Surface Spectroscopy

CHE-524

MS-I and MS-II

 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:

❑ Scanning Probe Microscopy (STM/AFM).

Scanning Tunneling Microscopy
Scanning tunneling microscope work on quantum tunneling
effect.

“Particle having energy less than “energy barrier” cross the

barrier”
➢ The name of the technique arises from the quantum mechanical tunnelling-type
mechanism by which the electrons can move between the tip and
substrate.

➢ Quantum mechanical tunnelling permits particles to tunnel

through a potential barrier which they could not surmount
according to the classical laws of physics
➢ When electric potential difference is applied between the tip and
sample, electrons from the sample tunnel to the tip.

➢ This small current produced by the tunneling electrons is

amplified and send to the computer to prepare the image.

The magnitude of tunneling current depends in the distance

between the tip and the sample.
Scanning Tunneling Microscopy

The interaction that is monitored in :

➢ STM - is the tunnelling current between a metallic tip and a
conducting substrate which are in very close proximity
but not actually in physical contact.
➢ AFM - is the van der Waals force between the tip and the surface; this
may be either the short range repulsive force (in contact-mode) or the
longer range attractive force (in non-contact mode).
 ➢ In this model, the probability of tunnelling is exponentially-
dependent upon the distance of separation between the tip and
surface

➢ The tunnelling
current is therefore
a very sensitive
probe of this
separation.

Imaging of the surface topology may then be carried out in one of two
ways:
1) In constant height mode (in which the tunnelling current is monitored as
the tip is scanned parallel to the surface)

2) In constant current mode (in which the tunnelling current is maintained

constant as the tip is scanned across the surface; takes more time since the tip
has to go up and down again and again)
Constant height Mode
➢ If the tip is scanned at what is nominally a constant height above
the surface, then there is actually a periodic variation in the
separation distance between the tip and surface atoms.

➢ At one point the tip will be directly above a surface atom and
the tunnelling current will be large

➢ whilst at other points the tip will be above hollow sites on the
surface and the tunnelling current will be much smaller.
“A plot of the tunnelling current v's tip position”

therefore shows a periodic variation which matches that of the

surface structure - hence it provides a direct "image" of the surface
(and by the time the data has been processed it may even look like a real
picture of the surface !).

In practice, however, the normal way of imaging the surface is to maintain the
tunnelling current constant whilst the tip is scanned across the surface. This is
achieved by adjusting the tip's height above the surface so that the tunnelling
current does not vary with the lateral tip position. In this mode the tip will
move slightly upwards as it passes over a surface atom, and conversely, slightly
Constant current Mode
➢ In practice, however, the normal way of imaging the surface is to
maintain the tunnelling current constant whilst the tip is scanned
across the surface.
➢ This is achieved by adjusting the tip's height above the surface so
that the tunnelling current does not vary with the lateral tip
position.

In this mode the tip will move slightly upwards as it passes over a surface
atom, and conversely, slightly in towards the surface as it passes
over a hollow.

Tip of single atom

Constant height Mode

Tip of single atom

The image is then formed by plotting the tip height (strictly,

the voltage applied to the z-piezo) v's the lateral tip position.
For the techniques to provide information on the surface structure at the atomic
level

1) The position of the tip with respect to the surface must be very accurately
controlled (to within about 0.1 Å) by moving either the surface or the tip.
2) The tip must be very sharp - ideally terminating in just a single
atom at its closest point of approach to the surface.
Let us look at the region where the tip approaches the surface in greater
detail ....
 Magnification

and if we now go down to the atomic scale ....

Magnification

Tip of single atom

a truly atomic tip

STM images

The silicon atoms on the surface of a

crystal of silicon carbide (SiC). Image
obtained using an STM
STM invention

➢ The invention of the scanning

tunneling microscope (STM) in 1981
allowed

➢ scientists to view the world from an

atomic perspective for the first time.

➢ The revolutionary microscope, for

which two IBM researchers Gerd
Binnig and Heinrich Rohrer
received the 1986 Nobel Prize in
physics, revealed the topography of
surfaces, atom by atom.
 https://www.youtube.com/watch?v=FQzUrb
KTLVU

https://www.youtube.com/watch?v=P4ywnN0htQI
Q. Explain the basic principles of quantum tunneling through a
potential barrier.

Q. Calculate the tunneling probability for a particle of mass m and

energy E that encounters a potential barrier of height U0 and width

Q. Describe the operating principles of a scanning tunneling

microscope.

Q. Explain the role played by quantum tunneling in a field emission

electrode, anodic etching, alpha decay, and nuclear fusion, and
describe the analogy between quantum tunneling and evanescent
waves.

Name two scanning probe instruments.

How Does the Scanning Tunneling Microscope (STM) Work?
The STM doesn’t work the way a conventional microscope does - it
doesn’t magnify a sample until it is big enough to see with an
unaided eye. Instead, a fine needlelike tip that is electrically
conductive is scanned just above the surface of an electrically
conductive sample. The distance between the tip and the sample is
only a few Angstroms (a nanometer is 10 times bigger than an
Angstrom). When a tiny voltage is applied, the rules of quantum
mechanics allow electrons to jump - or “tunnel” - across the space
between tip and sample. Though very small, the flow of electrons
can be detected easily. As the tip moves along the surface of the
sample, the tip’s position is constantly adjusted to make sure the
distance (and hence, the electrical current) remains constant. These
adjustments trace the surface features of the sample. When the
features are graphically displayed on a computer screen, it is possible
to “see” the individual atoms and molecules that make up the
sample.
Scanning tunneling microscopes (STMs)
Among the newest electron microscopes, STMs were invented by Gerd Binnig
and Heinrich Rohrer in 1981. Unlike TEMs, which produce images of the
insides of materials, and SEMs, which show up 3D surfaces, STMs are designed
to make detailed images of the atoms or molecules on the surface of something
like a crystal.

They work differently to TEMs and SEMs too: they have an extremely sharp
metallic probe that scans back and forth across the surface of the specimen. As
it does so, electrons try to wriggle out of the specimen and jump across the gap,
into the probe, by an unusual quantum phenomenon called "tunneling." The
closer the probe is to the surface, the easier it is for electrons to tunnel into it,
the more electrons escape, and the greater the tunneling current.

The microscope constantly moves the probe up or down by tiny amounts to

keep the tunneling current constant. By recording how much the probe has to
move, it effectively measures the peaks and troughs of the specimen's surface.
A computer turns this information into a map of the specimen that shows up
its detailed atomic structure.
Scanning tunneling microscopes (STMs)
One big drawback of ordinary electron microscopes is that they produce
amazing detail using high-energy beams of electrons, which tend to damage the
objects they're imaging. STMs avoid this problem by using much lower energies.
How an STM works:
1) The sample (blue) is sealed inside a vacuum chamber. 2) The chamber is
cooled down to almost absolute zero by a cryogenic source, such as a liquid
helium refrigerator.

3) A pump creates a very high

vacuum in the chamber. 4) The
sample being scanned serves as
one electrode.

5) The probe tip, an incredibly small

distance above, serves as the other
electrode. The two electrodes can be
scanned past one another by a drive
that moves in three dimensions.
6) The tunneling current output
from the probe is analyzed by a
measuring device.
How an STM works:
7) Results can be displayed on a screen or plotter, showing up (in this case) the
pattern of atoms on the surface of the sample.
Atomic Force Microscopy (AFMs)

➢ If you STMs are amazing, AFMs (atomic force

think
microscopes), also invented by Gerd Binnig, are even better!

➢ One of the big drawbacks of STMs is that

they rely on electrical currents (flows of electrons) passing through
materials, so they can only make images of conductors.

➢ AFMs don't suffer from this problem because, although they use
still tuneling, they don't rely on a current flowing between
the specimen and a probe, so we can use them to make atomic-
scale images of materials such as plastics, which don't conduct
electricity.
Atomic Force Microscopy (AFMs)

➢ An AFM is a microscope with a little arm called a cantilever with a

tip on the end that scans across the surface of a specimen.

➢ As the tip sweeps across the surface, the force between the atoms
from which it's made and the atoms on the surface
constantly changes, causing the cantilever to bend by minute
amounts.

➢ The amount by which the cantilever bends is detected by bouncing a

laser beam off its surface. By measuring how far the laser beam travels,
we can measure how much the cantilever bends and the forces acting on
it from moment to moment, and that information can be used to figure
out and plot the contours of the surface. Other versions of AFMs (like
the one illustrated here) make an image by measuring a current that
"tunnels" between the scanning tip and a tunneling probe mounted just
behind it. AFMs can make images of things at the atomic level and they
can also be used to manipulate individual atoms and molecules—one of
Atomic Force Microscopy (AFMs)

➢ An AFM is a microscope with a little arm called a cantilever with a

tip on the end that scans across the surface of a specimen.

➢ As the tip sweeps across the surface, the force between the atoms
from which it's made and the atoms on the surface
constantly changes, causing the cantilever to bend by minute
amounts.

➢ The amount by which the cantilever bends is detected by bouncing a

laser beam off its surface.

➢ By measuring how far the laser beam travels, we can measure how
much the cantilever bends and the forces acting on it from moment to
moment, and that information can be used to figure out and plot the
contours of the surface.
➢ The atomic force microscope (AFM) probe is mounted onto a
flexible cantilever that is manipulated by a vertical piezoelectric into
interacting with the sample.
➢ The piezoelectric expands and exerts a force on the cantilever
proportional to the potential voltage.
➢ The force is balanced by those acting on the probe by its interaction
with the surface and the stain on the cantilever.
A Pizoelectric materials where if you apply a voltage it will deform
the crystal in it and if u apply a known voltage the crystals contract
and expands by some known amount and that how you can control
the matter of the cantilever.
AFM: How it works?

➢ The specimen to be
scanned (1) is
mounted on a drive
mechanism (2) that
can move it in three
dimensions.

➢ To prevent unwanted vibrations, that mechanism is fixed to a rubber

cushion (3) mounted on a firm aluminum base (4), which is further
cushioned by multiple layers of aluminum plates and rubber pads (not
shown).
➢ To create an image, the specimen is slowly moved around the sharp,
fixed imaging point (5), which is mounted on a spring cantilever made
of thin gold foil (6), attached to a piezoelectric crystal (7), and fixed to
the same aluminum base.
AFM: How it works?
At the other end of
the apparatus, a
tunneling probe (8) is
moved very close (to
within about 0.3nm)
of the spring
cantilever by a second
drive mechanism (9),
isolated by another
rubber cushion (10).

As the sample (1) moves around the imaging point (5), the current that
tunnels between the spring cantilever (6) and the tunneling tip (8) is
constantly measured. These measurements are converted into data that can
be used to draw a detailed surface map of the specimen.
 “ Wavelength”

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 7 x 10-7 metres for red to
about 4 x 10-7 metres for violet. Electrons in a typical electron microscope have
wavelengths measured in picometres. One picometre is 10-12 of a metre,
meaning that electron microscopes can resolve things hundreds of thousands
of times smaller than optical microscopes

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.
.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).
Scanning Electron Microscope: SEM
➢ Conventional scanning electron
microscopy depends on the
emission of secondary electrons
from the surface of a specimen.

➢ Because of its great depth of

focus, a scanning electron
microscope is the EM analog
of a stereo light microscope.

➢ 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.
Scanning Electron Microscope: SEM
How does SEM Works
Generation of electrons: Thermoionic emission
Acceleration of electrons: Anode
Electromagnetic lenses
Sample Chamber
Signals from the Samples
http://virtual.itg.uiuc.edu/training/EM_tutorial/
Electron microscopes use signals arising from the interaction of an electron
beam with the sample to obtain information about structure,
morphology, and composition.
1.The electron gun generates electrons.
2.Two sets of condenser lenses focus the electron beam on the specimen and
then into a thin tight beam.
3.To move electrons down the column, an accelerating voltage (mostly
between 100 kV-1000 kV) is applied between tungsten filament and anode.
4.The specimen to be examined is made extremely thin, at least 200 times
thinner than those used in the optical microscope. Ultra-thin sections of 20-
100 nm are cut which is already placed on the specimen holder.
5.The electronic beam passes through the specimen and electrons are
scattered depending upon the thickness or refractive index of different parts
of the specimen.
6.The denser regions in the specimen scatter more electrons and therefore
appear darker in the image since fewer electrons strike that area of the screen.
In contrast, transparent regions are brighter.
7.The electron beam coming out of the specimen passes to the objective lens,
which has high power and forms the intermediate magnified image.
8.The ocular lenses then produce the final further magnified image.
“ Wavelength”
Parts of Electron microscope
EM is in the form of a tall vacuum column which is vertically mounted. It has
the following components:
1.Electron gun
•The electron gun is a heated tungsten filament, which generates electrons.
2.Electromagnetic lenses
•Condenser lens focuses the electron beam on the specimen. A second condenser
lens forms the electrons into a thin tight beam.
•The electron beam coming out of the specimen passes down the second of magnetic
coils called the objective lens, which has high power and forms the intermediate
magnified image.
•The third set of magnetic lenses called projector (ocular) lenses produce the final
further magnified image.
•Each of these lenses acts as an image magnifier all the while maintaining an
incredible level of detail and resolution.
3.Specimen Holder
•The specimen holder is an extremely thin film of carbon or collodion held by a metal
grid.
4.Image viewing and Recording System.
•The final image is projected on a fluorescent screen.
https://www.youtube.com/watch?v=d7ch1X
SmOgI
 Principle of Light Microscope

http://virtual.itg.uiuc.edu/training/LM_tutoria
l/
http://virtual.itg.uiuc.edu/training/AFM_tutor
ial/
https://www.youtube.com/watch?v=ljTEG-B-kGc
https://www.slideshare.net/drbhargava5745
/scanning-electron-microscopy-sem-lecture
Basic Principle
Auger electron spectroscopy (AES) uses the energy of emitted electrons to
identify the elements present in a sample, similar to XPS.

The main difference is that XPS uses an X-ray beam to eject an

electron while AES uses an electron beam to eject an electron.

Like XPS, AES measures the kinetic energy (Ek) of an electron to determine
its binding energy (Eb). The binding energy can be found from eq. 1, ΔΦ is
the difference in work function between the sample and the detector material.

Eb = hν − Ek + ΔΦ (1)

Since the Eb is dependent on the element and the electronic environment of

the nucleus, AES can be used to distinguish elements and their oxidation
states. For instance, the energy required to remove an electron from Fe3+ is
more than in Fe0. Therefore, the Fe3+ peak will have a lower Ek than the Fe0
peak, effectively distinguishing the oxidation states.
The basic Auger process:

Schematic diagram of the Auger Process

First, an electron beam comes in with sufficient energy to eject a core electron
creating a vacancy ( Figure a).

A secondary electron (imaging electron) of higher energy drops down to fill the
vacancy (see Figure b) and emits sufficient energy to eject a tertiary electron
(Auger electron) from a higher shell (see Figure c).
The shells from which the
electrons move from lowest
to highest energy are
described as the K shell, L
shell, and M shell.

The K shell represents the 1s

orbital, the L shell represents
the 2s and 2p orbitals, and
the M shell represents the 3s,
3p, and 3d orbitals.

Movement of an L shell electron into the K shell vacancy.

Then, either an L shell electron or M shell electron is ejected.

The peak seen in the spectrum is labeled according to the shells involved in the
movement of the electrons. For example, an electron ejected from a gold atom
could be labeled as Au KLL or Au KLM.
The intensity of the peak depends on the amount of material present, while
the peak position is element dependent.
Auger transitions characteristic of each elements can be found in the
literature.
https://www.yourarticlelibrary.com/microeco
nomics/working-principle-of-a-electron-
microscopes-with-diagram/26479
Primary Electron Emission

– Core Electrons absorb incoming X-ray’s kinetic energy

– If incoming KE > electron’s binding energy
• Electron leaves sample and enters vacuum
– Due to photoelectric effect
– Called a photoelectron
L2,3 or 2p

L1 or 2s

X-ray
Photoelectron

K or 1s
Secondary Electron Emission (Auger Electron)
– Low Energy “hole” produced
– High Energy electron fills hole
– Secondary Electron can absorb excess energy
and enter vacuum
Auger
• Called Auger Electron
Electron

L2,3 or 2p

L1 or 2s

K or 1s
Auger Electron Spectroscopy (Auger spectroscopy or AES) was developed in the
late 1960's , deriving its name from the effect first observed by Pierre Auger, a
French Physicist, in the mid-1920's. It is a surface specific technique utilising
the emission of low energy electrons in the Auger process and is one of the
most commonly employed surface analytical techniques for determining the
composition of the surface layers of a sample.
 The Auger Process & Auger Spectroscopy
The Auger process is illustrated using the K, L1 & L2,3 levels. These could be
the inner core levels of an atom in either a molecular or solid-state
environment.
I. Ionization
The Auger process is initiated by creation of a core hole - this is typically
carried out by exposing the sample to a beam of high energy electrons
(typically having a primary energy in the range 2 - 10 keV). Such electrons
have sufficient energy to ionise all levels of the lighter elements, and higher
core levels of the heavier elements.
In the diagram above, ionisation is shown to occur by removal of a K-shell
electron, but in practice such a crude method of ionisation will lead to ions with
holes in a variety of inner shell levels.
In some studies, the initial ionisation process is instead carried out
using soft x-rays ( 1000 - 2000 eV ). In this case, the acronym XAES is
sometimes used. As we shall see, however, this change in the method of
ionisation has no significant effect on the final Auger spectrum.
II. Relaxation & Auger Emission
The ionized atom that remains after the removal of the core hole electron is,
of course, in a highly excited state and will rapidly relax back to a lower
energy state by one of two routes :

X-ray fluorescence , or Auger emission

We will only consider the latter mechanism, an example of which is illustrated
schematically below ....
In this example, one electron falls from a higher level to fill an
initial core hole in the K-shell and the energy liberated in this
process is simultaneously transferred to a second electron ;
a fraction of this energy is required to overcome the binding energy of this
second electron,
the remainder is retained by this emitted Auger electron as kinetic energy.

In the Auger process illustrated, the final state is a doubly-ionized atom with
core holes in the L1 and L2,3 shells.
Experimental Setup:

Important elements of an Auger spectrometer include a vacuum system, an

electron source, and a detector. AES must be performed at pressures less than
10-3 pascal (Pa) to keep residual gases from adsorbing to the sample surface.
This can be achieved using an ultra-high-vacuum system with pressures from
10-8 to 10-9 Pa.
Experimental Setup:

Typical electron sources include tungsten filaments with an electron beam

diameter of 3 - 5 μm, LaB6 electron sources with a beam diameter of less than
40 nm, and Schottky barrier filaments with a 20 nm beam diameter and high
beam current density. Two common detectors are the cylindrical mirror
analyzer and the concentric hemispherical analyzer discussed below. Notably,
concentric hemispherical analyzers typically have better energy resolution.
Limitations
While AES is a very valuable surface analysis technique, there are limitations.

1) Because AES is a three-electron process, elements with less than three

electrons cannot be analyzed. Therefore, hydrogen and helium cannot be
detected.

2) The numerous transition peaks in heavier elements can cause

peak overlap, as can the increased peak width of higher energy transitions.
3) Another limitation is sample destruction. Although focusing of the
electron beam can improve resolution; the high-energy electrons can destroy
the sample.
4) Furthermore, charging of the electron beam on insulating
samples can deteriorate the sample and result in high-energy
peak shifts or the appearance of large peaks.
Q.
Q
We can make a rough estimate of the KE of the Auger electron from the binding
energies of the various levels involved. In this particular example,

KE = ( EK - EL1 ) - EL23

The expression for the energy can also be re-written in the form :

KE = EK - ( EL1 + EL23 )

It should be clear from this expression that the latter two energy terms could be
interchanged without any effect - i.e. it is actually impossible to say which electron
fills the initial core hole and which is ejected as an Auger electron ; they are
indistinguishable.

An Auger transition is therefore characterized primarily by :-

1.the location of the initial hole
2.the location of the final two holes
although the existence of different electronic states (terms) of the final doubly-ionized
atom may lead to fine structure in high resolution spectra.
When describing the transition, the initial hole location is given first, followed by the
locations of the final two holes in order of decreasing binding energy.
i.e. the transition illustrated is a KL1L2,3 transition .
If we just consider these three electronic levels there are clearly several possible Auger
transitions : specifically,

K L2,3
K L1 L1 K L1 L2,3
L2,3

In general, since the initial ionisation is non-selective and the initial hole may therefore
be in various shells, there will be many possible Auger transitions for a given element -
some weak, some strong in intensity. AUGER SPECTROSCOPY is based upon the
measurement of the kinetic energies of the emitted electrons. Each element in a sample
being studied will give rise to a characteristic spectrum of peaks at various kinetic
energies.
This is an Auger spectrum of Pd metal - generated using a 2.5 keV electron beam to
produce the initial core vacancies and hence to stimulate the Auger emission process.
The main peaks for palladium occur between 220 & 340 eV. The peaks are situated on
a high background which arises from the vast number of so-called secondary electrons
generated by a multitude of inelastic scattering processes.
Auger spectra are also often shown in a differentiated form : the reasons for this are
partly historical, partly because it is possible to actually measure spectra directly in this
form and by doing so get a better sensitivity for detection. The plot below shows the
same spectrum in such a differentiated form.