Department of Chemical Engineering

1 Nanomaterials and Nanotechnology

(10626598)
Electron Microscopy

Transmission Electron Microscope (TEM)

Dr. Shadi Sawalha

Spring 2023 - 2024

9/28/2023
 The first electron microscope
2

Ernst Ruska:
Nobel Prize in physics 1986

Knoll and Ruska, first TEM in 1931

Idea and first images published in 1932
By 1933 they had produced a TEM Electron Microscope Deutsches
Museum, 1933 model
with two magnetic lenses which gave
12 000 times magnification.
9/28/2023
3 Overview
 Transmission electron microscopy (TEM) is a technique for achieving high
resolution images of thin specimens. A beam of high energy electrons
passes through the specimen and is then focussed to form an image.

 The resolution of the TEM is greater than that of the scanning electron
microscope, and is typically of the order of 0.2 nm. This compares with
approximately 2 nm for the SEM and around 0.2 m for the conventional
optical microscope.

 Imaging in the TEM must be carried out under vacuum, as electrons

cannot travel through air.

Units:

1 nm = 10-9 m; 1 m = 10-6 m 9/28/2023

4 Resolution limit

Year Resolution
1940s ~10nm
1950s ~0.5-2nm
0.3nm (transmission)
1960s
~15-20nm (scanning)
0.2nm (transmission)
1970s
7nm (standard scanning)
0.15nm (transmission)
1980s
5nm (scanning at 1kV)
0.1nm (transmission)
1990s
3nm (scanning at 1kV)
2000s <0.1 nm (Cs correctors)
http://www.sfc.fr/Material/hrst.mit.edu/hrs/materials/public/ElecMicr.htm

9/28/2023
5 Components of the TEM

Electrons emitted by the gun are

accelerated, typically by 80 - 200 kV.
The condenser lenses focus the beam
onto the specimen, which is introduced
into the microscope through an airlock.
The objective lens forms a focussed
image, which is enlarged by the projector
lenses.
The image is viewed on a fluorescent
screen or a computer monitor.

9/28/2023
6

electron source

condenser system

specimen (thin)

objective lens

projector lens

9/28/2023
7 Basic TEM

Electron source (HV= 200kV)

Apertures
Magnetic lenses
Sample holder
Vacuum in the column
better than 10-6 Pa

Fluorescence screen

Recording media
(Film/CCD/ TV)

Pedals for tilting the sample

9/28/2023
 The electron source

• Two types of emission guns:

– Thermionic emission
• W or LaB6

– Field emission
• W Cold FEG ZrO/W Schottky FEG

9/28/2023
9 The electron source

The transmission electron microscopes mainly use lanthanum

hexaboride (LaB6) filaments. These consist of a small crystal of LaB6,
with a pointed tip, supported between two electrodes.

A current is passed through the crystal and

electrons are emitted. Lanthanum
hexaboride is used because it has a low
work function, meaning that the yield of
electrons is high, and because it produces
electrons with a narrow spread of energies.

LaB6 crystal

9/28/2023
10

W Advantages: LaB6 advantages: FEG advantages:

Rugged and easy to High brightness Extremely high brightness
handle
Requires only moderat High total beam current Long life time, more than
vacuum 1000 h.
Good long time stability Long life time (500-
1000h)
High total beam current
W disadvantages: LaB6 disadvantages: FEG disadvantages:
Low brightness Fragile and delicate to Very fragile
handle
Limited life time (100 h) Requires better vacuum Current instabilities
Long time instabilities Ultra high vacuum to
remain stable
9/28/2023
11 Accelerating voltage

Electrons emitted by the filament are accelerated by a series of anodes.

For transmission electron microscopy, accelerating voltages typically
range from 60 kV to 200 kV. Higher accelerating voltages give higher
resolution, but less contrast. High accelerating voltages can also result in
greater specimen damage. For these reasons, studies of biological
samples tend to employ low accelerating voltages (60 kV to 100 kV),
while studies of inorganic materials, which often require higher
resolution, usually employ an accelerating voltage of 200 kV.

9/28/2023
12 Electromagnetic lenses

All modern TEMs use electromagnetic lenses. These consist of a coil of

copper wires inside iron pole pieces.

A current through the coils creates a magnetic

field, symbolized by red lines in the diagram
on the left. Electrons close to the centre are
less strongly deflected than those passing
through the lens far from the axis.

9/28/2023
13 Apertures

The condenser aperture controls

the fraction of the beam which is
allowed to hit the specimen. It
therefore helps to control the
intensity of illumination.
The objective aperture is used to
select which beams in the diffraction
pattern contribute to the image, thus
producing diffraction contrast.
The selected area aperture is used
to selected a region of the specimen
from which a diffraction pattern is
obtained.

9/28/2023
14 Electron diffraction in the TEM
Because electrons have wave-like properties, they can be diffracted by
crystalline specimens. The resulting diffraction patterns give information
about the crystal structure of the specimen. A typical diffraction pattern (in
this case from a crystal of C60) is shown below.

Diffraction patterns can be recorded

in two ways – by inserting a selected
area aperture (as mentioned on the
previous slide), or by focussing the
beam onto a small region of the
specimen.

9/28/2023
15 Contrast in the TEM: Diffraction contrast - 1

The most important contrast

mechanism for crystalline materials
is diffraction contrast.
To produce diffraction contrast, the
objective aperture is placed around
the central beam in the diffraction
pattern.

9/28/2023
16 Contrast in the TEM: Diffraction contrast - 2

The effect of introducing the

objective aperture is to
exclude scattered beams, as
illustrated in the diagram.
The result is that regions of
the specimen which scatter
electrons will appear dark in
the image.

9/28/2023
17 Specimen preparation for TEM - 1
 Specimens for TEM are typically supported on 3 mm diameter grids, usually made of
copper. These grids often have thin carbon films suspended across them, which may
be continuous, holey or “lacey”.

3 mm TEM Carbon films

grid

 Specimens for TEM need to be less than ~ 100 nm in thickness, in order for the
electrons to pass through and form an image. For some materials, e.g. inorganic
powders, specimen preparation is extremely straightforward and simply involves
grinding the material to a fine powder, dispersing in a liquid, pipetting onto a grid and
allowing to dry. For organic or biological materials more specialised techniques are
needed.

9/28/2023
18 Specimen preparation for TEM - 2
 Small biological structures such as viruses and bacteria can be deposited onto
carbon films from solution, but would give very little contrast in their untreated state.
In such cases the technique of negative staining is often used to reveal structure.

 Negative staining involves surrounding

the biomolecules with thin amorphous
layer of heavy metal salt. This reveals
the structure, and reduces the
structural flattening that occurs in the
absence of stain.

 Commonly used stains: uranyl acetate,

uranyl formate, sodium/potassium
phosphotungstate, ammonium Adenovirus negatively stained
molybdate. with uranyl acetate

9/28/2023
19 Specimen preparation for TEM - 3
 An alternative to negative staining is positive staining, in which the heavy metal salt
selectively stains certain features within the sample, enabling them to be visualised.
Salts used for positive staining include uranyl acetate, lead citrate, osmium tetroxide
and ruthenium tetroxide.

 Positive staining is often used in

studying polymer samples in which
two different phases are present. It is
necessary to choose a stain which
attaches itself to one component but
not the other. The example on the right
is the block copolymer polystyrene-b-
methylmethacrylate, stained with
RuO4. The RuO4 preferentially stains
the polystyrene, so this component
appears dark in the image.

9/28/2023
20 Specimen preparation for TEM - 4

Microtomy – in order to prepare

TEM specimens from biological
tissue it is necessary to embed the
fixed tissue in a resin and then
produce thin sections using a
microtome. The sections are then
deposited onto grids and stained.
Microtomy is also used for other
“soft” materials such as polymers.

9/28/2023
21 Astigmatism 1‫ﺍﻟﻼﺑﺅﺭﻳﺔ‬
Astigmatism is an aberration ‫ ﺍﻧﺣﺭﺍﻑ‬of lenses that causes rays in a plane
parallel to the optical axis to be focused at a different focal point from
rays in a plane at 90° to it. In the TEM, both the condenser and objective
lenses are affected by astigmatism.

Condenser astigmatism has the effect

of distorting the beam to an elliptical
shape either side of focus as shown on
the right. This needs to be corrected in
order to achieve even illumination of
the specimen. All electron microscopes
are equipped with stigmators, which
enable this correction to be carried out.

9/28/2023
22 Astigmatism 2

The effect of objective astigmatism is that the image appears “streaked”

in one direction, and then in the other direction, as you go through focus.
The TEM images shown below illustrate how astigmatism affects the
image as you go through focus.

9/28/2023
23 TEM image 3.8 nm

TEM image of CNDs (a) and size distribution histogram (b)

250000X
9/28/2023
 Department of Chemical Engineering

Nanomaterials and Nanotechnology

1 (10626598)

Introduction to Molecular Spectroscopy

Dr. Shadi Sawalha

Fall 2023-2024

10/18/2023
 Contents
• Introduction to spectroscopy

• Classification of spectroscopic techniques

• Common types and their introduction

• Infra-Red spectroscopy: Fundamental concepts

• Vibrations in IR- Region and calculations of different

vibrational energies in terms of frequencie.

10/18/2023 2
 Spectroscopy
Definition:
The study of the interaction between radiations and matter as a function of
wavelength λ.
Interactions with particle radiation or a response of a material to an alternating
field or varying frequency ν.
Spectrum:
A plot of the response as a function of wavelength or more commonly
frequency is referred to as a spectrum.
Spectrometry:
It is the measurement of these responses and an instrument which performs
such measurements is a spectrometer or spectrograph, although these terms
are more limited in use to the original field of optics from which the concept
sprang.
Spectroscopy is often used in physical and analytical chemistry for the
identification of substances through the spectrum emitted from or absorbed by
them. Spectroscopy is also heavily used in astronomy and remote sensing. Most
large telescopes have spectrometers, which are used either to measure the
chemical composition and physical properties of astronomical objects or to
measure their velocities from the Doppler Shift of their spectral lines.

10/18/2023 3
 Classification of Methods
The type of spectroscopy depends on the physical quantity measured. Normally, the
quantity that is measured is an intensity, either of energy absorbed or produced.
Most spectroscopic methods are differentiated as either atomic or molecular based on
whether or not they apply to atoms or molecules. Along with that distinction, they can
be classified on the nature of their interaction:
Absorption spectroscopy
It uses the range of the electromagnetic spectra in which a substance absorbs. This
includes atomic absorption spectroscopy and various molecular techniques, such as
infra-red spectroscopy in that region and Nuclear Magnetic resonance spectroscopy in
the radio region.
Emission spectroscopy
It uses the range of electromagnetic spectra in which a substance radiates (emits). The
substance first must absorb energy. This energy can be from a variety of sources, which
determines the name of the subsequent emission, like luminescence. Molecular
luminescence techniques include spectroflourimetry.
Scattering spectroscopy
It measures the amount of light that a substance scatters at certain wavelengths,
incident angles, and polarization angles. The scattering process is much faster than the
absorption/emission process. One of the most useful applications of light scattering
spectroscopy is Raman Spectroscopy.

10/18/2023 4
 Common types
• Fluorescence spectroscopy
• X.ray spectroscopy and crystallography
• Flame spectroscopy
1. Atomic emission spectroscopy
2. Atomic absorption spectroscopy
3. Atomic fluorescence spectroscopy
• Plasma emission spectroscopy
• Spark or arc emission spectroscopy
• UV/VIS spectroscopy
• IR spectroscopy
• Raman spectroscopy
• NMR spectroscopy
• Photo thermal spectroscopy
• Thermal infra-red spectroscopy
• Mass Spectroscopy

10/18/2023 5
Brief about spectroscopy

1- Fluorescence spectroscopy:
Fluorescence spectroscopy uses higher energy photons to excite a sample,
which will then emit lower energy photons. This technique has become
popular for its biochemical and medical applications.

10/18/2023 6
Cont’d
2- X-ray spectroscopy:
X-rays of sufficient frequencies interact with material and excite the atoms
contained. Due to this excitation Auger Effect is produced and some
excitation radiations are absorbed or evolved if vice versa occurs.
X-ray absorption and emission spectroscopy is used in chemistry and
material sciences to determine elemental composition and chemical
bonding.

Very good and versatile technique but a little complex. It needs some
scattering light detectors along with X-ray source. Overall X-ray
diffraction technique is one that is used most widely for bond length and
angle measurements.

Examples as: X-ray diffraction (XRD) and X-ray photoelectron

spectroscopy (XPS)

10/18/2023 7
 Cont’d
3 Flame Spectroscopy:
Liquid solution samples are aspirated into a burner or nebulizer/burner
combination, desolvated, atomized, and sometimes excited to a higher
energy electronic state. The use of a flame during analysis requires fuel
and oxidant, typically in the form of gases. Common fuel gases used are
acetylene (ethyne) or hydrogen. Common oxidant gases used are oxygen,
air, or nitrous oxide. These methods are often capable of analyzing
metallic element in the PPM, billion, or possibly lower concentration
ranges. Light detectors are needed to detect light with the analysis
information coming from the flame.
- Atomic absorption Spectroscopy
- Atomic emission spectroscopy
- Atomic fluorescence spectroscopy

How would you differentiate in them?

10/18/2023 8
4- Spark or arc (emission) spectroscopy :
It is used for the analysis of metallic elements in solid samples.
For non-conductive materials, a sample is ground with graphite powder to
make it conductive.
In traditional arc spectroscopy methods, Since the conditions producing
the arc emission typically are not controlled quantitatively, the analysis
for the elements is qualitative. Nowadays, the spark sources with
controlled discharges under an argon atmosphere allow that this method
can be considered eminently quantitative, and its use is widely expanded
worldwide through production control laboratories of foundries and steel
mills.

10/18/2023 9
 Cont’d

5- UV/VIS spectroscopy:
• It basically involves the spectroscopy of photons and spectrophotometery.
• It uses light in the visible and adjacent near ultraviolet (UV) and near
infrared (NIR) ranges.
• UV/Vis spectroscopy is routinely used in the quantitative determination of
solutions of transition metal ions and highly conjugated
organic compounds.
• For the quantitative measurements, Beer-Lambert law is followed.
• The Beer-Lambert Law is useful for characterizing many compounds but
does not hold as a universal relationship for the concentration and
absorption of all substances. A 2nd order polynomial relationship
between absorption and concentration is sometimes encountered for
very large, complex molecules such as organic dyes.

10/18/2023 10
10/18/2023 11
 Cont’d

6- Infra-red Spectroscopy:
• (IR spectroscopy) is the subset of spectroscopy that deals with the
infrared region of the electromagnetic spectrum. It covers a range of
techniques, the most common being a form of absorption spectroscopy.
As with all spectroscopic techniques, it can be used to identify compounds
or investigate sample composition.
• Infrared spectroscopy offers the possibility to measure different
types of inter atomic bond vibrations at different frequencies. Especially in
organic chemistry the analysis of IR absorption spectra shows what type of
bonds are present in the sample.
• Infrared spectroscopy exploits the fact that molecules have specific
frequencies at which they rotate or vibrate corresponding to discrete
energy levels.

10/18/2023 12
10/18/2023 13
 Infra Red Spectroscopy
Introduction:
The absorption of infra-red radiations causes the various bands in a
molecule to stretch or bend w.r.t. one another.

Near IR-Region 0.8 – 2.5 micron Rotational Spec.

Mid infra red region 2.5 – 1.5 micron Vib-Roto Spec.
Far IR-Region 15 – 200 micron Overtone or harmonic

Band intensity is either expressed as absorbance or transmittance.

10/18/2023 14
10/18/2023 15
10/18/2023 16
 Cont’d

• To establish the identity of two compounds (comparative study)

• To determine the structure of a new compound from its functional groups

• To determine the nature of contaminants in a sample

• For quantitative analysis of a component in the overall mixture

• For the quantitative analysis of contaminants in given sample

• Some advanced physical properties of the materials

10/18/2023 17
 Basic Principles: Molecular Vibrations
• Absorption in the infra-red region is due to the changes in the vibrational
and Rotational levels.
• With low energy radiations, molecular rotations occur
• With high energy radiations, molecular vibrations occur

• Due to IR-radiation energy, a vib-rotational spectrum is obtained. The

vibrational energy depends upon the followings:
1- masses of atoms present in the molecule
2- Strength of bonds and bond distances
3- The arrangement of atoms within a molecule

10/18/2023 18
 Types of vibrations in a molecule
Two fundaments types:
1 Stretching
2 Bending

Stretching:
The distance between the two atoms increases or decreases but the
atoms remain in the same bond axis.

Bending:
The position of the atoms changes with respect to the original bond axis.

Stretching occurs at high frequencies and bending at low ?

10/18/2023 19
 Cont’d

Stretching Vibrations:
c) Symmetric stretch
d) Asymmetric stretch

Bending Vibrations:
g) Scissoring
h) Rocking
i) Wagging
j) Twisting

https://www.youtube.com/watch?v=W6mjL7t
NwJ8

10/18/2023 20
 Vibrational Frequency
Stretching vibrational frequency of a bond can be calculated through
Hook’s Law as:

K = 5 x 105 g/cm2 for single bonds

C = Velocity of radiation = 2.99 X 1010cm/s

10/18/2023 21
m1,m2 are masses of bonded atoms
 If the stretching frequency of a hydrogen molecule is 1.2 × 1014
vibrations/sec. Calculate the wavenumber where hydrogen
molecule absorption band will be observed in an IR spectrum.

Ans: The frequency of hydrogen stretching can be represented in terms

of wavenumbers as follows:
̅= 1/ = / cm-1
̅= 1.2 × 1014 −1/3 × 1010 / = 4000 cm-1

10/18/2023 22
 Do yourself
Calculate the bond vibrating frequencies and the wave numbers
for the followings:
• C–C 11. O=O
• C–O 12. C=S
• H–H 13. C=P
• O–H 14. C = Si
• O–O 15. C =_ C
• O – F 16. C – Cl
• C = C 17. C - Al
• C=O
• C=N
• C = Fe Extract the conclusions?

10/18/2023 23
 https://www.youtube.com/watch?v=6Oe7j4QM5HA

10/18/2023 24
 Energy of an electromagnetic radiation is given by:

=ℎν=ℎ /
h is Planck’s constant and has a value of 6.626 × 10-34 m2·kg·s-1

10/18/2023 One electronvolt equals 1.602 × 10-19 Joules 25

10/18/2023 26
 Cont’d

7- Raman Spectroscopy:
• It relies on inelastic scattering, or Raman scattering of
monochromatic light, usually from a laser in the visible, near infrared, or
near ultraviolet range. The laser light interacts with phonons or other
excitations in the system, resulting in the energy of the laser photons
being shifted up or down. The shift in energy gives information about the
phonon modes in the system.
• Spontaneous Raman scattering is typically very weak, and as a result
the main difficulty of Raman spectroscopy is separating the weak
inelastically scattered light from the intense Rayleigh scattered laser light.
Raman spectrometers typically use holographic diffraction gratings and
multiple dispersion stages to achieve a high degree of laser rejection.

10/18/2023 27
10/18/2023 28
 G-band arises from the
stretching of the C-C bond in
graphitic materials, and is
common to all sp2 carbon
systems. If there are some
randomly distributed impurities
or surface charges in the
graphene, the G-peak can
split into two peaks, G-
peak (1583 cm-1) and D'-
peak (1620 cm-1).

We also see a
prominent band around
1350 cm-1. This band is
Combined with the G-band, this spectrum is known as the D band.
a Raman signature of graphitic sp2 The D band originates from
materials and is called 2D(G*)-band. 2D- a hybridized vibrational
band is a second-order two-phonon process mode associated with
and exhibits a strong frequency dependence graphene edges and it
on the excitation laser energy. indicates the presence of
some disorder to the
graphene structure

10/18/2023 29
 Cont’d
8 Nuclear magnetic resonance:
Nuclear magnetic resonance spectroscopy analyzes the magnetic
properties of certain atomic nuclei to determine different electronic local
environments of hydrogen, carbon, or other atoms in an organic
compound or other compound. This is used to help determine the
structure of the compound.

NMR spectrum of fullerene C60

10/18/2023 30
9 Photo thermal spectroscopy:
It is a group of high sensitivity spectroscopy techniques used to measure
optical absorption and thermal characteristics of a sample. The basis of
photo-thermal spectroscopy is the change in thermal state of the sample
resulting from the absorption of radiation. Light absorbed and not lost by
emission results in heating. The heat raises temperature thereby
influencing the sample thermodynamic properties. Measurement of the
temperature, pressure, and/or density changes that occur due to optical
absorption are ultimately the basis for the photo-thermal spectroscopic
measurements.

10/18/2023 31
 Department of Chemical Engineering

Nanomaterials and Nanotechnology

(10626598)
1
Atomic Force Microscopy (AFM)

Dr. Shadi Sawalha

Fall 2023-2024
 Atomic Force Microscope (AFM)

• Binnig, Quate, and Gerber invented the Atomic Force

Microscope in 1985
• It can image almost any type of surface, including
polymers, ceramics, composites, glass, and biological
samples

Calvin Quate (1923) Gerd Binnig (1947) Christoph Gerber (1942)

The first Atomic Force Microscope - Science Museum London
AFM at CIC biomaGUNE
Main Components of an AFM

• Cantilever with a sharp tip

• Laser beam deflection
system (introduced by Meyer
and Amer)
• Detector and Feedback
electronics
• Piezoelectric tube
•Image display system
 AFM COMPONENTS

Figures from Wikipedia

 How It Works
• Invented in 1986
• Cantilever
• Tip
• Surface
• Laser
• Multi-segment photodetector

Figure 4. Three common types of AFM tip. (a) normal tip (3 µm tall); (b)
supertip; (c) Ultralever (also 3 µm tall). Electron micrographs by Jean-
Paul Revel, Caltech. Tips from Park Scientific Instruments; supertip
made by Jean-Paul Revel.
http://stm2.nrl.navy.mil/how-afm/how-afm.html#imaging%20modes
http://www.molec.com/what_is_afm.html
AFM cantilever (after use) in the
SEM, magnification 1,000 x AFM cantilever (after use) in the
SEM, magnification 3,000 x

AFM cantilever (after use) in the

SEM, magnification 50,000 x
The atoms of a Sodium Chloride crystal viewed with an Atomic Force Microscope
 How does AFM work?
Measure the forces between the sharp tip and sample surface
Long-range forces Short-range forces
Van der Waals forces Chemical forces:
Capillary forces ionic bonds, covalent
Magnetic forces bonds, metallic bonds
Electrostatic force Repulsion forces:
Pauli repulsion, ionic
repulsion
 How are forces measured?

Hooke’s law: F= -ks

Laser Beam Deflection Method

 Fabrication of Cantilever
• Made from Si₃N₄ or Si
• As soft as possible to achieve high sensitivity
• Spring constant < equivalent spring constant between
atoms of sample in order not to dragging the atoms out of
its atomic site
 Fabrication of Tip
• Made from Si₃N₄ or Si
• As sharp as possible
• The radius of curvature of the tip does not
influence the height of a feature but the lateral
resolution
 Modes of Imaging
Constant Height
• Cantilever is "dragged" across the
surface of the sample
• Tip is free to move up and down
• Force between tip and sample
surface is measured directly using the
deflection of the cantilever
No need to wait for the response of
feedback system, scan in high speed
No signal error
x If surface is rough, can cause damage
to tip and surface
 Modes of Imaging
Constant Force
• Move the cantilever up and down using the
piezoelectric tube
• so that the position of laser beam is
unchanged
• i.e. force between tip and sample surface
remain constant

Suited for almost every surface

x Scan slowly, need to wait for the response of
feedback system
x Sensitive to random noise, has signal error
 Constant Force Modes
• Contact Mode (<0.5nm tip-surface separation)
• Tapping Mode (0.5-2nm tip-surface separation)
• Non-contact Mode (0.1-10nm tip-surface separation)
 Topography
• Contact Mode
– High resolution
– Damage to sample
– Can measure
frictional forces
• Non-Contact Mode
– Lower resolution
– No damage to sample
• Tapping Mode
– Better resolution
2.5 x 2.5 nm simultaneous topographic and friction image of highly
– Minimal damage to oriented pyrolytic graphic (HOPG). The bumps represent the
topographic atomic corrugation, while the coloring reflects the lateral
sample forces on the tip. The scan direction was right to left
http://stm2.nrl.navy.mil/how-afm/how-afm.html#imaging%20modes
 Contact Mode

• Tip almost touches the surface

• Force on the tip is repulsive
• Force between the tip and the surface is kept constant
during scanning by maintaining a constant deflection

Advantages:
 Better resolution than tapping mode and non-contact mode
 Fast scanning
 Good for rough surface

Disadvantages:
x Force can damage or deform soft samples
 Tapping Mode
• Cantilever is driven to oscillated up and down at its resonant
frequency
• Probe slightly taps on the surface during scanning, contacting
the surface at the bottom of its swing
• Adjust the height of cantilever by the piezoelectric tube to
maintain a constant oscillation amplitude
i.e. constant force between tip and surface is maintained
Advantages:
High resolution for the samples that are easily damaged
(biological sample)
Disadvantages:
x Slower scanning speed needed
 Non-contact Mode
• Tip does not contact the surface
• Similar to tapping mode, cantilever is oscillated at
its resonant frequency
• Adjust height of cantilever to keep constant
oscillation amplitude, constant force between tip
and surface
Advantages:
 Prevent tip from sticking to the surface (Note: all samples unless in a
controlled UHV or environmental chamber have some liquid adsorbed on the
surface).
 Low force exerted on surface
 No damage to tip and surface
Disadvantages:
x Lower resolution
x Slower speed
 Applications
• Biological Science : Live cell

Human Lung Cancer

Scan size: 60 µCell m
 Applications

• Materials Science
DVD
• Polymer Science
• Data Storage : Help in design hard disk drive at nanoscale level
• Semi conductor

Surface topography of ZnO film Image of polymer blend

 Lateral Force Microscopy

• The probe is scanned sideways. The degree of torsion of the cantilever is used as
a relative measure of surface friction caused by the lateral force exerted on the
probe.

• Identify transitions between different components in a polymer blend, in

composites or other mixtures

• This mode can also be used to reveal fine structural details in the sample.
 Lateral Force Microscopy
Images/photo taken with NanoScope® SPM, courtesy Digital Instruments, Santa Barbara ,CA

Natural rubber/
EDPM blend

20 micron scan

Polished poly-
crystalle silicon
carbide film.

Grain structures

30 micron scan
Magnetic recording
head

Al oxide grains
and contamination
 Phase Imaging
• Accessible via TappingMode
• Oscillate the cantilever at its resonant frequency. The amplitude is used as a
feedback signal. The phase lag is dependent on several things, including
composition, adhesion, friction and viscoelastic properties.

l Identify two-phase structure of polymer blends

l Identify surface contaminants that are not seen in height images
l Less damaging to soft samples than lateral force microscopy
 Phase Imaging
Image/photo taken with NanoScope® SPM, courtesy Digital Instruments, Santa Barbara ,CA

Compositepolymer
imbedded in a matrix

1 micron scan

Bond pad on an
integrated circuit

Contamination

1.5 micron scan

MoO3 crystallites
on a MoS2 substrate

6 micron scan
 Magnetic Force Microscopy

• Special probes are used for MFM. These are magnetically sensitized by sputter
coating with a ferromagnetic material.
• The cantilever is oscillated near its resonant frequency (around 100 kHz).
• The tip is oscillated 10’s to 100’s of nm above the surface
• Gradients in the magnetic forces on the tip shift the resonant frequency of the
cantilever .
• Monitoring this shift, or related changes in oscillation amplitude or phase,
produces a magnetic force image.
• Many applications for data storage technology
 Magnetic Force Microscopy
Image/photo taken with NanoScope® SPM, courtesy Digital Instruments, Santa Barbara ,CA

Overwritten tracks on a textured hard disk, 25 micron scan

Domains in a 80 micron garnet film

 Force Modulation Imaging

• Oscillate the cantilever vertically at a rate that is significantly faster than the scan
rate.
• The amplitude of the oscillations changes in response to the sample stiffness.
• Used in conjunction with LiftMode to separate topography and elasticity data.
Force Modulation Imaging
 Other Techniques
Image/photo taken with NanoScope® SPM, courtesy Digital Instruments, Santa Barbara ,CA

• Scanning capacitance microscopy

– Apply a constant amplitude sine wave voltage to the sample.
The image is then reconstructed from the changes in the
amplitude of the capacitance oscillations.
– Location of defects in wafers (pinning of electrical carriers)
– Image carrier concentration

• Scanning thermal microscopy

– Uses a temperature sensitive probe with a special holder.
– Location of “hot-spot” defects in semiconductor wafers
90 micron
scan size
 Other Techniques
• Nanoindenting and scratching
– A diamond tip is mounted on a metal cantilever and
scanned either with contact or TappingMode.
– Indenting mode presses the tip into the sample
– Scratch mode drags the tip across the sample at a
specific rate and with a specified force.
– The use of TappingMode makes it possible to
simultaneously image soft samples.

• Imaging of biological samples

– cells, DNA (TappingMode in solution)
 Reference
• Wikipedia – Scanning Tunneling Microscope http://en.wikipedia.org/wiki/Scanning_tunneling_microscope
Atomic Force Microscope http://en.wikipedia.org/wiki/Atomic_force_microscope
• http://ww.parkafm.com/
• Atomic Force Microscopy lecture notes by HuiWen Cheng
• Introduction to Scanning Probe Microscopy (SPM), Basic Theory, Atomic Force Microscopy (AFM) by
Robert A. Wilson and Heather A. Bullen, Department of Chemistry, Northern Kentucky University, Highland
Heights, KY 41099.
 Department of Chemical Engineering

Nanomaterials and Nanotechnology

1 (10626598)

X-Ray Photoelectron Spectroscopy (XPS)

Dr. Shadi Sawalha

Fall 2023-2024

10/30/2023
Copyright to Prof. Nizam M. El-Ashgar
2 Photoelectron Spectroscopy XPS

• What is XPS?

• Aim of XPS Analysis.

• General Theory

• How can we identify elements and compounds?

• Instrumentation for XPS

• Examples of materials analysis with XPS

10/30/2023
3 What is XPS?
• X-ray Photoelectron Spectroscopy (XPS), also known as Electron Spectroscopy for
Chemical Analysis (ESCA) is a widely used technique to investigate the chemical
composition of surfaces.

• Sample is illuminated with soft (1.5kV) X-ray radiation in an ultrahigh vacuum.

• The photoelectric effect leads to the production of photoelectrons, the energy

spectrum of which can be determined in a beta-ray spectrometer.

X.ray Photoelectron spectroscopy, based on the photoelectric effect,1,2 was

developed in the mid-1960’s by Kai Siegbahn and his research group at the
University of Uppsala, Sweden.3

1. H. Hertz, Ann. Physik 31,983(1887).

2.A. Einstein, Ann. Physik 17,132 (1905). 1921 Nobel Prize in Physics.

3.K. Siegbahn, Et. Al.,Nova Acta Regiae Soc.Sci., Ser. IV, Vol. 20 (1967). 1981 Nobel Prize in Physics.

10/30/2023
 4

The Atom and the X-Ray

X-Rays on the Surface
X-Ray
Free electron e- lower layer
e- top layer
but no collisions Outer surface

Valenceelectrons e- lower layer X-Rays Inner surface

with collisions 10/30/2023
proton
neutron

Core electrons electron

electron vacancy

The core electrons respond very

well to the X-Ray energy

Atoms layers
5 X-Rays on the Surface

• The X-Rays will penetrate to the core e- of the atoms in the

sample.

• Some e-s are going to be released without any problem giving

the Kinetic Energies (KE) characteristic of their elements.

• Other e-s will come from inner layers and collide with other e-s
of upper layers
–These e- will be lower in energy.
–They will contribute to the noise signal of the spectrum.

10/30/2023
6 X-Rays and the Electrons

X-Ray
Electron without collision
Electron with collision

The noise signal comes

from the electrons that
collide with other electrons
of different layers. The
collisions cause a decrease
in energy of the electron
and it no longer will
contribute to the
characteristic energy of the
element.

10/30/2023
7 Aim of XPS Analysis

• Identification of elements at surfaces (depth: 10 nm).

• Identification of functional groups and redox states.
• Concentration and depth profiling.
• Estimation of over layer thickness.
• Comparison of bulk and surface composition.
• Surface homogeneity/heterogeneity
• Possible surface morphology of adlayers.

10/30/2023
8 Physical Bases

• Based upon photon in/electron out process.

• Photon E (Einstein ): E= h
where: h - Planck constant( 6.62 x 10 -34 J s ).
- frequency (Hz) of the radiation.
• In XPS the photon is absorbed by an atom in a molecule or solid,
leading to ionization and the emission of a core (inner shell)
electron.
• If the photon interacts with valence levels (ionization by lost of one
of them) the technique is different and called UPS, Ultraviolet
photoelectron spectroscopy .

10/30/2023
9 Photoelectric effect

10/30/2023
10
Process of Photoionization

A + h  = A+ + e-

E(A)+ h  = E(A+ ) + E(e-)

KE= h  – [ E(A+ ) - E(A)]

• The difference in energy between the ionized and neutral

atoms, is generally called the binding energy (BE) of the
electron:
KE = h  - BE

10/30/2023
11 The Photoelectric Process

 XPS spectral lines are

Ejected Photoelectron identified by the shell
Incident X-ray from which the electron
was ejected (1s, 2s, 2p,
Free
etc.).
Electron Level
Conduction Band  The ejected
Fermi
photoelectron has kinetic
Level energy:
ValenceBand

2p L2,L3 KE = hv – BE - 
2s L1  Following this process,
the atom will release
1s K energy by the emission
of an Auger Electron.
12 Binding Energy (BE)
The BE is a direct measure of the energy required to just remove the electron concerned
from its initial level to the vacuum level and the KE of the photoelectron is again given
by:
KE = hν - BE
NOTE - the binding energies (BE) of energy levels in solids are conventionally measured
with respect to the Fermi-level of the solid, rather than the vacuum level.
This involves a small correction to the equation given above in order to account for the
work function () of the solid, but for the purposes of the discussion below this
correction will be neglected.

 The Binding Energy (BE) is characteristic of the core electrons for

each element.
 The BE is determined by the attraction of the electrons to the nucleus.
 If an electron with energy x is pulled away from the nucleus, the attraction between the
electron and the nucleus decreases and the BE decreases.
 Eventually, there will be a point when the electron will be free of the nucleus.

This is the point with 0 energy

of attraction between the
electron and the nucleus. At
this point the electron is free
0 B.E. from the atom.
10/30/2023
x
These electrons are
p+ attracted to the proton
with certain binding
energyx
13 Why the Core Electrons?

• An electron near the Fermi level is far from the nucleus, moving in different directions all over the
place, and will not carry information about any single atom.

– Fermi level is the highest energy level occupied by an electron ina neutral solid at absolute 0
temperature.

– Electron binding energy (BE) is calculated with respect to the Fermi level.

• The core e-s are local close to the nucleus and have binding energies characteristic of their particular
element.

• The core e-s have a higher probability of matching the energies of AlK and MgK X rays.

Valence e-

Atom
Core e-

10/30/2023
14 XPS Spectra

1. Characteristic binding energy associated with each core atomic

orbital i.e. each element will give rise to a characteristic set of
peaks in the photoelectron spectrum at kinetic
energies determined by the photon energy and the
respective binding energies.
2. The presence of peaks at particular energies therefore
indicates the presence of a specific element in the sample
under study.
3. The intensity of the peaks is related to the concentration of the
element within the sampled region. (quantitative analysis of the
surface composition).

10/30/2023
15 KE versus BE

KE = hv – BE - Ø

KE can be plotted depending on BE

# of electrons

Each peak represents the amount of e-s at a certain

energy that is characteristic of some element

BE increase from right to left

1000 eV 0 eV
E E E
Binding energy
(eV) KE increase from left to right

XPS Spectrum

• The XPS peaks are sharp.

• In a XPS graph it is possible to see Auger electron peaks.

• The Auger peaks are usually wider peaks in a XPS spectrum.

• Aluminum foil is used as an example on the next slide. 10/30/2023

16
Identification of XPS Peaks

• The plot has characteristic peaks

XPS Spectrum for each element found in the
surface of the sample.

• There are tables with the KE and

BE already assigned to each
element.

• After the spectrum is plotted you

can look for the designated
value of the peak energy from
the graph and find the element
present on the surface.

10/30/2023
17 X-rays vs. e- Beam

• X-Rays
– Hit all sample area simultaneously permitting data acquisition that will
give an idea of the average composition of the whole surface.

• Electron Beam
– It can be focused on a particular area of the sample to determine the
composition of selected areas of the sample surface.

10/30/2023
18 XPS Technology

• Consider as nondestructive.
– because it produces soft x-rays to induce photoelectron emission
from the sample surface

• Provide information about surface layers or thin film structures

• Applications in the industry:

– Polymer surface
– Catalyst
– Corrosion
– Adhesion
– Semiconductors
– Dielectric materials
– Electronics packaging
– Magnetic media
– Thin film coatings

10/30/2023
19 How Does XPS Technology Work?

• A monoenergetic x-ray beam emits photoelectrons from the surface of the

sample.
• The penetration of the x-ray photons about a micrometer of the sample
• The XPS spectrum contains information only about the top 10 - 100 Ǻ
thickness of the sample.
• Ultrahigh vacuum environment to eliminate excessive surface
contamination.
• Cylindrical Mirror Analyzer (CMA) or hemispherical sector analyzer

(HSA) measure the KE of emitted e s.-

• The spectrum plotted by the computer from the analyzer signal.

• The binding energies can be determined from the peak positions and the
elements present in the sample identified.
10/30/2023
20 Instrumentation: COMPONENTS OF XPS

 A source of X-rays
 An ultra high vacuum (UHV)
 An electron energy analyzer
 magnetic field shielding
 An electron detector system
 A set of stage manipulators

10/30/2023
21

The basic requirements:

• A source of fixed-energy radiation (an x-ray source).
• An electron energy analyzer (which can disperse the emitted electrons
according to their kinetic energy, and thereby measure the flux of emitted
electrons of a particular energy).
• A high vacuum environment (to enable the emitted photoelectrons to be
analyzed without interference from gas phase collisions).

10/30/2023
22

10/30/2023
23 Diagram of the Side View of XPS System

10/30/2023
24 X-Ray Sources
• Irradiate the sample surface, hitting the core electrons (e-) of the
atoms.

• The X-Rays penetrate the sample to a depth on the order of a

micrometer.
• Useful e- signal is obtained only from a depth of around 10 to 100 Ǻ
on the surface.

• Normally, the sample will be radiated with photons of a single

energy (MgK or AlK).

• This is known as a monoenergetic X-Ray beam.

• The X-Ray source produces photons with certain
energies:
– MgK photon with an energy: hn = 1253.6 eV
– AlK photon with an energy :h n = 1486.6 eV

The emitted photoelectrons will therefore have kinetic energies in the

range of ca. 0 - 1250 eV or 0 - 1480 eV 10/30/2023
25 The X-ray source for XPS:

• In contrast to the electron source, the X-ray source energy

depends on the choice of the anode material, resulting in the
availability of a number of discrete energies rather than a
continuous variation of the energy, as exists for electron and ion
guns.
• The photon energy must be sufficiently high to excite intense
photoelectron peaks from all elements of the periodic table.
• For XPS analysis, it is very important to consider the energy
resolution of the primary X-rays.

10/30/2023
26 Sample Preparation & Surface Damage in XPS

1. Any Sample that is vacuum stable can be analyzed by XPS.

2. Sample containing volatile components can be cooled to low

temp. to avoid devolatilization
3. Normally, Solid materials, such as metals ceramics & polymer,
are fairly stable under X-ray irradiation and damage caused by X-
ray is minimal during a typical XPS experiment
4. Films, plaques ‫الواح‬or powders can be mounted on a sample
holder with a double-sided sticky tap of low volatility first and then
examined as bulk samples.

10/30/2023
27

5. Certain Polymer & Biological samples would undergo some

chemical changes under prolonged X-ray exposures in an XPS
experiment. Examples are: PTFE, PVC, PVA, especially., when
the materials are in thin films.
6. To minimize the damage, the exposure time should be as short
as possible, and the samples are cooled to low temperatures.
7. The causes for the XPS induced damage include: secondary
electrons generated at X-ray source & impinging on the polymer
or biological sample surface.

10/30/2023
28

XPS Instrument

The XPS is controlled by using a computer system.

The computer system will control the X-Ray type
and prepare the instrument for analysis.

10/30/2023
29

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30

10/30/2023
31 Chemical Shifts
The exact binding energy of an electron depends not only upon the
level from which photoemission is occurring, but also upon :
1) The formal oxidation state of the atom.
2) The local chemical and physical environment.

Changes in either (1) or (2) give rise to small shifts in the peak
positions in the spectrum - so-called chemical shifts .
Atoms of a higher positive oxidation state exhibit a higher binding
energy due to the extra coulombic interaction between the photo-
emitted electron and the ion core.

10/30/2023
32 • The shifts are typically a few to 10 eV or more, and therefore
detectors with a high energy resolution are used.
• To subtract chemical information , it is imperative to
determine peak positions as accurately as possible.
• The line of interest is preferentially evoked ‫ایضاح‬by means
of a monochromatic X-ray source, and recorded with the highest
possible energy resolution.
• When dealing with small chemical shifts, overlapping peaks may
anyway occur in the spectra.
• Peak deconvolution ‫فك التداخل‬and peak fitting tools are available in
the commercial data handling systems.

10/30/2023
33
• The capability to distinguish between different chemical
states is the main characteristic of XPS.

• Due to this, another acronym is in use for this technique: ESCA,

which stands for ‘Electron Spectroscopy for Chemical Analysis’.

10/30/2023
34

10/30/2023
35 Chemical Shifts- Electronegativity Effects

10/30/2023
 Element At % C 1s
2,0x10
5 O1s
C 58.5 Raw
O 37.6 Fitted
N 3.9 284.8eV, C-C
36 5 286.3eV, C-O/C-N

Intensity (a.u.)
1,5x10
288.2eV, C=O
Intensity
289.2eV, O-C=O

5 C1s
1,0x10

N1s
4
5,0x10

0,0
1000 800 600 400 200 0 294 291 288 285 282

Binding Energy (eV) Binding Energy (eV)

O 1s N 1s
Raw Raw
Fitted Fitted
531.8eV, O=C 399.8eV, amine
Pyridinic-N

Intensity (a.u.)
533 eV, HO-C, C-O-C
Intensity (a.u.)

401.4, Pyrrolic N

542 540 538 536 534 532 530 528 526 410 405 400 395 390
10/30/2023
Binding Energy (eV)
Binding Energy (eV)

XPS spectra of CNDs from olive solid wastes

37

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38

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39

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40

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