“An Introduction to Auger Electron

Spectroscopy : Applications and

Fundamental Studies on Electronic
Structure of Atoms Molecules and
Solids”

Lecture delivered by Dr. Ashish

 Outline
First Part: Second Part: Fundamental Studies

• Historical Introduction • Motivation

• Basics principles • Theoretical simulation for Auger process:
- Auger emission - coupling schemes and selection rules
- Energies determination - multiplets calculation
- Nomenclature - transition probabilities (intensities)
- Analysis Volume - examples of line shape calculation
- Advantages and Disadvantages • Different Mechanisms associated with
• Experimental Setups Auger emission:
- RFA, CMA, HA - satellites: Coster-Kronig (C-K), Shake-up,
- Simple methods for quantification plasmons
• Applications: some examples. • Examples of opened possibilities with
synchrotron radiation and XAES:
- chemical shift analysis
- shake-up versus C-K
- Auger Depth Profile
- Sudden and Adiabatic Approximation
- SAM – Scanning Auger Microscopy
- Auger Cascade and Screening mechanisms
 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 loss 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    Za  e EB (a)   fN 1   iN
Auger
Za  e   Zbc

 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

45
Excited with

LM M
45
Ti K=4511 eV

3
45
LM M
23

45
23

LM M
3
23
(u.a.)

LM M

23
LM M

23
23
Intensity (a.u.)

2
2

45
3

LM M
45
Intensidade

45 45
LM N
3
XPS peaks

45

45 45
LM M

LM N
45
3p

2
3s
3d
LMM + LMN
2200 2400 2600 2800 3000 3200 3400 3600 3800 4000

Energia
Kinetic Cinética (eV)
Energy (eV)

For a given element, several lines of Auger emissions can be observed.

 Auger Transitions lines for different elements

Red dots are

indicating the
most intensity
lines
 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
Retarding H.V.
computer
Supply
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
 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 Ax ( XYZ )  I 0 Ax ( E p ) 1  rM ( EAx ,  )  T ( EAx ) D( EAx )  N A ( z ) exp   z / M ( EA x ) cos  dz
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 surface analysis, but be careful when you start to write “ % “ for
your sample !
 Examples for AES

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/
 SAM

Conventional SEM image SAM

 Second Part: Fundamental Studies in AES

Motivation:

• Understanding the electronic structure:

-Chemical bonds, charge transfer, material properties,…

• Possibilities to verify simple models:

-Atomic Theory, Complete Screening Model,
- helpful in the development of other techniques example AED

• AES is a ”laboratory of excited states”

- theoretical determinations of branching ratios, fluorescent yields, ...
 Theoretical simulation of Auger process
wq
(n 1 l 1 ) w 1 (n 2 l 2 ) w 2 . . . (n q l q ) electronic conf. of the atom .
Atomistic approach:
2 Z N i 1 2
N N N
  
Hamiltonian of the : H                i (ri )(li . si )   
2
i
i 1 i 1 ri i 1 j 1 ri  r j i 1
system (Leighton,R.B. “Principles of Modern Physics”)
Robert D. Cowan, “ The theory of Atomic Structure
And Spectra”
N N
2Z (more approximations:
“Average Energy”: b  i2    b'  bb' Ek
r
Close shell approximation,
i 1 i 1 i Central potential)

• Russell-Saunders ou LS: Coulomb >> Spin-Orbit [ Astrophs. J. 61,38 (1925)]

Coupling schemes: •jj: Spin-Orbit >> Coulomb [ Condon and Shortley- “The theory of Atomic Spectra”]

•Intermediate Coupling ( IC ): Coulomb  Spin-Orbit [ Condon and Shortley ...]

jj coupling (normally for the initial state) LS coupling (normally in the final State)
 Coulomb Interaction Spin Orbit
N i 1  
2
b    b'   LSJM , LS' ' J ' M '  f k F k ( l1l2 )  gk G k ( l1l2 ) b  i i )(li . si ) b   i d i
 ( r
i 1 j 1 rij
L O
i
k  1 3
2
F l k l IFl k l IR l l LU
di  li ji mi li . si li' ji'mi'   j , j '  m ,m' M
Nji ( ji  1)  li ( li  1)  P
Q
G
H0 0 0JKGH0 0 0 JKS
Tl l k V
i i i i
2 4
f k  ( 1) L  2li  1
1 1 2 2 1 2

i 1 W
2 1

2
Fl k l I Rl l LU
2l  1G J S
2

 H0 0 0KTl l k V
S 1 2 1 2
gk  ( 1)
i 1
i
W
1 2

R.D. Cowan in “ The Theory of Structure and Spectra”

Transition Probabilities (Auger Intensities)

2
2 1
(Fermi Golden Rule) Wifjj  LS 
a 
2 j1  1  M f
JMj1 j2
r12
l3l4 SLJM
2
2 e2
Wif  i   f
 r1  r2
For IC coupling f   C f ( LSJ ) l3l4 SLJM
LS

2
l 2 L l1  1 1 
1 4
  S 
Wifjj  IC  (1   l3 ,l4 )(2 J  1) ( 2li  1) ( 2 x  1)  Ci ( LSJ )( 1) L ( 2l  1)(2 S  1)  1  2 2  AS ( L, l 2 )
2 i 1 x LS  2 j1 x  L x J 
 Practical Examples : 1) Auger Lineshape calculation
Pd L M M
3 23 45 Shake-Up
Ag
Nb
LM M
jj-L S
2 2,3 2,3

LM M
2 2,3 2,3

h = 3 19 0 eV
Auger
L = 3 174 eV
3

Plasmons
Mo In

LM M
2 2,3 2,3
LM M
2 2,3 2,3

Plasmons
Rh Sn
Plasmons

jj-IC LM M
2 2,3 2,3

LM M
2 23 23

Plasmon
Pd Plasmons+L2M23M23 Sb
LM M
2 2,3 2,3

S hirley B a ck gro un d

-80 -60 -40 -20 0 20 40 -80 -60 -40 -20 0 20 40 60 80

21 80 2200 222 0 224 0 2260 22 80 2300 23 20
Energia Relativa à 1F (eV)
3
K in e tic E n e rgy (e V )
 Open possibilities for XAES using synchrotron radiation

Selecting channels for transition changing the photon energies: shake-up vs CK

Ag L M M
3 45 45

D - acima do L =3808 eV (h=3829 eV)

1
C - acima do L =3525 eV (h=3597 eV)
2
B - acima do L =3352.6 eV (h=3520 eV)
3
A - threshold L =3352.6 eV (h=3359 eV)
3

D
C
B

Intensidade (u.a)
A

B-A (somente shake-up)

C-B ( Contribuição do CK L L X)
2 3
D-C (Contribuição do CK L L X)
1 2,3

2550 2560 2570 2580 2590 2600

Energia Cinética (eV)
 From the Adiabatic to the Sudden Approximation
(B) Ag L M M
3 45 45
Excitado longe do limiar de L
3

Aproximação Abrupta h   = L + 167.4 eV

Sudden Approx. 3

Sat.1
Sat.2
Intensity (a.u.)

(A) Ag L M M Excitado próximo do limiar de L

3
3 45 45

Aproximação Adiabática h  = L + 6.4 eV

3

Adiabatic Approx.

Shirley Background

Sem satélites
1S
0
No satellites

2555 2560 2565 2570 2575 2580 2585 2590 2595

Energy (eV)
More Complex Auger Transitions : cascade Process
 MVV excited below and above L3 threshold

1. Enormous increase in normal MVV emission - attributed to

combination of normal MVV + fluorescence + Auger cascade.
Describe observed intensities.

2. Pd seems to behave as though it had a full d-band induced by

core hole. In Short, first observation of unambiguous
quasiatomic spectral structure produced purely by screening
mechanisms

A. de Siervo, R. Landers and G.G. Kleiman, PRL 86, (2001) 1362.

A. de Siervo, R. Landers, M.F. Carazzolle, et al. J.E.S.R.P 114 (2001) 679