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by Spectroscopy
• The surface of a solid in contact with a liquid or gaseous phase usually differs
substantially from the interior of the solid both in chemical composition and
physical properties.
• Characterization of these surface properties is often importance in a number
of fields such as:
• semiconductor thin film technology,
• corrosion and adhesion mechanisms, and
• studies of the behavior and functions of biological membranes
Definition of a solid surface
Vacuum, gas, or liquid
Top layer of atoms or molecules
Boundary,
Several atomic Transition layer
layers deep (non‐uniform composition that varies continuously)
(part of the solid that
differs in composition
from the average bulk
composition of the bulk )
• Ordinarily, the difference in composition of surface layer does not significantly affect
the measured overall average composition of the bulk
• From practical standpoint, it appears best to adopt an operational definition of a
surface as that volume of the solid that a specific measurement technique samples
Types of surface measurements
• Classical methods provide information about the physical nature of surfaces but
less about their chemical nature
• Methods involve:
• Obtaining optical and electron microscopic images
• Measurement of adsorption isotherms,
• Surface areas,
• Surface roughness,
• Pore sizes, and
• Reflectivity.
• Beginning in the 1950’s spectroscopic surface methods began to appear that
provided information about the chemical nature of surfaces.
General Technique in Surface Spectroscopy
To spectrometer
From source
• Most effective surface methods are
those in which the primary beam,
Secondary beam
Primary beam secondary beam, or both is made up
(photons,
(photons, electrons, electrons, ions, or of either electrons, ions, or molecules
ions, or molecules) molecules) and not photons.
Sample Æ this limitation assures that the
measurements are restricted to the
surface.
Example:
Beam Maximum penetration depth
Electrons or ions (1 keV) 25 Å
Photon of same energy 10,000 Å
Surface Spectroscopic Methods
Six of the more widely used spectroscopic methods:
Regardless of the type of spectroscopic surface methods being used, three
types of sampling are employed:
1) Focusing primary beam on a single small area of the sample and observing
the secondary beam.
2) Mapping the surface, in which a region of the surface is scanned by moving
the primary beam across the surface in a raster pattern of measured
increments and observing changes in the secondary beam that result.
3) Depth profiling. A beam of ions is used to etch a hole in the surface by
sputtering. During the process a finer primary beam is used to produce a
secondary beam from the center of the hole, which provides the analytical
data on the surface composition as a function of depth.
Surface Contamination
• A frequently encountered problem is contamination by adsorption of components
of the atmosphere such as oxygen, water, and carbon dioxide.
• Even in vacuum, this type of contamination occurs in a relatively short time.
Pressure (torr) Time for monolayer formation
10‐6 3 seconds
10‐8 1 hour
10‐10 10 hours
• Cleaning may involve:
• Baking sample at high temperature
• Sputtering sample with inert gas ions
• Mechanical scrapping or polishing the surface with an abrasive
• Ultrasonic washing in various solvents
• Bathing sample in reducing atmosphere to remove oxides
• The primary beam itself can alter the surface as measurement progresses
X‐ray Photoelectron Spectroscopy (XPS)
• Pioneered by Swedish physicist K. Siegbahn (Nobel prize, 1981)
• Chose to call the technique electron spectroscopy for chemical analysis (ESCA)
• Because XPS provides information about:
‐ atomic composition
‐ structure and oxidation state
Fundamental difference between electron
spectroscopy and other types of
spectroscopy:
• In electron spectroscopy, the kinetic
energy of emitted electrons is
recorded.
• Thus, the spectrum consists of a plot of
the number of emitted electrons, or
the power of the electron beam, as a
function of the energy (or the
frequency or wavelength) of the
emitted electrons.
Principles of XPS
One of the photons of a monoenergetic x‐ray
Physical process: beam of known energy hv displaces an electron e‐
from a K orbital Eb :
A + hν → A +∗ + e −
where:
A can be an atom, a molecule, or an ion,
Outer shell or
valence
electrons A+* is an electronically excited ion with
a positive charge greater than that of A.
Kinetic energy of emitted electron Ek is
measured
The binding energy of the electron Eb is
then calculated by means of:
Eb = hv − Ek − w
inner shell
K and L
electrons
• Eb is a characteristic of the atom and orbital from
which the electron is emitted.
• w is the work function
Example of a low resolution or survey XPS spectrum:
• X‐ray spectrum of Tetrapropylammonium‐
diflouridethiophosphate
• Peaks are labeled according to the element and
orbital from which the emitted electron
originated
• Analyte consisted of an organic compound
made up of 6 elements
• Presence of oxygen – suggesting that some
surface oxidation of the compound
• Binding energy of 1s electrons increase with
atomic number (due to increase positive
charge of nucleus)
• More than one peak for a given
element can be observed e.g.
peaks for 2s and 2p electrons of
S and P
• Large background count arises because associated with each peak is a tail due to ejected
electrons that have lost part of their energy by inelastic collisions within the slid sample.
• These electrons have less kinetic energy than their non‐scattered counterparts and will thus
appear at lower kinetic energies or higher binding energies.
Instrumentation
(3)
(4)
Components of XPS spectrometer:
1. Source
2. Sample holder
3. Analyzer
4. Detector (5)
5. Signal processor and read‐out
XPS spectrometers generally require elaborate (2)
vacuum systems to reduce pressure in all of the
components to as low as 10‐5 to 10‐10 torr (1)
1. Sources:
• Simplest sources
o X‐ray tubes equipped with magnesium or aluminum targets with suitable
filters
o Kα lines for Mg and Al have considerably narrower bandwidths (0.8 to 0.9
eV) compared to higher atomic number elements
o Narrow bands Æ higher resolution
• Solid samples are mounted in a fixed position as close to the photon or electron
source and entrance slit as possible
• Gas samples are leaked into the sample area through a slit
‐‐ slit sizes are such that a pressure of perhaps 10‐2 torr
‐‐ higher pressures lead to excessive attenuation of electron beam due to
inelastic collisions
‐‐ on the other hand, if sample pressure is too low, weakened signals are
obtained.
3. Analyzers:
• Mostly hemispherical type
• Electron beam is deflected by an electrostatic magnetic field
• Electron travel in a curved path
• Radius of curvature is dependent upon
• Kinetic energy of electron beam, and
• Magnitude of the field
• By varying the field, electron of various kinetic energies can be focused on
the detector
• Typically, pressures in the analyzer are maintained at or below 10‐5 torr.
4. Transducers:
• Mostly based on solid‐state, channel electron multipliers
• These consist of tubes of glass that have been doped with lead or
vanadium
• When a potential of several kilovolts is applied
ÆA cascade or pulse of 106 to 108 electrons are produced for each incident
electron
• The pulses are then counted electronically
• 2‐D multi‐channel electron transducers are now available
Application of XPS
XPS (or ESCA) provides
• qualitative, and
• quantitative information about elemental composition of
matter
• Useful structural information
a) Qualitative Analysis
• A low‐resolution, wide‐scan XPS spectrum (called a survey spectrum)
serves as a basis for the determination of elemental composition of
samples
• With Mg or Al Kα source, all elements (except H and He) emit core
electrons having characteristic binding energies
• Typical spectrum encompasses a kinetic energy range of 250 to 1500 eV
‐‐ (correspond to binding energies of about 0 to 1250 eV)
• Peaks are well resolved
ÆUnambiguous identification (provided the element is present in
concentration > 0.1 %
• Overlapping peaks are resolved by investigating other spectral regions
for additional peaks
• Often peaks resulting from Auger electrons are found in XPS spectra
• Such peaks are readily identified by comparing spectra produced by two x‐ray
sources (usually Mg and Al Kα)
• Auger peaks remain unchanged on the kinetic energy scale while photoelectric
peaks are displaced.
b) Chemical shifts and oxidation states
• Examination of a peak under conditions of higher energy resolution,
ÆPosition of maximum is found to depend to a small degree upon the
chemical environment of the atom responsible for the peak
• That is, variations in the number of valence electrons, and the type of bonds
they form, influence the binding energies of core electrons
Effect of number of valance electrons (thus, oxidation states)
• Binding energies increases as oxidation state becomes more positive
• Explanation for this chemical shift:
• Assume that attraction of the nucleus for core electrons is diminished by presence of
outer electrons
• When one of these electrons is removed, the effective charge sensed for the core
electrons is increased Æ increase in binding energy
• One of the most important application of XPS ÆIdentification of oxidation states of elements
in inorganic compounds
c) Chemical shifts and structure
Effect of structure on the position of peaks for an element
• Each peak correspond to the 1s electron of the carbon atom
located directly above it in the structural formula
The shift in binding energies can be rationalized by taking into
account the effect of the various functional groups on the
effective nuclear charge experienced by the 1s core electron.
• Of all the attached groups, fluorine atoms have the
greatest ability to withdraw electron density from
the carbon atom
• The effective nuclear charge felt by the carbon 1s
electron is therefore a maximum
Æ higher binding energy
Carbon 1s x‐ray photoelectron
spectrum for ethyl trifluoroacetate
d) Quantitative analysis
• Has not enjoyed widespread application
• Both peak intensities and peak areas have been used as the analytical parameter
• the relationship between these quantities and concentration are established
empirically
• Internal standards have been recommended
• Relative precisions of 3% to 10% have been claimed
• For analysis of solids and liquids,
ÆNecessary to assume surface composition is the same as bulk composition
Æleads to significant errors
Example:
Source: Mg Kα (λ = 9.89 Å)
Kinetic energy of XPS electron = 1073.5 eV
Work function = 14.7 eV
What is the binding energy for the emitted electrons?
If source is changed to Al Kα (λ = 8.3393 Å), what is the kinetic energy of the emitted
electron?
Eb = hv − Ek − w
hc
hv =
λ
6 .6 2 5 6 × 1 0 − 3 4 J ⋅ s × 2 .9 9 7 9 × 1 0 1 0 c m ⋅ s − 1
= −8 −1
× 6 .2 4 1 8 × 1 0 1 8 e V ⋅ J − 1
9 .8 9 0 × 1 0 c m ⋅ Α
= 1 2 5 3 .6 e V
A +∗ → A + + hv f
Fluorescence photon
or
A +∗ → A ++ + eA−
Auger electron
X‐ray fluorescence
A +∗ → A + + hv f
• Energy of fluorescence radiation
is independent of the excitation
energy
• Thus, polychromatic radiation
can be used for the excitation
step
Auger electron emission
+∗ ++ −
• The energy given up in relaxation results in the ejection of an
A →A +e
A electron (the Auger electron) with a kinetic energy Ek
• Energy of the Auger electron is independent of the energy of
the photon or electron that originally created the vacancy in
energy level Eb
ÆA monoenergetic source is not required for excitation
• This independence of Auger peaks from input energy makes
it possible to differentiate between the Auger peak in a
spectrum and the XPS peaks
• The kinetic energy of the Auger electron =
(energy released in relaxation of excited ion, Eb – E’b)
− (energy required to remove the second electron from its orbit, E’b)
a KLL Auger transition involves
• an initial removal of a K electron, followed by
• a transition of an L electron to the K orbital, with a simultaneous
• ejection of a second L electron
• Other common transitions are LMN and MNN
Typical Auger spectra for two samples of 70% Cu/30% Ni alloy
Sample A: passivated by anodic oxidation
Sample B: not passivated
• Derivative of the counting rate are used
to enhance the small peaks and to
repress the effect of the large but slowly
changing, scattered electron background
radiation
• Auger electron emission and x‐ray
fluorescence are competitive processes
• Their rates depend upon the
atomic number of the element
involved
• High atomic numbers favor
fluorescence
• Auger emission predominates with
atoms of low atomic numbers
Æ x‐ray fluorescence not a very
sensitive means of detecting
elements with Atm. No. < 10
• AES and XPS provide similar information about the composition of matter.
• The methods tend to be complimentary rather than competitive.
• AES is more reliable and efficient for certain applications, while XPS for others.
• Particular strength of AES:
• Its sensitivity for atoms of low atomic numbers,
• Its minimal matrix effects,
• Its high spatial resolution
• High spatial resolution arises because the primary beam is made up of
electrons that can be more tightly focused on a surface than can x‐
rays.
Instrumentation
• Similar to that of XPS except that the source is usually an electron gun rather
than an x‐ray tube.
Schematic of electron gun
• Heated tungsten filament
≈ 0.1 mm in diameter bent into the
shape of a hairpin with a V‐shaped tip
• The cathodic filament is maintained at a
potential of 1 to 50 kV with respect to the
anode
• Wehnelt cylinder is biased negatively with
respect to filament
• Effect of field in the gun is to cause the
emitted electrons to converge on a tiny
spot called the crossover that has a
diameter of d0 (≈ 50 µm)
• the beam of electrons produced (energy of1 to 10 keV) can be focused on the surface
for Auger electron studies.
• Beam diameters ranging from 500 to 5 µm are used.
• Guns producing beams of approximately 5 µm are called Auger microprobes.
Applications of Auger Electron Spectroscopy
a) Qualitative analysis of solid surface
• Typically, an Auger spectrum is obtained by bombarding a small area of a
surface ( diameter from 5 to 500 µm) with a beam of electrons from a gun
• An advantage of AES for surface studies is the low‐energy Auger electrons
(20 to 1000 eV) are able to penetrate only a few atomic layers (3 to 20 Å)
of solid
Æ while electrons from the electron guns penetrate to a
considerably greater depth below the sample surface, only
those Auger electrons from the first four or five atomic layers
escape to reach the analyzer.
Æ consequently, an Auger spectrum is likely to reflect the true
surface composition of solids.
b) Depth profiling of surfaces
• Involves the determination of the elemental composition of a surface as it is
being etched away (sputtered) by a beam of argon ions.
• The microprobe and etching beams operate
simultaneously.
• The intensity of one or more Auger peaks
are recorded as a function of time.
• Since etching rate is related to time, a depth
profile of elemental composition is obtained.
• Such information is of importance in a
variety of studies such as
• Corrosion chemistry
• Catalyst behavior
• Properties of semiconductor junctions