Angle resolved x-ray photoelectron spectroscopy:

Introduction:
Surface composition of sample can be obtained by using XPS analysis. In conventional XPS analysis the
angle at which photo emitted electrons are collected by the electron energy analyzer is fixed relative to
the surface plane. Angle resolved XPS refers to the systematic variation of the angle of emission or
photo emission “take-off” angle in order to enhance surface sensitivity. By decreasing take off angle, the
surface to volume single rations increases in a predictable manner. Surface enhancements of up to 10
times are possible at very shallow angles.
Principle:
The basic principle of classical XPS analysis depends upon photoelectric effects. Whe n photons with
sufficient energy(hv) from the soft x-ray beam hit an atom of the sample, the atom ionized resulting in
the ejection of electrons from the core levels of the atom with kinetic energy Ek. The kinetic energy Ek of
the ejected electron depends on the following relation
hv= Ef + Ek + Фspect.
Or, Ef = hv- Ek - Фspect.= Eb
Where, Eb is binding energy and Ef is the ionization energy related with the Fermi level.
Angle resolved XPS is non-destructive technique suitable for the investigation of the in-depth
composition of very thin surface films. Photo emitted electrons travelling through a solid have a
relatively high probability of interacting with neighboring atoms and undergoing atoms and undergoing
inelastic energy loss processes before leaving the sample surface. Those electrons that are able to
escape without a loss in energy appear in the XPS spectrum at discrete energies above a smooth
background of in elastically scattered electrons. The distance that an electron can traverse through the
solid before experiencing inelastic scattering is defined as the mean free path(λ). The value of λ is
dependent upon the electron kinetic energy and varies from (0.5-5nm) over the energy range of 100-
2000eV but is independent of the trajectory of the electron for most samples. However, the sampling
depth which is measured normal to the plane of the sample is highly dependent on the electron
trajectory. As can be seen in figure below, the sampling depth (d) is at a maximum for a corresponding
take off angle θ of 90°. If λ is known then (d) can be calculated at any take-off angle by,
Sampling depth (d) = λ sinθ
Thus, enhancement in surface sensitivity by a factor of greater than 10 can be obtained by changing the
take-off angle from 90° to 5°.

d1 and d2 are sampling depth θ1 and θ2 are takeoff

angle λ is mean free path. Since, θ 1>θ2 so that d1>d2.
Figure: schematic representation of basic ARXPS experiment.
Theoretical models for ARXPS:
There are different theoretical models of the angle resolved XPS technique mainly based on the types of
sample surface and spectrometer conditions. Simple smooth surface and rough surface models are
some important topics to be discussed for the theoretical aspects of ARXPS measurement.
A) Simple smooth surface model:
It is desire to calculate the number of photoelectrons, emitted per second, escape from points on the
surface, enter the spectrophotometer and finally are detected so to continue photoelectro n peak. Some
assumptions are
i) The sample specimen surface is assumed to be atomically smooth.
ii) The incident x-ray flux (I0 ) is assumed to be uniform throughout the region in sample.
iii) The mean free path of the x-ray dependent upon the wavelength but independent of the angle of
incident.
iv) The mean free path is strong function of kinetic energy.
B) Rough surface model:
a rough surface of a sample specimen is any surface deviating from the atomically smooth or flat. The
basic effects of the roughness are twofold. Firstly, the portion of the rough surface is shaded from either
x-ray incident or photoelectron escape and secondly the true angle of x -ray incident (Ф’) and
photoelectron escape (θ’) are different form the smooth surface values. The main important difference
for the rough surface model is that the average angle of escape or takes off angle of photoelectron θ ’ is
not equal to θ. The true take off angle of photoelectron θ’ determines the average depth of sample by
λesinθ’.
Instrumentation:
The principle elements of an ARXPS are x-ray source, sample holder with UHV chamber, and analyzer
allowing to measure the kinetic energy of the ejected photoelectrons and a system of detection as same
as in conventional XPS measurement.
A) UHV chamber:
An ultra-high vacuum condition is necessary for the ARXPS measurements to be undertaken for three
reasons.
i) Low pressure is required to insure a sufficient inelastic mean free path for the photoelectrons to
escape form the sample surface and reach to the XPS analyzer without being dissipated.
ii) Low pressure (<10-7torr) is required to operate the x-ray anode and filaments without damage.
iii) UHV condition is generally needed to minimize surface contamination from interfering with analysis
in surface sciences.
B) X-ray source:
X-ray source of XPS and ARXPS generally consists of both Mg and Al coated anodes struck by electrons
form high voltage (10-15kV) MgKα and AlKα radiation line. The x-ray emission form anode is constituted
by a principal ray and satellite ray. Therefore, the use of monochromator allows to eliminate these
satellite rays and to reduce width of x-ray so that it improves the spectrometer performance. Some x-
ray radiation lines used in XPS with their energy and width are listed below.
Line MgKα AlKα CuKα CuLα
Energy(eV) 1253.6 1486.6 8048 929.7
Width(eV) 0.7 0.85 2.6 3.8

C) Analyzer:
In order to vary the sensitivity performance of the ARXPS measurement, various inlet slit widths and
analyzer pass energies can be used. The slit width must not be too large to avoid a large angular
aperture, so it is better to record XPS spectra at high analyzer pass energy. In general, two types of
analyzers(i.e. CHA and CMA) are in practice. Among them cylindrical mirror analyzer is not in use due to
large solid angle which impairs its ability to detect photoelectrons coming from a single direction .
Therefore, CMA system in ARXPS gives the advantages of the in depth surface analysis capabilities of the
sample specimens because the entrance slit of the CHS is narrow and one dimensional.
D) Sample preparation and mounting:
Sample surface to be analyzed should not be contaminated with any substances. For this propose,
sample surface is washed with distilled water followed by suitable organic solvent. Volatile organic
solvents should be removed. If the sample shows affinity towards oxygen then sample should be
preserved in inert environment. Preparation of sample should be well characterized in terms of surface
geometry including composition, layer thickness and roughness. The rotation of the sample on the axes
can performs in situ and requires a somewhat more sophisticated sample holder for the angle resolved
XPS.
Applications:
a)relative photoionization cross section of element:
Relative photoionization cross section (σ) is defined as the probability of exciting a photoelectro n from
the atom by one photon of x-ray radiation. The surface composition of the materials can be obtained if
all the photoionization cross section in the electron level under consideration is known. When σ is
unknown a plot of the corrected intensity ratio versus expected atomic weight between elements
contained in the compound , which is used to obtained relative photoionization cross -section.
b) Electronic structure of surface film:
It is used to find out the electronic structure of the surface film by analysis of the chemical shift value of
atoms or molecules present in the film.
c) In-depth compositional analysis:
It is used for in depth compositional analysis of materials. On increasing take-off angle, depth of
sampling is increases so that the ejection of electron form depth materials is carried out by x -ray
photon. Due to this fact composition on the depth of sample can be measured by varying take off angle.
Limitations:
Some limitations of ARXPS are listed here. In addition with these limitations, several other additional
factors most be considered.
i) Angle of electron emission must be precisely defined.
ii) The technique requires that the sample surface must be relatively flat.
iii) The angular data acquisition them relative to comparable angular resolved analysis.
iv) Potential sample damage as a result of radiation exposure must be closely monitored.
Auger electron spectroscopy:

Introduction:
Observation of Auger electrons was first reported by Auger (1925) through the study of particle tracks in
cloud chambers. Auger spectroscopy has received less attention than other types of spectroscopy until
recently, primarily because the Auger process and Auger electrons were viewed more as an impediment
to the quantification of other processes (e.g., fluorescence yields and modeling of X-ray lines) than as a
technique to obtain compositional and chemical-state information about gases and solids. As a result,
understanding of the Auger process grew more as a result of its "nuisance value" than of any desire to
develop it as an analytical method.
Corrosion, metallurgical and semiconductor studies have increased sharply during the last 30 years, and
with these studies there has been an increased need for accurate compositional analysis of surfaces and
interfaces.
Auger electrons are derived from within the near-surface region of solids (the uppermost 50 A), and
reflect the elemental concentrations of the surface region; consequently, Auger applications and
instrumentation have developed rapidly in the last three decades. Auger spectroscopy now is recognized
as fundamentally important to the comparatively new field of Surface Science because of its surface
sensitivity. Application of Auger spectroscopy now includes study of ionization of gases, chemical-state
properties of molecular ions, catalysis and interactions occurring at solution-mineral interfaces.

Principle:
Energy levels of electrons in an atom can be divided into valence (outer) and core (inner) levels (or
shells), as in Figure 1. Valence electrons are affected both by the nucleus of the atom with which they
are associated and by neighboring atoms or ions surrounding the central atom. Core electrons are
"closer'' to the nucleus of the central atom than are valence electrons, and hence are strongly affected
by the charge on the nucleus; however, they are also affected by ions and atoms of the surrounding
environment.
Bombardment of solids by X-rays or electrons may dislodge core electrons from their inner shells. The
energy required to dislodge a core electron may be derived from X-rays. The energy imparted to a core
electron must be greater than the energy binding the electron to the nucleus; otherwise the electron
remains in its shell rather than being ejected. In fact, the energy of the incident electron must be
approximately five times greater than the binding energy to obtain removal of appreciable quantities of
core-level electrons. The ejected electron is called a photoelectron.

After emission of a core electron, the resulting ion is energetically, and the remaining electrons are
rapidly rearranged. The ion may achieve a lower energy-state, although not ground states, by having
another core electron jump from a higher-level inner shell to the vacated site in the lower-level shell.
The jump is energetically favored because electrons in higher level shells have greater energy (potential
and kinetic) than electrons in lower-level shells. For our example, electrons of the L1 shell have greater
energy than electrons of the K shell. Upon transfer of an electron from the L1 to K shell, the excess
energy resulting from the transfer is dissipated through one of two processes, emission of X-rays
(fluorescence) or ejection of a second electron.
Through ejection of a second electron, energy is dissipated dominantly in the form of kinetic energy of
the ejected electron. This ejected electron is the Auger electron. After emission of the Auger electron,
the atom lacks two electrons, one from each of the L1 and L2,3 shells, and hence has become a doubly-
charged ion.
The energy of ejected electron is independent to energy of x-ray and given as
KE=EK-(EL2 +EL3) ………………… (1)
Figure: schematic representation of auger electron spectroscopy

A minimum of three electrons are associated with the production of an Auger electron. From this, it is
apparent that the Auger process does not occur in H and He. Auger electrons are generated from all
other elements; consequently, AES can be used to detect almost all elements in the near-surface region
of solids. This is a major advantage of the technique.

Instrumental design
The major components of the instrument are a primary beam (X-ray or electron source), an analyzer of
electron energy to detect Auger electrons and measure their energies, an ion gun to sputter the surface
of the sample, and an ultra-high vacuum system. X-ray or electron beams can be used to generate Auger
electrons, but the latter beam is preferable for two reasons. An electron beam can be much more
intense than an X-ray beam, and the resulting Auger signal generally is correspondingly more intense

High-resolution electron analyzer is used for development of the current instruments. X-ray and primary
electron beams do not remove significant amounts of material from the surface of the solid; hence the
technique is nondestructive. As the escape-depth of Auger electrons is small; consequently, a high
vacuum (less than 10-9 torr) is required to ensure minimum attenuation of the Auger signal and little
contamination of the sample surface during analyses.

Oxygen, carbon and nitrogen can be detected by Auger electron spectroscopy (A ES) on the surfaces of
most solids exposed to the atmosphere. Contamination dilutes the Auger signal of elements in the
underlying solid, and is to be avoided if quantitative analyses of surfaces are required. Samples reacted
in solutions may acquire a surface film of solutes as samples are removed from solution and the solvent
evaporates. The ultra-high vacuum required to prevent attenuation of Auger electrons requires all
samples to be properly dried before analysis. Therefore, the vacuum must be constantly monitored after
insertion of new samples into the instrument. Some materials are unstable in vacuum and may require
long periods of pumping to obtain a vacuum appropriate for analysis

Sample preparation
Sample holders are made of a conducting material, commonly aluminum, to prevent charging of
samples, and good electrical contact must be made between sample and holder. With good contact,
charging during analysis is no problem for metals and semiconductors. Insulators, such as silicate
minerals become charged during Auger analysis, rendering the results of the analysis useless. In
electron-microprobe analysis, the bulk of the X rays are derived from a depth of a few micrometers;
hence thin, conductive coatings are applied to surfaces to prevent charging without deleterious effects
to analyses. Coatings generally cannot be applied to samples analyzed by Auger spectroscopy because
Auger electrons are derived from the uppermost 50A; even exceptionally thin coatings less than 10 A)
cause extreme dilution and attenuation of the Auger signal derived from the sample beneath a coating.

Applications and limitaitons:

a. AES is very much surface sensitive so that it is used for the surface compositional analysis
b. This is mainly applicable for lower elements in periodic table except H and He . There is much greater
probability for the light elements to release energy through ejection of
Auger electrons than through emission of X rays, but the probability decreases with increasing atomic
number. There is approximately equal probability that arsenic will yield an Auger electron and a photon
(X ray). This can be shown is given graph.

c. Auger electrons have relatively low kinetic energy, which limits their escape depth.

Properties of Auger electron and X rays

The incident electron may penetrate a few micrometers into the solid and still dislodge core electrons.
As a result photoelectron, Auger and X-ray processes occur well beyond the near-surface of the solid.
Whereas photons have sufficient energy to escape the solid from a depth of a few micrometers,
photoelectrons and Auger electrons cannot penetrate more than a few atomic diameters from their site
of generation. As a result, only photoelectrons and Auger electrons generated within the first few
monolayers (approximately 50 A) escape the solid to be detected by analyzers. This extreme attenuation
of photoelectrons and Auger electrons results in exceptional sensitivity of Auger spectroscopy and X -ray
photoelectron spectroscopy to surface layers.
As mentioned previously, an ion in the excited state may dissipate energy through emission of X - rays
(photons) as well as Auger electrons. The energy lost by emission of a photon yields the final state for
the ion without an increase of charge on the ion. Study of these X-rays is the domain of X-ray
fluorescence ( XRF) spectroscopy. Once generated, X rays escape from a depth of many micrometers; in
contrast to photoelectrons and Auger electrons, X rays are derived from a large volume of the solid,
increasing the likelihood that the compositions obtained by XRF are representative of the entire sample.
X -ray fluorescence spectroscopy is an important tool for determination of bulk compositions of solids.
The kinetic energy of an emitted Auger electron is primarily a function of the energy levels of the atom
involved in the Auger process. As no two elements have identical orbital energies of the electrons, the
binding energies of their electrons are likewise unique, and measurement of the kinetic energy of the
Auger electron leads immediately to identification of the elements. In practice, identification is a matter
of comparing an experimental result against spectra in atlases or tables of known spectra. Furthermore,
there is a direct (but complex) relationship between the intensity of the Auger signal (number of counts)
for a given transition and the abundance of the element in which the transition occurs; consequently,
Auger spectroscopy can be used to obtain the composition of solid surfaces.

Comparision between XPS and AES

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
utilizing 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.
Auger spectroscopy can be considered as involving three basic steps :
(1) Atomic ionization (by removal of a core electron)
(2) Electron emission (the Auger process)
(3) Analysis of the emitted Auger electrons

X-ray photoelectron spectroscopy (XPS) is a powerful technique widely used for the surface analysis of materials.
At low energy resolution it provides qualitative and quantitative information on the elements present whereas at
high energy resolution it gives information on the chemical state and bonding of those elements. High -Resolution
XPS (HR-XPS) uses a monochromator which provides the following advantages over a standard x -ray source:
• An x-ray energy distribution with reduced energy width improves chemical selectivity by narrowing the spectral
peaks.
• A lower spectral background.
• The elimination of unwanted x-rays from satellites and anode impurities, which simplifies spectral analysis.
• The elimination of Bremsstrahlung and thermal radiation from the x -ray source, which greatly reduces x-ray
source induced damage.
• A focused x-ray spot on the sample i ncreases the sensitivity on small samples.

AES ARXPS
AES does not depend up on intensity of x ray ARXPS depends up on intensity of x ray
Surface compositional analysis only Surface as well as in depth composition
Depth= λ sinθ
Kinetic energy of emitted electron is very low Kinetic energy of emitted electron is very high
Given by KE=E(1)-E(2,3,4) Given by KE=hv-Ef-Ф
Applicable only for lower elements except H and Applicable for all elements except H and He
He
CME is used as analyzer CHA is used as analyzer