) & (½, ½, ½) and equivalent positions Body centred cell

1 1 1
[2 i ( h  + k  + l  )]
[2 i ( h 0 + k  0 + l  0)]
F f e +f e 2 2 2

h + k +l
[2 i ( )]
 f e0 + f e 2
 f [1 + ei ( h + k +l ) ]

F 2f F2  4 f 2
i ( h + k + l )
F  f [1 + e
e.g. (110), (200), (211); (220), (022), (310)
]
F 0 F2  0
e.g. (100), (001), (111); (210), (032), (133)
 D Atom at (0,0,0) & (½, ½, 0) and equivalent positions Face Centred Cubic

(½, ½, 0), (½, 0, ½), (0, ½, ½)

 [2 i (0)] [2 i ( h +2 k )] [2 i ( k 2+l )] [2 i ( l +2h )] 

F  f e +e +e +e 
 
 f [1 + ei ( h + k ) + ei ( k +l ) + ei (l + h ) ]

F  f [1 + ei ( h + k ) + ei ( k +l ) + ei (l + h ) ]

(h, k, l) unmixed F 4f F  16 f

2 2

e.g. (111), (200), (220), (333), (420)

(h, k, l) mixed F 0 F2  0
e.g. (100), (211); (210), (032), (033)

Two odd and one even (e.g. 112); two even and one odd (e.g. 122)
Mixed indices Two odd and one even (e.g. 112); two even and one odd (e.g. 122)

Mixed indices CASE h k l

A o o e
B o e e

CASE A : [1 + ei ( e ) + ei ( o ) + ei ( o ) ]  [1 + 1  1  1]  0

CASE B : [1 + ei ( o ) + ei ( e ) + ei ( o ) ]  [1  1 + 1  1]  0

(h, k, l) mixed F 0 F2  0 e.g. (100), (211); (210), (032), (033)

Unmixed indices All odd (e.g. 111); all even (e.g. 222)

Unmixed indices CASE h k l

A o o o
B e e e
CASE A : [1 + ei ( e ) + ei ( e ) + ei ( e ) ]  [1 + 1 + 1 + 1]  4
CASE B : [1 + ei ( e ) + ei ( e ) + ei ( e ) ]  [1 + 1 + 1 + 1]  4

(h, k, l) unmixed F 4f F 2  16 f 2

e.g. (111), (200), (220), (333), (420)
 Atoms at (0,0,0) & (1/3, 2/3, 1/2) and equivalent positions
h 2k l
[2 i ( + + )]
F  f e[2 i ( h 0+ k  0+l  0)] + f e 3 3 2 Close packed
hexagonal cell
 + 
 ( h+2k ) l 
2 i 
 f 1 + e  3 2

 
  h + 2k  l 
Putting , 
 3  2 
+   g (
F  f 1 + e2 ig )
( )( ) (
F  f 2 1 + e 2 ig 1 + e 2 ig  f 2 2 + e 2 ig + e 2 ig
2
) h+2k l F
2

 f 2
( 2 + 2 cos 2 g ) 3m odd 0
 f 2  2 + 2(2 cos 2  g  1)  3m even 4f2
 f 2 (4 cos 2  g )
3m ± 1 odd 3f2
 h + 2k l 
 4 f 2 cos 2   +  3m ± 1 even f2
 3 2
 Sodium chloride (NaCl)

4 Na+ at 0 0 0, ½ ½ 0, ½ 0 ½ and 0 ½ ½
4 Cl- at ½ ½ ½ , 0 0 ½, 0 ½ 0 and ½ 0 0
E
Na+ at (0,0,0) + Face Centering Translations  (½, ½, 0), (½, 0, ½), (0, ½, ½)
Cl− at (½, ½, ½) + FCT  (0, ½, 0), (0, 0, ½), (½, ½, ½) NaCl:
Face Centred Cubic
 i[ 2 ( 0)] i[ 2 ( h +2 k )] i[ 2 ( k 2+l )] i[ 2 ( l +2h )] 
F  f Na+ e +e +e +e +
 
 i[ 2 ( h2 )] i[ 2 ( k2 )] i[ 2 ( 2l )] i[ 2 ( h +2k +l )] 
f Cl   e +e +e +e 
 
F  f Na+ [1 + ei ( h + k ) + ei ( k +l ) + ei (l + h ) ] +
f Cl  [ei ( h ) + ei ( k ) + ei ( l ) + ei ( h + k +l ) ]

F  f Na+ [1 + ei ( h + k ) + ei ( k +l ) + ei (l + h ) ] +

f Cl  ei ( h + k +l ) [ei (  k l ) + ei (  l  h ) + ei (  h  k ) + 1]

F  [ f Na+ + f Cl  ei ( h + k +l ) ][1 + ei ( h + k ) + ei ( k +l ) + ei (l + h ) ]

F  [ f Na+ + f Cl  ei ( h + k +l ) ][1 + ei ( h + k ) + ei ( k +l ) + ei (l + h ) ]
F  [Term 1][Term  2] Zero for mixed indices

Mixed indices CASE h k l

Mixed indices
A o o e o: Odd
e: Even
B o e e

CASE A : Term  2  [1 + ei ( e ) + ei ( o ) + ei ( o ) ]  [1 + 1  1  1]  0

CASE B : Term  2  [1 + ei ( o ) + ei ( e ) + ei ( o ) ]  [1  1 + 1  1]  0

(h, k, l) mixed F 0 F 02 e.g. (100), (211); (210), (032), (033)

 Unmixed indices CASE h k l
Unmixed indices
A o o o
B e e e

CASE A : Term  2  [1 + ei ( e ) + ei ( e ) + ei ( e ) ]  [1 + 1 + 1 + 1]  4

CASE B : Term  2  [1 + ei ( e ) + ei ( e ) + ei ( e ) ]  [1 + 1 + 1 + 1]  4

(h, k, l) unmixed F  4[ f Na+ + f Cl  ei ( h + k +l ) ]

e.g. (111), (222); (133), (244)

F  4[ f Na+ + f Cl  ] If (h + k + l) is even F 2  16[ f Na+ + f Cl  ]2

e.g. (222),(244)

F  4[ f Na+  f Cl  ] If (h + k + l) is odd F 2  16[ f Na+  f Cl  ]2

e.g. (111), (133)
Relative Intensity of diffraction lines in a powder pattern

Structure Factor (F) Scattering from UC

Multiplicity factor (p) Number of planes in a form having the same spacing

Polarization factor Effect of wave polarization

1 + Cos 2 ( 2q )
IP 
2

Lorentz factor Combination of 3 geometric factors

 1   1 
Lorentz factor   (Cosq ) 
 Sin2q   Sin2q 

Absorption factor Specimen absorption

Temperature factor Thermal diffuse scattering

 Multiplicity factor

hkl hhl hk0 hh0 hhh h00

Cubic
48* 24 24* 12 8 6
hk.l hh.l h0.l hk.0 hh.0 h0.0 00.l
Hexagonal
24* 12* 12* 12* 6 6 2
hkl hhl h0l hk0 hh0 h00 00l
Tetragonal
16* 8 8 8* 4 4 2
hkl hk0 h0l 0kl h00 0k0 00l
Orthorhombic
8 4 4 4 2 2 2
hkl h0l 0k0
Monoclinic
4 2 2
hkl
Triclinic
2

* Altered in crystals with lower symmetry (of the same crystal class)
 Lorentz factor

1.

 1 
I max   
 sinq B 

 1 
B  
 cos q B 

 1   1 
I max B   
 sinq B cos q B   sin 2q B 
 Lorentz factor

2. No. of crystals favorably oriented for reflection is proportional to cosqB

3. The relative intensity per unit length of the line is proportional to 1/sin2qB

 1   1  cos q 1
Lorentz factor    ( Cosq )   
 Sin2q   Sin2q  sin 2q 4sin q cos q
2 2
 Lorentz factor
1.  1 
I max   
q  1   1 
 sin B  I max B   
 1   sinq B cos q B   sin 2q B 
B  
 cos q B 

2. No. of crystals favorably oriented for reflection is proportional to cosqB

3. The relative intensity per unit length of the line is proportional to 1/sin2qB

 1   1  cos q 1
Lorentz factor    ( Cosq )   
 Sin2q   Sin2q  sin 2q 4sin q cos q
2 2
Polarization factor Lorentz factor


(1 + Cos ( 2q ) )
2  1 
Lorentz factor   (Cosq ) 1 
 
IP  Sin2q   Sin2q 
2
 1 + Cos 2 (2q ) 
Lorentz Polarization factor   
 Sin q Cosq 
2

30

25

Lorentz-Polarization factor
20

15

10

0
0 20 40 60 80
Bragg Angle (q, degrees)
 Absorption factor

The absorption factor A is equal to 1/2m, independent

of q (for diffractometer)
 Temperature factor

Increased thermal vibration of the atoms, as the result of an

increase in temperature, has three main effects:
1. The unit cell expands, causing changes in plane spacings
d and therefore in the 2q positions of the diffraction lines.
2. The intensities of the diffraction lines decrease.
3. The intensity of the background scattering between lines
increases.
 Temperature factor

2M
Temperature factor  e

 _2 
2 2  sin q   sin q 
_ 2 2
2 u 
M  2  8 u    B 
 d 
2
     
 
_
u 2
Mean square displacement of the atom in a direction
normal to the reflecting planes
Effect of thermal vibration of the atoms on a powder pattern (very schematic)

1.Thermal vibration of atoms decreases the intensity of diffraction lines.

2. It causes some general coherent scattering in all directions, known as

temperature-diffuse scattering. It contributes only to the general
background of the pattern and its intensity gradually increases with 2q
Intensity of powder pattern lines
(ignoring Temperature & Absorption factors)

 1 + Cos 2q 
2
I  F p 
2

 Sin q Cosq 
2

 Valid for Debye-Scherrer geometry

 I → Relative Integrated “Intensity”
 F → Structure factor
 p → Multiplicity factor
 Choice of Radiation
The characteristic wavelength used should not be shorter than the K
absorption edge of the specimen, or the fluorescent radiation will be
produced.

The Bragg law shows that the shorter the wavelength, the smaller the
Bragg angle for planes of a given spacing. Decreasing the wavelength
will therefore shift every diffraction line to lower Bragg angles and
increase the total number of diffraction lines/peaks, while increasing the
wavelength will have the opposite effect. The choice of a short or long
wavelength depends on the particular problem involved.