2018-19 session

CHE 524 (Surface Chemistry and Spectroscopy)

3 hours/week; 3.00 credits
1.Surface Sensitivity & Surface Specificity: General Sensitivity Problems, surface
sensitive technique, Inelastic Mean Free Path (IMFP) of electrons, UHV (Ultra High
Vacuum (UHV), Effects of Gas Pressure.
2.Adsorption of Molecules on Surfaces: Kinetics of adsorption, Adsorption Isotherms,
Langmuir, Hinshelwood, BET, Tempkin, Elley-Rideal etc. Adsorption with dissociation,
Competitive adsorption, Non ideal adsoroption Thermodynamics and statistical
mechanics of adsorption.
3.Surface reactions: Unimolecular surface reactions, Inhibition and Activation.
Bimolecular surface reactions, Reactions between two adsorbed molecules, Reaction
between a adsorbed molecule and a gas molecule, Adsorption of two gases without
mutual displacement, Inhibition, Activation Energies.
4. Surface Analytical Techniques: Auger Electron Spectroscopy (AES); Principle,
instrumentation, application. X-ray Photoelectron Spectroscopy (XPS); Principle,
instrumentation, application. Infra red Spectroscopy; IR Spectroscopy of various forms,
e.g. RAIRS, MIR, Electron Energy Loss Spectroscopy (EELS), Applications of
Vibrational spectroscopy, LEED (low energy electron diffraction); principles and
application, NEXAFS Near edge X-ray absorption fine structure analysis; basic
principle and application.
5.Surface Imaging and Depth Profiling: Basic Concepts in Imaging & Localised
Spectroscopy, Electron Microscopy (SEM & TEM), Imaging XPS, SIMS Imaging &
Depth Profiling, Auger Depth Profiling, Scanning Probe Microscopy (STM/AFM).
5. Surface Imaging and Depth Profiling:

❑ Basic Concepts in Imaging & Localised Spectroscopy,

❑ Electron Microscopy (SEM & TEM),
❑ Imaging XPS,
❑ SIMS Imaging & Depth Profiling,
❑ Auger Depth Profiling,
❑ Scanning Probe Microscopy (STM/AFM).
Surface Spectroscopy

CHE-524

MS-I and MS-II

Resolving Power/ Resolution
In order to compare the electron microscope with the light microscope, we
need to know what factors control the resolution (often called resolving
power) which is define as

The closet spacing of two points which can clearly be seen

through the microscope to be separate entities.

➢ A human eye cannot distinguish objects smaller than

200 μm (0.2 mm). In other words, the resolution
of a human eye is 200 μm, while,

➢ a light microscope can typically magnify images up

to 1000× to resolve details down to 0.2 μm. ... Thus 0.2
μm can be defined as the resolution limit of the
light microscope.
➢ The following equation can be used to determine the typical
magnification of a microscope:

➢ For a light microscope, useful magnification is therefore

➢ For electron microscope, useful magnification is there

Principle of Electron Microscope

An electron microscope is a microscope that uses a beam of

accelerated electrons as a source of illumination.
Principle of Electron Microscope
➢ It is a special type of microscope having a high resolution of
images, able to magnify objects in nanometres, which are
formed by controlled use of electrons in vacuum captured on a
phosphorescent screen.

Ernst Ruska (1906-1988)

German engineer and academic
professor, built the first Electron
Microscope in 1931, and the same
principles behind his prototype still
govern modern EMs.

Nobel Prize
in Physics in
1986 for this
work.
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Electron microscopes use signals arising from the interaction of an
electron beam with the sample to obtain information about
structure, morphology, and composition.
Light Microscopy vs. Electron Microscopy
➢ Light microscopy used optical
lenses to focus light.

➢ Electron microscopy is also limited

by the wavelength of electrons.
(wave/particle duality). But since
the wavelength of electrons is
so small, sub-atomic resolution The image is for gold
particles. Atoms can
can be obtained. This is the main ben seen.
advantage of electron microscopy.

➢ The ultimate resolution of

light microscopy is limited
by the wavelength of light,
400-700 nm.
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Wavelength
Long wavelength waves gently lift Mallard up and down but continue
undisturbed by his presence. Phyllis, flying over the other side of the pond and
detecting the waves, would not be able to tell that Mallard was in the way. In
other words, long wavelength waves do not reflect off Mallard.

When the wavelength gets smaller, Mallard is tossed about more

violently because shorter wavelength waves carry more energy. The waves
themselves are modified by Mallard's presence and this time Phyllis would be
able to tell that Mallard, or something, is out there on the pond.

http://physik.uibk.ac.at/hephy/
CERN_PPE20/accelerators/m
ain-2.html
Wavelength Type text here

➢ It's just the same when it comes to tiny things. The smaller the
object we want to study, the shorter the wavelength and the
higher the energy of the probe we need to use.

➢ Electrons in an electron microscope have shorter wavelengths

than visible light, which is why they can resolve smaller things.

➢ Visible light has wavelengths ranging

from about (700-400 nm).

➢ Electrons in a typical electron

microscope have wavelengths
measured in picometres (1 pm= 10-12
m). Electrons have wavelengths of
0.005 nm).
Electron microscopes can resolve things hundreds of thousands of
times smaller than optical microscopes
Wavelength
Electron microscopes can resolve atoms, which are about 10-10 metres
across. To get a glimpse of what is inside a proton, which is about 10-
15 metres across, a wavelength of 10-16 metres would be needed.

Theoretically, the maximum resolution of the EM is 0.005 nm which is

less than the diameter of a single atom, or 40,000 times the resolution
of the light microscope and 2 million times that of the naked eye.
However, the practical resolution of modern EM is of 0.1 nm (1 A).

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Wavelength and Resolution
Louis de Broglie showed that every particle or matter propagates
like a wave. The wavelength of a particle or a matter can be calculated as
follows.

where λ is the wavelength of a particle, h is Planck’s constant (6.626 x 10-34 J

seconds), and p is the momentum of a particle. Since the momentum is the
product of the mass and the velocity of a particle,

Because the velocity of the electrons is determined by the

accelerating voltage, or electron potential where

The velocity of electrons can be calculated by

Therefore, the wavelength of propagating electrons at a given
accelerating voltage can be determined by

mass of an electron = 9.1 x 10-31 kg and e (charge) = 1.6 x 10-19coloumbs

Thus, the wavelength of electrons is calculated to be 3.88 pm when

the microscope is operated at 100 keV, 2.74 pm at 200 keV, and 2.24
pm at 300 keV.
However, because the velocities of electrons in an electron microscope reach
about 70% the speed of light with an accelerating voltage of 200 keV, there are
relativistic effects on these electrons. These effects include significant length
contraction, time dilation, and an increase in mass. By accounting for these
changes,
 where c is the speed of light, which is ~3 x 108 m/s. Therefore, the
wavelength at 100 keV, 200 keV, and 300 keV in electron microscopes is 3.70
pm, 2.51 pm and 1.96 pm, respectively.

The wavelength of electrons is much smaller than that of

photons (2.5 pm at 200 keV). Thus the resolution of an electron
microscope is theoretically unlimited for imaging cellular structure or
proteins.

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Scanning Electron Microscope Type text here

➢ Scanning electron microscope is a microscope that uses electrons

rather than light to form an image.
Scanning Electron Microscope: SEM
➢ Conventional scanning electron
microscopy depends on the
emission of secondary
electrons from the surface
of a specimen.

➢ It is termed a scanning
electron microscope
because the image is
formed by scanning a
focused electron beam
onto the surface of the
specimen in a raster
pattern (line-by-line
scanning). Type text here
Type text here
How does SEM Works?
➢ The electrons from the electron gun
pass through magnetic lens
(condenser lens) which focus
them to a spot, and then through
a scanning coil/objective lens
which bends the beam to the
spot on the sample we want to
image.

➢ By varying the current through the

scanning coils with time, the position
of the beam can be rastered.
➢ SEM images are not created all
at once. The beam is rastered in
a grid you specify, and for each
pixel in the grid, data is
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collected.
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Scanning Electron Microscope: SEM

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Scanning Electron Microscope: SEM
The signals used by a scanning electron microscope to produce an
image result from interactions of the electron beam with atoms at
various depths within the sample.

Various types of signals are produced including

➢ secondary electrons (SE),

➢ reflected or back-scattered electrons (BSE),
➢ characteristic X-rays and
➢ light (cathodoluminescence) (CL),
➢ and transmitted electrons.

Secondary electron detectors are standard equipment in all SEMs, but it is

rare for a single machine to have detectors for all other possible signals.
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