CHMS 5130: Materials Analysis

WEEK 7-8: Microscopic Analysis

Course Instructor:
Prof. Jonathan Halpert
 CHMS 5130: Microscopic Analysis
LECTURE OUTLINE
1. Optical Microscopy
2. Electron Microscopy
• SEM
• HRTEM
• STEM
3. Surface Microscopy
• STM
• AFM

Reference and Suggested Reading:

 Microscopy: Basics
Several inventors are credited and
many others may have developed
it independently over centuries

Zach Janssen & father Hans

experimented with magnifying
lenses in tubes around 1590.

Leeuwenhoek is considered the

“father” of microbiology due to
his observations using
microscopes

Another lens maker in Holland Hans Lippershey also claims to have invented arrangement of two lenses to
produce higher magnification. He also filed first patent on telescope around same time.
 Microscopy: Basics

A magnifying lens & a

compound microscope of two
magnifiers

A convex lens spreads apart the

image of the object, making it
seem much larger to your eye

In a multi-stage optical
microscope, each lens focuses
on the image produced by the
previous lens
 Microscopy: Basics

1. Secure stand
2. Light source (attached or external)
3. Angled mirror for light source
4. Stage
5. Focus (raise or lower stage)
6. Object/Specimen
7. Mount (here for a glass slide)
8. Clips to hold mount
9. Objective Lens (spreads image)
10. Other Objective Lenses (usually several to change mag)
11. Thumb wheel to select lens
12. Eyepiece Lens (magnifies image from Obj Lens)
13. Fine focus (Eyepiece lens)
14. User
 Microscopy: Basics

Resolution (r) is determined by

various factors including
Numerical Aperture NA (power)
but also the wavelength of light

k
R
NA

k/NA typically between 0.5 - 1.2 Resolution in microscopy is defined

as the limit of distinguishing two
For k/NA = 0.55 and visible light objects
500 nm get 275 nm resolution http://www.microscopyu.com/articles/form
ulas/formulasresolution.html
 Microscopy: Basics
Optical Electron
Hooke and van Leeuwenhoek
were early pioneers investigating
biological structures

However, electron microscopy

has much higher resolution

This is because the wavelength of Optical Electron

electrons is much smaller than (false color)
that of light
determines
k resolution
R directly
NA

,
Louisa Howard, Dartmouth Electron Microscope Facility Wikimedia
Optical Microscopy: Examples

Crystallized nanorods of buckminsterfullerene (C60) in a top (center) and bottom

illumination mode in an optical microscope [Halpert Group]

A number of other important methodologies can be employed eg microscopy gives

important information on purity crystallinity and morphology
 Microscopy: Fluorescence Microscopy
Fluorescence Microscopy:

A microscope with attached

camera to record images,
detector must match emission

An excitation source matched to

absorption states on the dye

Filters to block excitation from

camera

Suitable dyes for staining, if

sample is not naturally Cells stained with emissive red,
fluorescent green and blue emitting dyes
 Other forms of microscopy: EM and SPM

EM: electron microscopy, uses electrons

instead of photons to magnify images.
Includes:

TEM: transmission electron microscopy

SEM: scanning electron microscopy
STEM: scanning transmission electron
microscopy (not shown)

SPM: scanning probe microscopy, uses

force (van der Waals, EM or magnetic
to “feel” the surface, includes:

AFM: atomic force microscopy

STM: scanning tunneling microscopy
 CHMS 5130: Microscopic Analysis
LECTURE OUTLINE
1. Optical Microscopy
2. Electron Microscopy
• SEM
• HRTEM
• STEM
3. Surface Microscopy
• STM
• AFM

Reference and Suggested Reading:

 Microscopy: What do you want to see?
OPTICAL: Resolution & brightness limited by light source & Size/Resolution
visible wavelengths; cheap
mm → μm → nm → 0.1 Å
FLUORESCENCE: Sample tagged with emissive dyes – brighter, Thickness/Sample Type
contrasting & components well differentiated
mm → μm → nm → atomic
ELECTRON: Higher resolutions possible, but now need vacuum
Time/Cost/Difficulty
SEM: Image created from e- scattered on sample surface. Need
conductive surface of sample (coat with C, Cr or Ag/Au) Fast (minutes) /Slow (weeks)
Cheap / Expensive ; Easy/Hard
TEM/HRTEM: Electrons pass through sample (transmitted) –
can get imaging or diffraction pattern depending on optics. Other considerations:
High resolution - can get to sub-atomic resolution, but fluorescent, magnetic, air-sensitive,
increasingly expensive (HK$20M+) suspensions, organic/soft, flatness,
ATOMIC: STM and AFM are techniques using piezo-electric tip volatility, temperature stability,
scanned over sample surface & force or e-potential measured oxidation/reduction potential,
conductivity, composition needed
Microscopy: Basics
 CHMS 5130: Microscopic Analysis
LECTURE OUTLINE
1. Optical Microscopy
2. Electron Microscopy
• SEM
• HRTEM
• STEM
3. Surface Microscopy
• STM
• AFM

Reference and Suggested Reading:

 SEM (and EDAX)
Scanning Electron Microscopy was invented in 1937 by
German industrialist Manfred von Ardenne. He used
electron beam to create magnified images. Later
developments included analysis of X-rays emitted by sample
The technique of
after being bombarded with e- beam.
EDAX was born;
analysis of emitted
X-rays is very
similar to XRF, but
SEM allows us to
look at tiny objects
or small areas of a
sample.

Many names:
EDS/EDX/EDAX/
EDXS/XEDS
Scanning Electron Microscopy (SEM)

E- beam is scanned over the surface & back-scattered

e- collected to ‘image’ it. Note that separate detection
of X-rays can give complementary compositional info
Scanning Electron Microscopy (SEM)

Samples mounted on metallic SEM ‘stubs’

(sticky tape) may need different preparation
depending on their nature

SEM for Biological samples complex - otherwise may just need

conductive coating for chemically stable insulating samples
 Scanning Electron Microscopy (SEM)
• Carbon coating is applied for SEM and TEM insulating samples. It is suitable for high resolution observation. The use of
Carbon Films in Electron Microscopy with their LOW background signal, and relatively good electrical conductivity is well
known. Thin films, nominally 5nm or 50 Angstroms, are used in TEM, while a range of somewhat thicker films, ranging from
50nm or 500 Angstroms, may be used in SEM for such applications as X-Ray Microanalysis.

• Gold coating produce grains about 50 nm in size. This is not suitable for SEM high resolution observation. This electrically
conductive thin coating improves secondary electron emission which is beneficial for SEM

Nanomaterial samples cannot be gold coated

and still resolved…however other methods
may be used to improve conduction:

-conductive ligands
-conductive substrates
-thin/dispersed samples
 Scanning Electron Microscopy (SEM)

Iron oxides prepared from different

precursor salts give different
nanomaterials – morphology
(shape) and size from SEM.

[Scale bar should be clearly visible]

SEM images of shaped iron oxides with six different shapes

(a) Nanorod, (b) Nanohusk, (c) Distorted cubes
(d) Nanocubes, (e) Porous spheres & (f) Self-oriented flowers
 Scanning Electron Microscopy (SEM)
The SEM results complementary info to those from other materials analyses -
principally p-XRD which indicates phase type
 CHMS 5130: Microscopic Analysis
LECTURE OUTLINE
1. Optical Microscopy
2. Electron Microscopy
• SEM
• In situ X-ray methods
• HRTEM
• STEM
3. Surface Microscopy
• STM
• AFM
Reference and Suggested Reading:
 Scanning Electron Microscopy (SEM)
Principle of XRF (X-ray fluorescence) Principle of EDAX

EDAX is similar, characteristic X-rays also analyzed, but initial ionization event is by electron beam of
Scanning Electron Microscope (SEM)
 EDAX in SEM
Also called EDS, EDX

ENERGY OF X-RAY
LINES BY ELEMENT
Energy of X-rays in XRF and EDAX depends on the
atomic number of the element Z and the type of line
(i.e which principal quantum shells are involved)

2 ---> 1 Ka 3 ---> 1 Kb

3 ---> 2 La 4 ---> 2 Lb

4 ---> 3 Ma

Ka line is usually the strongest

 Scanning Electron Microscopy (SEM)
Single crystal XRD EDAX Result

F Cl
F

Crystal structure determination S-XRD

implies both F and Cl present; have just
<1mg of sample; ran EDAX on one
Cl crystal: both Cl and F peaks are clear
Scanning Electron Microscopy (SEM)

In some modern SEMs the spatial

distribution of characteristic X-rays
can be examined

Elemental Mapping scans an image

and records EDAX spectra at
intervals, creating a map of target
elements

This can be useful for elemental

identification and locations of
concentration but can be
inaccurate for exact composition
without good controls
 SEM: Composition

Elemental mapping is a good way to TEM SEM

find out which elements are present

In TEM the ratio of elements must be

carefully calibrated, leading to
erroneous quantitative data

Additionally many x-ray peaks

overlap, causing problems (*)

Vashishtha P, Metin DZ, Cryer M, Chen K, Hodgkiss JM, Gaston N, Halpert JE, Chem. Mater. 2018 In Press
 SEM: morphology study
TiO2 PbI2/TiO2 SDSC MAPbI3

MAPbI3 MAPbI3 MAPbI3

>PbI2 >PbI2

Y. Ma, P. Vashishtha, K. Chen, E. Peach, D. Ohayon, J. Hodgkiss, J. Halpert, ChemSusChem, 2017, ASAP
 Looking at electronic devices
TiO2 PbI2/TiO2 SDSC MAPbI3
perovskite DSSCs

on edge

SEM holder for chips, edge view

CuInS2 NC solar cells

Y. Ma, P. Vashishtha, K. Chen, E. Peach, D. Ohayon, J. Hodgkiss, J. Halpert, ChemSusChem, 2017, ASAP Halpert et al. ACS Nano 2015
 CHMS 5130: Microscopic Analysis
LECTURE OUTLINE
1. Optical Microscopy
2. Electron Microscopy
• SEM
• HRTEM
• STEM
3. Surface Microscopy
• STM
• AFM

Reference and Suggested Reading:

 High-Resolution Transmission Electron
Microscopy (HRTEM)

Also need stable power source, high V up to 300 kV, vibration-free floor,
no external magnetic fields, lots of Pb shielding, electrical shielding
High-Resolution Transmission Electron
Microscopy (HRTEM)
FEI Titan Aberration Corrected
resolution: 200 pm at 200 kV
80 pm STEM mode
JEOL JEM-ARM300F U-Wisconsin
resolution: 55 pm @ 300 kV

Can see nanostructured materials, crystal

planes, single molecules, defects, proteins
& DNA (cryo modes), atomic spacing in
molecules (large error)
TEM: working principle

If electrons have wave-like properties then similar to light they

can be used in microscopy – they can be scattered & diffracted

The resolution for visible light microscopy ca. 0.2 microns.

(Limit ca 0.5 x ) How does e.m. improve on this ?

Since the mass of an electron is 9.1 x 10-31 kg and e = 1.6 x 10-19,

Thus, the wavelength of electrons is calculated to be

3.88 pm at 100 keV,

2.74 pm at 200 keV
2.24 pm at 300 keV

In principle this is well below atomic resolution using highly

energetic electrons (moving about 0.7c) Note higher res for higher
accelerating voltage
HRTEM: examples

20nm 20nm
TEM sample prep: solids

Key difference to SEM is that sample must be thin enough to be

‘transparent’ to e- beam.

Ceramic samples may have several stages of thinning

Cutting may be done with

diamond saw,

grinding & polishing with

corundum/SiC ‘papers’

Ion milling
using argon (Ar+)
 TEM sample prep: nanoparticles
Preparing liquid or dispersed nanocrystalline samples is much easier

1. Sonicate liquid to
aid in nanomaterial
dispersion

2. Drop cast with 22

gauge needle (small
drop) onto grid
TEM grid
3. Consider: (Ted Pella)
population effects,
drying, solvent
compatibility
https://www.tedpella.com/grids_html/grids.htm
 TEM modes

There are two principle modes of

operation for TEM:

A: diffraction mode: shows the diffraction

pattern of a spot at the center of the
sample using SAD aperture to concentrate
and focus beam on specimen

B: Image mode: shows the image, uses

objective aperture to spread beam in focus
at specimen

The intermediate lens selects either a) the

back focal plane or b) the image plane of
the objective lens
 TEM sample prep: nanoparticles

Both imaging and diffraction are

possible depending on the optics used.

The lenses for e- beams are

magnetic fields

On left the geometry for imaging

is shown and on right the geometry
for obtaining a diffraction pattern
Diffraction using electrons

Resolving power related to λ of e-beam (at

100keV = 0.037Å)
HRTEM may be above 200keV.
Usually take a single crystallite from powder to get
single crystal diffraction pattern
 SAD analysis

1. Use Bragg’s Law 2. Reaarange Bragg’s Law

2  sin 2  R / L
  2d sin    2d sin   d (2 )
R/L/d
Rd   L
L is camera length
But with much smaller λ ~ 2.5 pm at 200 kV
λL is camera constant
(if d=2.5 Å, θ=0.288°)

3. Get transmission spots 4. 2D pattern matches some orientation of xstal

 SAD analysis

5. Measure 3 reflections, apply 6. Compare with known d spacings

equations, get spacings for given crystal planes

7. Choose indices so that vectors 8. Find crystal axis from

add properly – index other cross product of any two
reflections by vector sums + (hkl) and reduce
differences (202)  (220)  [444]  [1 11]
 Crystallinity

The purity of the SAD image shows whether you have a single or
polycrystalline materials, lack of rings would indicate amorphous phases

two crystals

many crystals

polycrstalline BaTiO3 (spotty Debye rings)

 Varying Ring Patterns Indicate Crystallinity

Amorphous Crystalline Polycrystalline

Diffraction pattern gives information about crystallinity lattice parameters, unit cell details, angle of observation

Lattice indices help determine: direction of growth, phases present (XRD is better), orientation at grain boundaries,
changes in phase → however d values not as precise, intensity data hard to interpret…used as support to XRD
 TEM sample prep: nanoparticles

Scattering of e- based on atomic potentials –

generally scattering power 104 greater than X-rays
and approximately proportional to Z (atomic no).

Scattering patterns then dominated by heavy

elements which show up as brighter spots.

Computer programs can be used to simulate

patterns of bright/dark from different defocus
positions

For example seen for the Gallium nitride

[001]direction opposite
 Particle Size Analysis

“small” “large”
Here we want to see the
difference between the
populations that easily
disperse, and those that
do not in a sample of
CZTS nanocrystals

100 nm 100 nm

Particles can be size selected by selective precipitation, with the larger particles
precipitating from solution first as polar solvent is added to the growth solution
 Effect of Particle Size
Semiconductor Nanocrystal
a) NC 28.0 µ = 28.0 nm b) NC 20.9 µ = 20.9 nm
Under the r
1-10nm
σ = 2.5 nm σ = 3.0 nm

Relative frequency (a.u.)

Relative frequency (a.u.)

confinement effect, ~9% ~ 14 %
Absorbance
particle size affects
the absorption and Decreasing
Size
emission band edge
of the nanocrystal
Decreasing
Size
20 22 24 26 28 30 32 34 10 12 14 16 18 20 22 24 26 28
“Particle in a Box” 400 500 600 700 Particles size (nm) Particle size (nm)
Electronic States Wavelength (nm)
C.B. Murray, PhD Thesis, MIT 1995
c) NC 16.5 µ = 16.5 nm d) NC28.0
FWHM- 44 nm
Sizing particles using ImageJ (free σ = 2.5nm 333 nm

Relative frequency (a.u.)

software) permits an accurate ~ 15 %

Absorbance
326 nm NC20.9
measurement of particles and can FWHM- 38 nm

be fit to the Brus equation:

321 nm
NC16.9

 
2 2 * FWHM- 30 nm
1.8e2  1 1 
E  Eg    *ex   *  * 
ex

2r 2 4 r  0 r  me mh  8 10 12 14 16
Particle size (nm)
18 20 22
300 400 500 600 700 800
Wavelength (nm)
 HRTEM: Control of Nanoparticle Growth
Figures below show Transmission
Electron Micrograph (TEM)
images of Spinel-type Ni0.5Zn0.5Fe2O4
particles from a related plasma
torch synthesis

Under varying conditions, growth

may proceed to fill out the corner
positions or to truncate them,
leading to the presentation of
different crystalline facets

This can produce better catalytic

surfaces for some reactions

Control of nano-particle nucleation and growth and thus size and morphology (shape) by variation of preparation
conditions is a key aim, in order to tune the materials’ properties.
 HRTEM: tetrapods

Have been prepared

for several materials
including ZnO and CdX

Basis is first nucleation of cubic symmetry nanoparticle

followed by growth of hexagonal phase on the (111) type
faces to give final micron scale

http://www.london-nano.com/lib/tmp/cmsfiles/File/papers/MT1005_review4_MarcusNewton%20and%20Warburton%20article.pdf
 TEM: assessing growth over time
Here a reaction proceeds from
Cesium halide precursor: Cs-oleate
the injection point, samples can
be removed at intervals and the
Injection of surfactant at 1200C
TEM is used to monitor growth
and compare to changes in
Hot injection of metal precursor at 1500C
optical properties (UV-vis)
Cooling the reaction medium at time t≈5s
This gives information about
formation mechanism and Solvent/anti-solvent purification
growth rate and size vs optical
properties

2 nm 10 nm 20 nm
Reaction time
Vashishtha and Halpert, 2015 unpublished
 HRTEM: Assessing shell coatings
CZTS

3.2 Å
<111>

HR-TEM images show lattice fringes of the (111) zinc-blend lattice plane of ZnS
Particle Size Analysis
TEM: nanoparticles dimensionality
 TEM: composition information

Various interactions can take place

Primary beam can be transmitted/ diffracted – as in

TEM

Secondary electrons are collected and imaged for

SEM or analyzed for energy (Auger e-) giving
composition information

Inelastically scattered e- is used in EELS spectroscopy

useful for detecting light elements

Emitted characteristic X-rays basis of EDAX (EDX) for

elemental analysis (micro-probe)
 Interaction Volumes

The penetration or interaction volume

depends:

• the accelerating voltage (energy of

electron)

• the atomic number of the specimen

(diffracting power of the electron cloud)
 Interaction Volumes

Pear shape

Electron interaction volume in

polymethylmethacrylate (PMMA, a plastic =
Schematic Illustration of electron beam interaction in Ni
low Z atoms) indirectly revealed by etching
 Escape Volumes of Various Signals

If the diameter of the electron beam is ~5 nm

• Secondary electron: diameter ~10 nm;

depth ~10 nm

• Backscattered electron: diameter ~1 μm;

depth ~1 μ m

• X-ray emission: from the whole

interaction diameter volume
~5 μm diameter; ~5 μ m depth
 TEM: Composition
ZnO tetrapods

Elemental analysis using

EDX can be a good way to
determine whether
elements are present

However, it should be used

with other methods to
confirm the results,
especially for quantitative
results
 TEM: Composition
Dual functional optoelectronic and magnetic nanocrystals
Elemental mapping is a good way to
find out which elements are present

Here we have coated pyrite with an

FeSe coating to make it ferromagnetic
and passivate surface traps

The elemental mapping (top right)

shows Fe and S throughout the cubic
crystals but Se is only present on the
I
surface of the cubes.

This confirms the procedure has

worked (in addition to the other data)

A.J. McGrath, et al, J. Phys. Chem. C, 2017, 121 (14), 8220–8226

 TEM: other techniques
One of the main strength of the TEM is the ability to obtain diffraction and image from the same small volume
at the same time

There are many other analysis techniques available:

• Energy Dispersive Spectroscopy (EDS) for compositional analysis
• Electron Diffraction – for crystallographic analysis
• Dark Field imaging – enhanced contrast technique for crystallography
• HRTEM – atomic scale imaging
• STEM – for increased resolution/contrast and improved compositional analysis
• Electron Energy Loss Spectroscopy (EELS) – to examine local environment and allow mapping of elements at
atomic level
• Tomography – produces 3-dimensional images of samples
• Low-dose and cryo-TEM to allow analysis of beam sensitive materials (e.g. polymers and biological samples)
HR-TEM: defect analysis

The characterization of such

defects by transmission
electron microscopy.

Left TEM image showing a

Wadsley type shear in
tungsten oxide & right,
modeling of the image.

[Note some O atoms now 3-

coordinate, since all W remain
octahedral]
HR-TEM: defect analysis

The characterization of
defects by transmission
electron microscopy.

Left TEM image showing “as

twinning
grown” silicon on sapphire
boundary
with complex twinning and
stacking defects

stacking faults
HR-TEM: defect analysis

tilt boundary

The characterization of
defects by transmission
electron microscopy.

Left TEM image showing

<100> tilt boundary in nickel
[II] oxide (NiO)
 CHMS 5130: Microscopic Analysis
LECTURE OUTLINE
1. Optical Microscopy
2. Electron Microscopy
• SEM
• HRTEM
• STEM
3. Surface Microscopy
• STM
• AFM

Reference and Suggested Reading:

 Scanning Transmission Electron Microscopy
(STEM)
Similar to TEM except the beam is narrowed to a fine
point and rastered across the sample

This can be used to produce images, but more usually

to map elements using an EDX or EELS composition
detection.

The accuracy of the method is much greater than SEM

or TEM due to the very small probe volume at each
point

This is often used to detect differences in material

composition in parts of small nanomaterials

CC BY-SA 4.0, https://commons.wikimedia.org/w/index.php?curid=64503919

 EDX for Composition

EDX can be performed in TEM on very small

sized features

In SEM the interaction volume is ~1 μm3

In TEM the interaction volume can be as small

as ~10-8 μm3 due to very small probe size
Scanning Transmission Electron Microscopy
(STEM)
START START
C C Cu Cu START
Cd Cd C Cu
Here an attempt was made to Cd put CdTe
nanocrystals onTethe
Se
ends
Te of CdSe nanorods,
Se Se Te
O O
Te O Cu
Te Cu Cu
Te
Se Se
The image impliesCdthis has
Cdbeen achieved
Cd but aSe
Cu Cu Cu
STEM scan is needed to confirm theSechangeSe
in Se
materials across the length of these nanobarbells END
END END
100
120
100 Cd 100 Se
120 120

% of Total Anions
100 Cd Cd Se 80 Se Se Te

Intensity (arb)

% of Total Anions

% of Total Anions
100 100 Se Se80 Te 80 Te Te
Intensity (arb) 80

Intensity (arb)
Te Te 60
80 80 60
60 60
40
60 60 40

40 40 20
20
40 40

0 20 20 0
20 5 10 15 20 25 30 35 40 45
20 0 10 20 30 40 50

0 0
Distance Along Trace (nm)
0 0
Distance Along Trace (nm)
0 10 0 20 1030 2040 3050 40 50 5 10 15 20
5 25
10 30
15 35
20 40
25 45
30 35 40 45

DistanceDistance
Along Trace (nm)
Along Trace (nm) Distance Along Trace
Distance (nm)
Along Trace (nm)

Halpert et al., JACS 2006

Scanning Transmission Electron Microscopy
(STEM)
Molar ratios of regions of large particles show
different distributions of ions than smaller
particles…more diffuse measurements are
needed to be definitive but this result suggests
the particles have a significant distribution of
matter as well as size

Cu2ZnSnTe4 : “CZTS”
smaller larger
Zn 0.054 1.357
Sn 0.216 0.785
Cu 2 2
60 nm
S 2.27 4.142

Differences in size may be accompanied by differences in stoichiometry

 Scanning Transmission Electron Microscopy
(STEM)
population morphology population metrics
A standard analysis by HRTEM: 35
μ = 5.9 nm
30
for the sample below, we are σ = 1.0 nm (~17%)

Relative Frequency
25

interested in understanding why the 20

emission line is wide, what materials 15

10

are present in the sample 5

0
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Particle size (*nm)

2.0 5

493 nm
Absorbance
PL
single crystal properties SAD approximation by image FFT
4
1.5
PL Intensity
Absorbance

3
FWHM = 39 nm
1.0
2

400 nm
0.5 1
473 nm
451 nm 0
300 350 400 450 500 550 600 650 10 nm
Wavelength (nm)
 CHMS 5130: Microscopic Analysis
LECTURE OUTLINE
1. Optical Microscopy
2. Electron Microscopy
• SEM
• HRTEM
• STEM
3. Surface Microscopy
• STM
• AFM

Reference and Suggested Reading:

 Scanning Probe Microscopies (SPM)
The invention of Scanning Probe Microscopy (SPM) in 1980s was the
first of a whole new set of techniques for looking at the nano-world

(A) In Scanning Tunneling Microscopy (STM) a tiny piezoelectric tip senses the surface by the ‘tunnelling voltage’, so
senses atoms ‘indirectly’.
(B) In the related Atomic Force Microscopy (AFM) shown in the tip is dragged over the surface & directly feels the
contact force from the atoms.
Scanning Probe Microscopies (SPM)

http://spm.phy.bris.ac.uk/
 CHMS 5130: Microscopic Analysis
LECTURE OUTLINE
1. Optical Microscopy
2. Electron Microscopy
• SEM
• HRTEM
• STEM
3. Surface Microscopy
• STM
• AFM

Reference and Suggested Reading:

 Atomic Theory

The Ancient Philosophers: Democritus (460-370 BC, ancient Greek)

(thinking without doing) • In 400 BC, Democritus first proposed that
“matters are made of atoms”
• If you subdivide it into smaller and smaller
pieces you achieve a single indivisible piece
Democritus
(ahead of his time)
Dalton viewed the atom as a small solid
sphere (Billiard Ball Model)
• All matter is made of atoms and atoms are indivisible
• Each element corresponds to a different type of atom
• Compounds are composed of atoms in specific ratios
• Chemical reactions are rearrangements of the atoms
in different compounds/elements (mass is conserved)
John Dalton
As determined by hundreds of years of experiment…but no one expected to see these atoms (1766-1844)
 Is any of this real?

The modern atomic model has been confirmed experimentally in a number of ways. With new tools
in nanotechnology, we are now able to “see” atoms directly via scanning tip microscopy (STM)

Graphene on Ir(111) surface, ACS “phys.org”

Basic Principles

Nobel Laureates Heinrich Rohrer and Gerd Binnig

 STM Tips

How do you make a tip one atom sharp?

You make a sharp point, at some distance
from the base you will find a single atom

e-

×106 ×108 ×108

Source: http://www.chem.qmw.ac.uk/surfaces/scc/scat7_6.htm
 Scanning Tunneling Microscopy (STM)

Five basic components:

1) Metal Tip,
2) Piezoelectric scanner
3) Current amplifier (nA)
4) Bipotentiostat (applied voltage bias)
5) Feedback loop (current)

• Tunneling current from tip to sample or vice-versa

depends on bias
• Current is exponentially dependent on distance
• Raster scanning gives 2D image
• Feedback is normally based on constant current,
thus measuring the height (from piezo
adjustments to compensate)
 Tunneling Current
Three requirements for tunneling:
1. Small distance (~ 1 nm)
2. Overlap of the electron wavefunctions (donor and acceptor states)
3. Bias for net current flow in one direction

Electrons fill to the Fermi level EF. When the sample and tip are brought If the distance d is small, electrons can
For an electron to leave it needs together only a narrow space divides “tunnel” through the barrier. If a (-) voltage
more energy Φ, the work function them. States are filled to EF and must is applied (sample) the electron energy
exceed the energy barrier (Φ) to flow increases and the chance of tunneling back
diminishes, creating net flow (current)
 Tunneling Current

A cartoon illustrating
tunnel under bias
conditions

Raising the energy (+eV)

of the sample electrons
under (-V) voltage permits
electrons to find empty
states at same energy in
the tip

Filled donor state + empty

acceptor state + small d =
high tunneling probability
 Tunneling Current

I  d  tunneling current
 2 2m  e electron charge (-)
I  d   Constant  eV  exp   d  V applied voltage
  m electron mass
 metal work function
d distance
Planck's constant

• The sensitivity of this technique is due to the

exponential decay with distance

• For a WF of 4 eV, the current decreases by a factor of

10 for every 0.1 nm

• A typical atom has a diameter of 0.3 nm, so the This also explains why tips are easy to make → every sharp
current changes by 1000 times! point will end in a single atom…other atoms in tip will have
MUCH lower contribution to current
Work Functions of Common Metals
 Scanning Tunneling Microscopy (STM)
A hard metal tip (W or Pt/Ir alloy) is above the surface & given an electric potential the tunneling current to the tip
increases as gap d decreases, but also affected by the bias and local density of states (atomic wavefunctions)

Measurement Modes: constant height (variable

current) and constant current (variable height) imaging
modes are possible

Constant Height: imaging different atoms (different

work functions) revealing composition

Constant Current: Feedback loop alters height to

adjust current, very sensitive for same atoms to get
surface topography (only d is changing)

At apex of tip a single metal atom has either attractive (3<d<10Å) or repulsive (d<3Å) interactions.
[Note imaging only for metal or semiconductor surfaces]
 Scanning Tunneling Microscopy (STM)
In 1986 Binnig & Rohrer, won Nobel Prize in Physics for Scanning
Tunneling Microscopy, which allowed us to see atomic resolution images
 Scanning Tunneling Microscopy (STM)
Metal alloys are intimate structural mixtures of metal elements. STM image
below shows surface of Silicon (Si), with Tin (Sn)& Lead (Pb) that can be
discriminated and displayed with color coding.
 Scanning Tunneling Microscopy (STM)

Charge can be injected into

the LUMO or extracted from
the HOMO by adjusting the
sample bias relative to the tip

Thus the relative energy

levels and mapping of the
molecular orbitals (MOs) can
be achieved

a,b, Molecular orbital images of pentacene on two monolayer NaCl on Cu(111) obtained by STM using a pentacene-terminated tip. Image size 2.5 nm
× 2.0 nm; constant current. The HOMO (a) was imaged by setting sample voltage to the first resonance at negative bias at V = −2.5 V, thus tunnelling
out of the molecular orbital. The LUMO (b) is imaged by electrons tunnelling from the tip into the orbital at positive bias V = +1.7 V. c,d, Contours of
constant orbital probability distribution of the HOMO (c) and LUMO (d) of the free pentacene
Nature Chemistry Volume: 3, Pages:273–278 Year published:(2011) DOI:doi:10.1038/nchem.1008
 CHMS 5130: Microscopic Analysis
LECTURE OUTLINE
1. Optical Microscopy
2. Electron Microscopy
• SEM
• HRTEM
• STEM
3. Surface Microscopy
• STM
• AFM

Reference and Suggested Reading:

Atomic Force Microscopy (AFM)

In related AFM (also invented at IBM) a piezo tip is rastered

over the surface & the physical force registers as a movement
optically detected by laser interferometry

Operates in contact, tapping and non-contact modes

 Atomic Force Microscopy (AFM)

Monitors the force of attraction/repulsion between the

oscillating tip and the sample surface

The tip is attached to a cantilever which moves up and

down (while oscillating in tapping mode)

The position of the tip is detected by a laser that hits the

top of the cantilever and is reflected to a position detector

Because of the long laser beam and precise position

measurement, the tip height can be quickly and precisely
measured

…this allows rapid measurement in changes in height and

phase (oscillation)
Source: http://www.nanoscience.com/education/AFM.html
 Atomic Force Microscopy (AFM)

Tip size matters for AFM: many atoms close to Line broadening if the tip is on the same
tip atom will contribute to forces order as the features being measured

tip
image

STM

sample

Compression can occur if the tip is strongly

AFM attracted to the sample due to material interactions
in different areas of the sample
 Differences btw AFM and STM
1. AFM captures precise images by moving a nanometer sized tip across the
surface of the image. The STM captures images using quantum tunneling.

2. The probe makes a direct contact with the surface or calculates the incipient
chemical bonding in AFM. The STM images indirectly by calculating the quantum
degree tunneling between he probe and sample.

3. The tip in AFM touches the surface gently touches the surface whereas in STM,
the tip is kept at a short distance from the surface.

4. AFM resolution is better than the STM. This is why AFM is widely used in nano-
technology.

5. When Scanning Tunneling Microscope is normally applicable to conductors, the

Atomic Force Microscope is applicable to both conductors and insulators.

6. The AFM suits well with liquid and gas environments whereas STM operates
only in high vacuum.
 AFM: phase vs height imaging
This can be useful in assessing monolayer converage
Phase diagrams can be clearer in imaging than
from a spin casting process, where the height difference
“height” imaging
is small but the material difference matters greatly
Phase Height

Monolayers of QDs in an LED (flat organic surface)

Change in phase (of the tip vibration) indicates a

change in the material on the surface, and thus the
tip “delay” in vibrating from inc/dec attraction

Anikeeva, P. O.*; Halpert, J. E.*; Bawendi, M. G.; Bulovic, V. Nano. Lett. 2007, 7, 2196. Jonathan E. Halpert, Thesis MIT 2008 Seth Coe-Sullivan, Thesis MIT 2006
 Comparing STM to AFM

Using non-contact AFM, Professor

Xiaohui Qiu from the National
Center for Nanoscience and
Technology, Beijing, and
colleagues, imaged the hydrogen
bonds linking 8-hydroxyquiline
clusters at high resolution

http://www.microscopy-analysis.com/editorials/editorial-listings/researchers-reveal-first-afm-image-hydrogen-bond
 Conclusions: Microscopy
• After XRD, use of electron microscopy most important for solid state materials, there are many different types
of electron microscopes:
• SEM Scanning Electron Microscope – gives topological images of sample surface from 2o e–
-Limitation: samples should be coated with C or Au to assist imaging
• TEM can give direct imaging of atoms in a solid in the projection of the beam or using different optical setting
a diffraction pattern which establishes the crystalline structure
-Limitations: sample must be thin section (1mm) & e- beam damages the sample
• HRTEM can get down to atomic resolution ca 0.75A – ‘atomic imaging’
• STEM combines above give scanning Transmission image which reduces damage
• recently STM (Scanning Tunneling) and AFM (Atomic Force) use conducting or piezoelectric tips to scan
surface – getting surface characteristics/profiles.

Next time: not sure

Reading: none
Questions
Questions
Review Questions