“An Introduction to Auger
Electron Spectroscopy :
Applications and Fundamental
Studies on Electronic Structure
of Atoms Molecules and Solids”
Historical Introduction
AES means Auger Electron Spectroscopy – This spectroscopy technique uses Auger electrons
as probes for surface science analysis: chemical and elemental characterization.
TheAuger phenomenon is a not irradiative de-excitation process for excited atoms. The de-excitation
occur by a Columbic interaction where the atom loses energy by emission of one or more electrons. This
ejected electron to one continuum state is named Auger electron.
1923 or (1925) - This effect was discovered independently by
Lise Meitner (1923 -Journal Zeitschrift fur Physik)
and Pierre Auger (1925 -‘Radium’ )
1953 - J. Lander uses electron to excited Auger electrons
to study surface impurities.
Lise Meitner Pierre Auger
1968 - L. Harris demonstrates usefulness of technique when he
differentiates the energy distribution of Auger electrons
emitted from a bombarded surface. About the same time,
Weber and Peria employ LEED optics as Auger spectrometers.
1969 - Palmberg et. al invent the cylindrical mirror analyzer (CMA),
greatly improving speed and sensitivity of the technique.
The mid-80’s saw the implementation of Schottky field emitters as electron sources,
allowing analysis of features ~20 nm in size. Improvements in analyzers and sources have
pushed this limit to the 10 nm regime.
The Auger Process
or photons or
… (PE)
Ground State Ionization: Initial State Auger recombination
and e- transport : Final State
• IMPORTANT to Remember: In the Auger process doesn’t exist a REAL photon intermediating the transition.
Conservation Laws
Z + ω → Za+ + e (a ) ε Nf −1 − ε iN
EB =
Za+ + e → Zbc
Auger ++
+ e + eA EK A (abc) = EB (a ) − EB (b) − EB (c) -U
Observe: Auger electron energy is independent of the excitation energy !
U= Electron-Electron interaction in the final state + Relaxation energies
U is known as Auger parameter
Nomenclature for Auger Transitions
Spectroscopy Nomenclature From the X-Ray techniques
(example : XPS)
nlj 1s; (2s, 2p1/2,2p3/2), 3s, … nlj K, (L1, L2, L3), M1, …
Conventionally is used the X-Ray type in the nomenclature of Auger transition. In this example:
KL1L23 .
When the electronic levels are energetically well distinguishable is common to use more sub-
indices, for example L1,2,3M2,3M4,5.
For a group of transition, the sub-indices are in many times omitted (KLL, LMM, MVV) and for
transition involving level(s) in the valence band is common to use V instead (L,M,N,O ..): Example
M4,5VV.
Auger Transitions lines
In
L3M45M45
Excited with
Ti Kα=4511 eV
L3M23M45
L2M23M45
L2M23M23
L3M23M23
(u.a.)
Intensity (a.u.)
L2M45M45
Intensidade
L3M45N45
XPS peaks
L1M45M45
L2M45N45
3s 3p
3d
LMM + LMN
2200 2400 2600 2800 3000 3200 3400 3600 3800 4000
Kinetic Cinética
Energia Energy (eV)
(eV)
For a given element, several lines of Auger emissions can be observed.
A. de Siervo (MSc. Thesis University of Campinas, 1988)
Auger Transitions lines for different elements
Red dots are
indicating the
most intensity
lines
Auger Electron Yield
Direct and Differential Spectra
Direct and
Differential
Spectra
Analysis Volume
•Depending on the spot size of the e-gun
is possible to have spatial resolution in
the (nm) range.
• In the direction perpendicular to the
surface the analysis volume depends on
the electron mean free path.
Advantages and Limitations
Advantages:
• Surface sensitive
• Elemental and chemical composition analysis by comparison with standard samples of known composition
• Detection of elements heavier than Li. Very good sensitivity for light elements.
• Depth profiling analysis: quantitative compositional information as a function of depth below the surface
(destroy the sample)
• Spatial distribution of the elements (SAM): Elemental or even chemical Auger maps analysis in lines, points
and areas.
Disadvantages / Limitations:
• Samples must be compatible with UHV in most of cases.
• For samples not prepared in-situ is normally necessary cleaning procedures such as sputtering, heating or
scraping of the surface (some times, it is not possible)
• Samples must be conductive. In some cases is possible to avoid charging effects also for non-conductive
samples
• Possibility of beam damage of some surfaces, for example some organic samples and polymers
• Hydrogen and helium are not detectable (only by indirect ways when they are present in the compounds or
physically adsorbed).
• Quantitative detection is dependent on the element: light elements > 0.1%; heavier elements > 1%.
• Accuracy of quantitative analysis depending on the availability of adequate sensitivity factors (or
standards). Typical accuracy ± 10%.
Analyzer Setups
1) RFA in 4-grid LEED optics
Pre
Amplifier
Phase
shifter
2f f
Frequency Signal f
Lock in
doubler generator
Amplifier Isolated
f transformer
computer
Retarding H.V. Seah and Briggs in
Supply “ Partical Surface Analysis”
signal
2) CMA – Cylindrical Mirror Analyzer
Important Characteristics:
-Energy resolution scales with Ep.
- coaxial designing eliminates
shadowing
-Better transmission than an
Hemispherical Analyzers
- Relative Short work distance
- Normally uses the lock-in amplifier
to get the differential distribution
dN(E)/dE.
3) HA – Hemispherical
Analyzer
• Important Characteristics :
• Better Energy Resolution
• Long work distance possible
• -Angle-dependent
measurements possible
CHA – Concentric Hemispherical
Analyzer
Quantification in AES
Quantification analysis using first principle is possible but rarely done due the large
differences between coupling schemes that govern the Auger transitions in a multi ionized
atom. The most common analysis use sensitive factors derived from pure materials or
standards. This method also have a lot of imprecision and it should be judiciously used.
∞
Auger electron intensity: I 0σ Ax ( E p ) 1 + rM ( E Ax , α ) T ( E Ax ) D( E Ax ) ∫ N A ( z ) exp − z / λM ( E Ax ) cos θ dz
I Ax ( XYZ ) =
0
Sensitive factor
I i / Si
Xi =
∑Ij / Sj
Simplified formula for Homogeneous materials:
j
Relative Sensitivity Factor for primary e= 3KeV
PHI analyzers
The most important message is: AES is very useful, probably one of the best
way to carry out surface analysis.
Examples for AES
P. Weightman, (review article)
1) Chemical Analysis
AES is one of the best complementary
technique for XPS in the chemical
analysis. Depending on the kinetic energy
of the Auger electrons, AES is much more
sensitive to the surface that conventional
XPS.
Chemical shifts and Auger lineshape can
be used to determine the chemical state
for a given element in the sample, and in
studies as charge transfer in alloys.
Differences in the line shape and peak
Position for the C Auger (KVV) in different
CxHy compounds
Auger Depth Profiling
Sources of artifacts
• sample charging
• topographical features resulting of non-uniform sputtering of the sample
• preferential sputtering
• beam effects
• Ion beam mixing
R.Nix, http://www.chem.qmw.ac.uk/surfaces/scc/
Depth Profiling
SAM
Conventional SEM image SAM
http://www.aquila.infn.it/infm/Casti/Tech/Sam/Examples.html
