Auger Electron

Spectroscopy (AES)
 Introduction
First described by Pierre Auger in 1925. It was used to explain
the radiationless relaxation of excited ions observed in cloud
chambers. Only in 1953, J.J. Lander suggested to use it for
chemical analysis. In 1968 L.A. Harris realized its importance as
surface sensitive technique.

A specimen is irradiated with electrons, core electrons are

ejected in the same way that an X-ray beam will cause core
electrons to be ejected in XPS. Once an atom has been
ionized, it must return to its ground state.

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 Introduction
An incident exciting beam (normally electrons) is
directed at a surface.
The atoms in the surface enter an excited state and
can relax by the emission of an Auger electron,
which has a characteristic energy.
The energy spectrum of Auger electrons (20-2000
eV) emitted following the primary ionisation of a
core energy level can reveal the chemical
composition of the surface layers.

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 Principle of AES
A fine focused electron beam bombards the sample and
ejects an electron of the inner shell of the atom.

This vacancy must be refilled by an electron from a higher

energy level.

When the higher energy electron fills the hole, the release of
energy is transferred to an electron in an outer orbit electron.

That electron has sufficient energy to overcome the binding

energy and the work function to be ejected with a
characteristic kinetic energy.

The ejected electron is referred to as an Auger electron after

Pierre Auger who first discovered it in 1925.
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Principle of AES

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 Principle of AES
The Auger electron has an energy given by:

EAuger = EK EL1 EL2,3 -

where EK, EL1 and EL2,3 are the binding

energies of the K1, L1 and L2,3 electron
orbits of the atom. is the work function.

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Principal Auger Electron Energies

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Auger Electron Yield

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 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 monolavers (approximitely
50 Angstron) escape the solid to be detected by analyzers.
This extreme attenuation of photoelectrons and Auger
electronsr results in exceptional sensitivity of Auger
spectroscopy and X-ray photoelectron spectroscopy to
surface layers

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 Some incident electrons are reflected back towards the
surface and laterally (back-scattered electrons),and generate
additional Auger electrons after reflection.

Those generated within a few monolayers of the surface

escape and contribute to the Auger signal.

As a result, the surface area from which Auger electrons are

emitted is some what greater than the area on which the
incident beam is focused.

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 Sample preparation
1. 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.
2. Insulators, such as silicate minerals. Become charged during
Auger analysis, rendering the results of the analysis useless.
3. Coatings generally cannot be applied to samples analyzed by
Auger spectroscopy because Auger electrons are derived from
the uppermost 50 Angstron; even exceptionally thin coatings
less than 10 Angstron) cause extream dilution and attenuation
of the Auger signal derived from the sample beneath a coating.
4. Conducting samples which survive well in UHV are normally
studied.
5. Insulating or biological samples degrade in the beam.
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 Surface textures and morphology

An Auger instrument with the capability to raster and

focus the primary electron beam is referred to as a
Scanning Auger Microscope (SAM); it has the capability
to produce high-quality micrographs with resolution
much greater than reflected- or transmitted light
microscopy, but less than scanning electron microscopy
(SEM).

The SEM-like capability, combined with the ability to

carry out near-surface analyses and an analytical spot-
size less than 1 mm in diameter, make Auger
spectroscopy well suited to study geological materials
where surfaces of grains are small.

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Auger Maps

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Chemical Analysis
by Auger

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Chemical
Effects

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Chemical
Effects

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 AES Instrument Configuration

Elements of Typical Auger System:

Electron Gun
Analyzer
Secondary Electron Detector
Ion Gun
Sample Stage
Introduction System

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The measurement is carried out in an UHV chamber.

Fixed energy electrons from an electron gun in the

energy range 100 eV -10 keV are directed on to the
sample (beam diameter 0.1-1 mm).

An AES system employs an electron gun, either based

on a thermionic or on a field emitter source. A
thermionic source uses thermal energy to give electrons
sufficient energy to escape over the work function of the
source, while in a field emission source the work
function barrier is reduced.

The primary beam of electrons can also cause atoms in

the surface to emit Auger electrons, which have
energies characteristic of the element that emitted
them.

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Some of the electrons emitted from the surface pass through
an aperture and into an electron energy analyser, which
selects electrons over a narrow range of energies, and these
electrons are then detected.

A spectrum is obtained as the first or second derivative of the

secondary electron current by changing the voltages on the
electron energy analyser such that the energy of electrons
which pass through the analyser is gradually changed.

One or two ion guns (Ar +) are used with this technique. The
Ion guns provide a way to sputter the surface of the sample
and give chemical information as a function of depth

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 Cylindrical Mirror Analyzer (CMA)
Secondary electrons passing through a slit in the inner cylinder are
deflected by a negative potential applied to the outer cylinder
and pass through the exit slit onto an electron multiplier where
they are detected.
For any given potential applied to the cylinder, only electrons with
specific energy will pass through the exit slit.
A spectrum is built up by sweeping the outer cylinder potential.

Salient points

1. Resolution scales with Ep

2. Coaxial design eliminates
topography shadowing
3. Better transmission than an HSA
4. Relatively short working distance. 24
Salient points
1. Better energy resolution
2. Longer working distance possible
3. Angle-dependent measurements possible 25
 Retarding Field Analyzer (RFA)

Salient points
Grid Purposes
Low Energy Electron Diffraction
(LEED)
Applied Voltage without
suppressor
Broader energy absorbed
More imaging per run
Less luminescence
Less angular contact

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 Analytical Information
The first or second derivative of secondary electron
current, with respect to the analyser energy is
measured.
The secondary electron current can also be
measured by electron counting techniques.
The resultant electron spectrum reveals a series of
peaks at different electron energies.
The energy of the peaks is characteristic of the
element that produced the electrons and thus the
elements composing the top few monolayers of the
surface can be determined.

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Auger electron survey spectrum from a titanium dental implant
surface, showing that the surface consists of a titanium surface
oxide, with a carbon contamination overlayer and some trace
impurities (3 keV primary electrons, 250 nA primary beam current)

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 Analysis of
Surface
Contamination

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 Qualitative Analysis
Elemental Identification
Procedure Auger Sample

Main Auger Peaks IDd

Values compared to table
IDd elements labeled on
spec
Repeat procedure until
peaks found

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Qualitative Analysis

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 Performance Criteria
Energy resolution is normally in the range 0.52 eV.
Typically a content of ~0.5 at.% in the surface region
can be determined or alternatively ~2% of one
monolayer covering the surface. This depends on
the intensity of Auger emission for the element
concerned.
Typically, Auger electron emission is high for low
atomic number elements and gradually drops as
the atomic number increases.
Auger electrons are not emitted by hydrogen and
helium.

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 Applications

This method is a workhorse technique for

surface science experiments in UHV.
Typically it is used to determine surface,
cleanliness prior to the main experiment.
The usual contaminants are carbon and
oxygen.
It is also used in metallurgy,
microelectronics and corrosion science.
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 Applications
I. Microelectronics Technology
TFA (thin Film Analysis). AES signal is plotted vs. sputtering etch
time (Ar+). The graph composition versus the depth gives
information about composition, thickness and uniformity of the
film.
The technique is used in raw material evaluation, oxidation,
metallization, etc
SAM (scanning Auger Microscopy) looks for inhomogeneity on
surfaces. It is often used with SEM to detect defects and trace
of unwanted elements.
II. Metallurgy
Studies of Segregation at grain boundary (AES).
III. XPS and AES for studies of heterogeneous Catalysis

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 Other Techniques
If the primary beam consists of ions, then the technique is known
as ion excited AES or IAES.
This offers no major advantages in sensitivity, but simultaneous
Auger emission and depth profiling can be carried out.
By varying the take-off angle of the detected electrons, some
information regarding the depth profile of the elements under
study can be obtained. This technique is known as ARAES (angle
resolved AES).
Due to the longer path length, ARXPS (angle resolved Xray
photoelectron spectroscopy) is a better method in this regard.
Spin polarised AES is possible using a Mott detector as with other
spin polarised techniques.
This can provide information regarding the spin resolved density of
states for different elements (see also SPUPS, spin polarised
ultraviolet photoelectron spectroscopy).
The low detection rate of the Mott detector makes data 37
collection for SPAES very slow.
 Auger Photoelectron Coincidence
Spectroscopy
Introduction
In coincidence spectroscopy two or three particles originating
from a single event are detected simultaneously.
In APECS an X-ray beam is used to impact the sample to
excite photoelectrons from core levels, leaving behind
excited core hole states.
These decay virtually immediately by Auger emission of an
electron.
Simultaneous detection of the photoelectron/Auger electron
pair allows all other electrons not directly involved in that
event to be eliminated.
This produces spectra that are completely free of background
signal from scattered secondary electrons and eliminates
overlapping peaks from closely related decay events.
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 Instrumentation
An electron energy analyser such as a cylindrical mirror analyser
(CMA) is used to detect photoelectrons emitted at a kinetic energy
precisely corresponding to the core level of interest.

A second CMA is used to sweep continuously through the energy

range of the corresponding Auger peak. Only those Auger
electrons whose detection coincides exactly with the simultaneous
detection of a photoelectron by the first CMA are counted.

This eliminates all electrons not directly involved in the particular

photoemission process of interest; including secondary electrons or
Auger electrons that have been generated by photoemission from
other core levels with very similar energies.

This produces Auger spectra that are free of backgrounds and

other, superimposed, peaks, allowing the true Auger peak shape to
be determined. The process can also be reversed, scanning the first
(photoelectron) CMA whilst keeping the second CMA at a fixed
(Auger) energy to produce true, background free, photoelectron
peaks instead. 39
 Sample

UHV compatible conductors that are stable over an

extended period of UHV and X-ray exposure.
Previous sample concept may be applied.

Analytical Information
True peak shapes for Auger electron spectroscopy
(AES) or X-ray photoelectron spectroscopy (XPS) that
are free from the backgrounds, overlapping peaks
and satellite features that are present in conventional
AES or XPS are obtained.

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 Performance Criteria
The requirement that only events where both emitted
electrons are detected significantly reduces the count rate
compared to standard XPS or AES as the probability of both
electrons entering the correct analysers is very low.

Count rates are between one count per minute and one
count per second.

The energy resolution of 0.51 eV is significantly worse that in

conventional AES or XPS as emphasis must be placed on
maximizing the achievable count rate at the expense of
overall resolution.

Spatial resolution is around 0.5 mm.

Typical energy range is 50-2000 eV. APECS is sensitive to all

elements except H and He.

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 APECS is significantly more surface sensitive than either XPS or
AES alone, by about a factor of two. Hence, sensitivity is
negligible below about five atomic layers.

UHV is required for this technique.

High surface sensitivity combined with long acquisition times

means that it is limited to samples that will remain stable and
clean in vacuum for many hours under the X-ray beam.

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 Applications
APECS is used in studies where determining the true
shape of the XPS or Auger peaks free from
background subtraction errors or overlapping
features is important, such as for compiling standard
reference spectra, instrument calibration, and
verification of theoretical models of photoelectron
and Auger emission.

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 Other Techniques
PAES (positron annihilation Auger
electron spectroscopy) is another
technique for producing true AES peak
shapes that are free of the secondary
electron background.
PAES is identical to conventional Auger
electron spectroscopy except that the
sample excitation is done with a low
energy beam of positrons rather than a
higher energy beam of electrons.
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 ADVANTAGES AND DISADVANTAGES

The main advantages of AES can be summarized as follows:

Spatial resolution is high.

Analysis is relatively rapid.
Surface or subsurface analysis can be performed.
It is sensitive to light elements (except H and He).
It provides reliable semi quantitative analysis.
Chemical information is available in some cases.

The disadvantages of this technique are as follows:

Insulators are difficult to study due to surface charging.

Surface may be damaged by the incident electron beam.
Precise quantitative analysis may require extensive work.
Sensitivity is modest (0.1 to 1 atom %).
Depth profiling by ion sputtering or sectioning is destructive.
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