Auger electron spectroscopy

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 1. Introduction
 1923 or (1925) - This effect was
discovered independently by Lise
Meitner (1923 -Journal Zeitschrift fur
Physik) and Pierre Auger (1925
-‘Radium’ )
Pierre Auger
 Auger Electron Spectroscopy (Auger
spectroscopy or AES) was developed in
the late 1960's
 Surface specific technique utilising the
emission of low energy electrons in the
Auger process
 Useful in determining the composition of
the surface layers of a sample.
Lise Meitner
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2. Steps involved in AES

• (1) Atomic ionization (by

removal of a core electron)
• (2) Electron emission (the Auger
process)
• (3) Analysis of the emitted Auger
electrons

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3.1 Electronic Structure -

Isolated Atoms

Schematic of the energies of the

various electron energy levels in an
isolated, multi-electron atom
X-ray notation of electron energy states. The higher
transitions are N1 = 4s2, N2,3 = 4p6, N4,5 = 4d10, O1 = 5s2
etc., P1 = 6s2 etc. Q1 = 7s2 etc.

If an unpaired electron is in a degenerate orbital (i.e p,d,f..) the spin angular momentum s, and the
orbital angular momentum l, can combine in different ways and produce new states that are
characterized by the total electronic angular momentum, j
j  l s and degeneracy of this states is 2j+1

Richard P. Gunawardane and Christopher R. Arumainayagam in "Handbook of Applied Solid State Spectroscopy"
Chapter 10, Auger Electron Spectroscopy, Springer, pp 451 - 483 (2006)
 3.2 Electronic Structure - Solid State
o In the solid state the core levels
of atoms are little perturbed
and essentially remain as
discrete, localised (i.e. atomic-
like) levels.

o The valence orbitals, however,

overlap significantly with those
of neighbouring atoms
generating bands of spatially-
delocalised energy levels.

o The energy level diagram for

the solid is therefore closely Electronic structure of Na metal
resemblant of that of the
corresponding isolated atom,
except for the levels closest to
the vacuum level.
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 4. The Auger Process
(a) Ionization
 The Auger process is initiated by
creation of a core hole.

 This is typically carried out by

exposing the sample to a beam
of high energy electrons
(typically having a primary
energy in the range 2 - 10 keV).

 Such electrons have sufficient

In the diagram above, ionisation is shown
energy to ionise all levels of the to occur by removal of a K-shell electron,
but in practice such a crude method of
lighter elements, and higher core ionisation will lead to ions with holes in a
levels of the
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 (b) & (c) Relaxation & Auger
Emission
 The ionized atom that remains
after the removal of the core
hole electron is, of course, in a
highly excited state and will
rapidly relax back to a lower
energy state by one of two
routes :
X-ray fluorescence
or

Auger emission

In this example, one electron falls from a higher level

to fill an initial core hole in the K-shell and the energy
liberated in this process is simultaneously transferred
to a second electron ; a fraction of this energy is
required to overcome the binding energy of this
second electron, the remainder is retained by this
emitted Auger electron as kinetic energy. In the Auger
process illustrated, the final state is a doubly-ionized
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atom with core holes in the L2 and L3 shells.
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5.Some examples of Auger
transitions

Auger transition notation

•First letter - initial core

hole location

•Second letter - initial

location of relaxing electron

•Third letter - location of

second hole (initial location
of Auger electron)

H. Lüth, Surfaces and Interfaces of solid materials, Springer 1996

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6. Kinetic Energy of the Auger
electron
Consider as an example KL1L2 process

K.E of outgoing L2 electron is

is a correction factor which is

approximately given by

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 Example: KL1L2 Process for Fe atom
(Z=26)

H. Lüth, Surfaces and Interfaces of solid materials, Springer 1996

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 7. Auger electron energies as a
function of atomic number

•Atoms with less than 3

electrons cannot undergo
auger transitions.

•The strong z dependence

of the auger energy is
important for the
application of AES as a
chemical analysis
technique.

H. Lüth, Surfaces and Interfaces of solid materials, Springer 1996

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 8. Escape depth of auger electrons
The attenuation length of Auger electrons λ with a kinetic energy Ekin
determines the escape depth Λ according to:

 Λ= λcosθ -------(1)

θ is the Emission angle of the Auger electrons with respect to the surface
normal.
The probability for an electron to travel over a distance x without any
collision is propotional to exp(-x/ Λ) with 95% of the auger intensity coming
from within 3 Λ of the surface.

 λ=0.41a1.5Ekin0.5 -----------(2)

a (in nm) is the monolayer thickness of a cubic crystal calculated by ρNa3=A,

ρ the density (in Kg/m3); n the Avogrado constant;A the molecular mass
(kg/mol)of the matrix in which the Auger electron is created.
 Since the kinetic energy determines the escape depth, a measurement of
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element but of different energy can be used as a
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measure for the variation of composition with depth.
 9. Instrumentation

H. Lüth, Surfaces and Interfaces of solid materials, Springer 1996

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9.1 Electron sources

 (1) A tungsten cathode source consists of a wire filament, which is

bent in the form of a hairpin. The filament operates at ~2700 K by
resistive heating. The tungsten cathodes are widely used, because
they are both reliable and inexpensive. Lateral resolution is limited,
because the tungsten cathode current density is only about 1.75
A/cm2.

 (2) A lanthanum hexaboride (LaB6) cathode provides higher current

densities because LaB6 has a lower work function (3 eV) than
tungsten (4.5 eV). At 2000 K, the current density can be as high as
~100 A/cm2.

 (3) A field emission electron source consists of a very sharp

tungsten point at which the electric field can be >10 7 V/cm. Hence,
electrons tunnel directly through the barrier and leave the emitter.
A field emission gun provides the brightest beam (10 3 to 106 A/cm2).
The electron beam can be further focused to as small as 10 nm.
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9.2 Cylinderical Mirror Analyser

The electric field distribution is
created between concentric cylinders
which are biased at different voltages,
the inner one is usually grounded,
located at radius R1 from the rotational
axis of symmetry, and the outer one
located at radius R2 is biased to a
mirror voltage (-Vm). The source
(specimen) and focal point lie on the
rotational axis of symmetry

The electric field inside the analyzer is

propotional to the inverse of the
radius.

Pass energy, E0 can be found from the

relation
Layout of a cylinderical mirror analyser

where k is a constant that depends on

the distance L seperating the
specimen and the detector plane
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10. Typical AES spectrum

Auger spectrum contains many unwanted background electrons -

AES spectrum of Ag, (a) direct Auger peaks appear as small features on intense inelastic
spectrum, (b) differentiated background.
spectrum Inorder to minimise the contribution from the background noise,
spectra are differentiated N(E) N'(E) or dN(E)/dE
 11. Applications of AES
11.1 Probing the Growth Mechanisms of thin films
AES Intensity

Frank-van der Merwe (layer-by-layer), Stranski-Krastinov

(layer+island), Volmer-Weber (Island)
H. Lüth, Surfaces and Interfaces of solid materials, Springer 1996
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 11.2 AES depth profiling
Electron energy analyser
Electron beam

Ar+
Auger electron

Si/Mo multilayer film

Auger electron intensity as a

Gradually removing material from function of sputtering time
the surface region being analysed,
whilst continuing to monitor and
record the Auger spectra.
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 11.3 Elemental Mapping and line scans
- The Scanning Auger Microprobe (SAM)

Mapping and Line Scans - These

are imaging techniques that measure
the lateral distribution of elements on
the surface. The electron beam is
scanned across the sample surface,
either along a fixed line (line scan) or
Auger Maps, of a gold on graphite
across a given area (mapping) while
the AES signal is analyzed for specific
energy channels. The AES signal
intensity is a function of the relative
concentration of the element(s)
corresponding to the selected energy
channel(s). Spatial resolution is
approximately 0.3 μm.
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Secondary electron image and auger line
http://www.phi.com scan of a gold on graphite
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Summary
Basic concepts of AES

 Instrumentation

Experimental techniques

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