Transcript auger electron spectroscopy principles and applications

AUGER ELECTRON
SPECTROSCOPY
PRINCIPLES AND APPLICATIONS
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Auger Electron Spectroscopy
• Auger Electron Spectroscopy (AES), is a widely used
technique to investigate the composition of surfaces.
• First discovered in 1923 by Lise Meitner and later
independently discovered once again in 1925 by Pierre
Auger [1]
Lise Meitner
Pierre Victor Auger
1. P.
Auger,
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J. Phys. Radium,
6, 205
(1925).
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Particle-Surface Interactions
Auger Electron Spectroscopy
Ions
Electrons
Photons
Ions
Electrons
Photons
Vacuum
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Auger Electron Spectroscopy
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.
Electronic Structure - Isolated Atoms
Electronic Structure - Solid State
The diagram below schematically illustrates the energies of the
various electron energy levels in an isolated, multi-electron atom,
with the conventional chemical nomenclature for these orbitals
given on the right hand side. It is convenient to expand the part of
the energy scale close to the vacuum level in order to more clearly
distinguish between the higher levels ....
In the solid state the core levels of atoms
are little perturbed and essentially remain
as discrete, localized (i.e. atomic-like)
levels. The valence orbitals, however,
overlap significantly with those of
neighboring atoms generating bands of
spatially-delocalized energy levels
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For more
details,
http://www.chem.qmw.ac.uk/surfaces/scc/scat5_1.htm
electronic structure of Na metal :
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Physics basis
I.
II. Relaxation & Auger Emission
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 energy to ionize all levels of
the lighter elements, and higher core levels of the
heavier elements.
In the diagram below, ionization is shown to occur by
removal of a K-shell electron, but in practice such a
crude method of ionization will lead to ions with
holes in a variety of inner shell levels.
In some studies, the initial ionization process is instead
carried out using soft x-rays ( hn = 1000-2000 eV ).
In this case, the acronym XAES is sometimes used.
As we shall see, however, this change in the method
of ionization has no significant effect on the final
Auger spectrum
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
We will only consider the latter mechanism, an example of
which is illustrated schematically below ....
a rough estimate of the KE of the Auger electron from the
binding energies of the various levels involved.
In this particular example,
KE = ( EK - EL1 ) - EL23 = EK - ( EL1 + EL23 )
Note : the KE of the Auger electron is independent of the
mechanism of initial core hole formation.
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Photoelectron vs. Auger Electron Emission
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History
• Auger –history cloud chamber
• Although Auger emission is intense, it was
not used until 1950’s.
• Evolution of vacuum technology and the
application of Auger Spectroscopy Advances in space technology
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Various ways to estimate Auger electron kinetic energy
EKL1 L23 = Ek(z)–EL1(z)–EL23(z + Δ) -φA
= Ek(z)–EL1(z)–EL23(z)-Δ[EL2,3(z+1) –EL2,3(z)]
Exyz= Ex–½(Ex(z) + Ey(z+1)) –½(E2(z) + E2(z+1)) -φA
Δ has been found to vary from 0.5 + 1.5.
Relaxation more important than ESCA.
Auger energy is independent of sample work function. Electron
loses energy equal to the work function of the sample during
emission but gains or loses energy equal to the difference in the
work function of the sample and the analyzer. Thus the energy is
dependent only on the work function of the analyzer.
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Auger Electron Spectroscopy
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Physics basis
An Auger transition is therefore characterized primarily by :1. the location of the initial hole
2. the location of the final two holes
although the existence of different electronic states (terms) of the final doubly-ionized atom may lead to fine structure
in high resolution spectra.
When describing the transition, the initial hole location is given first, followed by the locations of the final two holes in
order of decreasing binding energy. i.e. the transition illustrated is a KL1L2,3 transition .
In general, since the initial ionisation is non-selective and the initial hole may therefore be in various shells, there will
be many possible Auger transitions for a given element - some weak, some strong in intensity. AUGER
SPECTROSCOPY is based upon the measurement of the kinetic energies of the emitted electrons. Each element in a
sample being studied will give rise to a characteristic spectrum of peaks at various kinetic energies.
This is an Auger spectrum of Pd metal - generated using a 2.5 keV electron beam to produce the initial core vacancies and hence to stimulate
the Auger emission process. The main peaks for palladium occur between 220 & 340 eV. The peaks are situated on a high background which
arises from the vast number of so-called secondary electrons generated by a multitude of inelastic scattering processes.
Auger spectra are also often shown in a differentiated form : the reasons for this are partly historical, partly because it is possible to actually
measure spectra directly in this form and by doing so get a better sensitivity for detection. The plot below shows the same spectrum in such a
differentiated form.
High secondary electron background
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Auger Signal
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Photoelectron Spectroscopy
Photoelectron spectroscopy utilizes photo-ionization and energy-dispersive analysis of
the emitted photoelectrons to study the composition and electronic state of the surface
region of a sample.
Traditionally, when the technique has been used for surface studies it has been
subdivided according to the source of exciting radiation into :
X-ray Photoelectron Spectroscopy (XPS)
Ultraviolet Photoelectron Spectroscopy (UPS)
- using soft x-ray (200-2000 eV) radiation to
examine core-levels.
- using vacuum UV (10-45 eV) radiation to
examine valence levels.
The development of synchrotron radiation sources has enabled high resolution studies to be
carried out with radiation spanning a much wider and more complete energy range ( 5 - 5000+
eV ) but such work is, and will remain, a very small minority of all photoelectron studies due to
the expense, complexity and limited availability of such sources.
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more
details, see http://www.chem.qmw.ac.uk/surfaces/scc/scat5_1.htm
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Physics Basis
- Photoelectron spectroscopy is based upon a single photon in/electron out process and from many
viewpoints this underlying process is a much simpler phenomenon than the Auger process.
- Photoelectron spectroscopy uses monochromatic sources of radiation (i.e. photons of fixed energy).
- In XPS the photon h n is absorbed by an atom in a molecule or solid, leading to ionization and the emission of a core
(inner shell) electron. By contrast, in UPS the photon interacts with valence levels of the molecule or solid, leading to
ionization by removal of one of these valence electrons.
- The kinetic energy distribution of the emitted photoelectrons (i.e. the number of emitted photoelectrons as a function of
their kinetic energy) can be measured using any appropriate electron energy analyser and a photoelectron spectrum
can thus be recorded.
KE: photoelectron's kinetic energy
BE: the binding energy of the electron
KE = hn - BE
NOTE - the binding energies (BE) of energy levels in solids are
conventionally measured with respect to the Fermi-level of the
solid, rather than the vacuum level. This involves a small
correction to the equation given above in order to account for the
work function (F) of the solid, but for the purposes of the
discussion below this correction will be neglected.
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Experimental Details
The basic requirements for a photoemission experiment (XPS or UPS) are:
1. a source of fixed-energy radiation (an x-ray source for XPS or, typically, a He discharge lamp for
UPS)
2. an electron energy analyzer (which can disperse the emitted electrons according to their kinetic
energy, and thereby measure the flux of emitted electrons of a particular energy)
3. a high vacuum environment (to enable the emitted photoelectrons to be analyzed without
interference from gas phase collisions)
Such a system is illustrated schematically below:
Note: There are many different designs of
electron energy analyzer but the preferred option
for photoemission experiments is a concentric
hemispherical analyzer (CHA) which uses an
electric field between two hemispherical surfaces
to disperse the electrons according to their
kinetic energy.
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X-ray Photoelectron Spectroscopy (XPS)
- For each and every element, there will be a characteristic binding energy associated with each core atomic orbital i.e.
each element will give rise to a characteristic set of peaks in the photoelectron spectrum at kinetic energies determined
by the photon energy and the respective binding energies.
- The presence of peaks at particular energies therefore indicates the presence of a specific element in the sample under
study - furthermore, the intensity of the peaks is related to the concentration of the element within the sampled region.
Thus, the technique provides a quantitative analysis of the surface composition and is sometimes known by the
alternative acronym , ESCA (Electron Spectroscopy for Chemical Analysis).
The most commonly employed x-ray sources are those giving rise to :
Mg Ka radiation : hn = 1253.6 eV
Al Ka radiation : hn = 1486.6 eV
- The emitted photoelectrons will therefore have kinetic energies in the range of ca. 0 - 1250 eV or 0 - 1480 eV .
Since such electrons have very short inelastic mean free paths (IMFPs) in solids, the technique is necessarily
surface sensitive.
- The diagram shows a real
XPS spectrum obtained from a
Pd metal sample using Mg Ka
radiation
the main peaks occur at kinetic
energies of ca. 330, 690, 720,
910 and 920 eV.
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Chemical Shifts
The exact binding energy of an electron depends not only upon the level from which photoemission is occurring, but
also upon :
- the formal oxidation state of the atom
- the local chemical and physical environment
Changes in either (1) or (2) give rise to small shifts in the peak positions in the spectrum - so-called chemical shifts .
Such shifts are readily observable and interpretable in XP spectra (unlike in Auger spectra) because the technique :
- is of high intrinsic resolution (as core levels are discrete and generally of a well-defined energy)
- is a one electron process (thus simplifying the interpretation)
Atoms of a higher positive oxidation state exhibit a higher binding energy due to the extra coulombic interaction
between the photo-emitted electron and the ion core. This ability to discriminate between different oxidation states
and chemical environments is one of the major strengths of the XPS technique.
Note: In practice, the ability to resolve between atoms
exhibiting slightly different chemical shifts is limited by
the peak widths which are governed by a combination
of factors ; especially
- the intrinsic width of the initial level and the lifetime
of the final state
- the line-width of the incident radiation - which for
traditional x-ray sources can only be improved by
using x-ray monochromators
- the resolving power of the electron-energy analyzer
In most cases, the second factor is the major
contribution to the overall line width.
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Example: Oxidation States of Titanium. Titanium exhibits very large
chemical shifts between different oxidation states of the metal; in
the diagram below a Ti 2p spectrum from the pure metal (Tio ) is
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compared with a spectrum of titanium dioxide (Ti4+ ).
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INSTURMENTATION
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ANALYSERS
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SITE DIFFERENTIATION
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CHEMICAL SHIFTS
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LIMITS OF THE TECHNIQUE
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COMPLICATIONS
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CHEMICAL EFFECTS
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PERIODIC VARIATION
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XAES
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OTHER EFFECTS
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DOUBLE IONIZATION SATELITE
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ENVIRONMENT EFFECTS
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ENVIRONMENT EFFECT
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ENVIRONMENT EFFECT
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ENVIRONMENT EFFECT
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AES vs. XPS
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Surface Analysis Depths
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Scanning Auger Electron Spectrometer
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Auger Energies vs. XPS
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Elemental Shifts
L. E. JAN
Davis,2009
N. C. MacDonald, Paul W. Palmberg,
G. E. Riach,
R. E. Weber, Handbook of Auger Electron Spectroscopy,
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2nd Edition, Physical Electronics Division, Perkin-Elmer Corp., Eden Prairie, MN 1976.
Quantitative surface analysis: AES
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Quantitative surface analysis: AES
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Scanning Auger
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Element and oxide
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Quantitative surface analysis: AES
By assuming the concentration to be a relative ratio of atoms,
we can neglect the terms that depend only on the instrument:
Ni = Ai/σiχi(1+r)T(Ei)λi(Ei)
It is difficult to accurately determine λi and r, so they are usually
neglected. Modern acquisition and analysis software can account for
the transmission function.
Ni = Ai / Si
Ci = Ai/Si / Σ Ai,j/Si,j
The values of S are determined theoretically or empirically with
standards.
AES is considered to be a semi-quantitative technique
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Quantitative surface analysis: AES
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Quantitative surface analysis: An Example
First-Row Transition Metal Nitrides: ScN, TiN, VN, and CrN
AES Analysis
ScN
VN
CrN
384.2
435.4
486.8
417.4
472.0
527.8
382.2a …
b
382.4
381.6
1.00 …
b
1.95
1.69
2.52b
1.43
1.30
…b
2.10
1.54
1.01
1.14
0.94
Metal L3M2,3M2,3 (α) 337.0
Peak energy Metal L3M2,3M4,5 (β)
N KL2,3L2,3 (γ)
As-deposited
Intensity
Iγ/Iα
367.2
Iγ/Iβ
2.00
Iγ/Iα
After ion
bombardment Iγ/Iβ
1.01
1.82
Bulk composition from RBS
1.06±0.03
TiN
1.02±0.02 1.04±0.02 1.02±0.02
a. The N KL2,3L2,3 peak overlaps with the weak Sc L3M4,5M4,5 peak (see spectra). The latter peak is ~6% of
the Sc L3M2,3M2,3 in the pure metal spectrum.
b. For the TiN AES spectrum, the N KL2,3L2,3 and the Ti L3M2,3M2,3 exhibit severe overlap (see spectra).
Therefore, the peak position of N KL2,3L2,3 is omitted in the table and the listed peak intensity ratio
corresponds to the sum of N KL2,3L2,3 and Ti L3M2,3M2,3 divided by Ti L3M2,3M4,5 (i.e., Iα+γ/Iβ).
peak ratioPRESCHOOL
decreases
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Surface Science Spectra, 7, 167-280, 2000.
after sputtering
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Depth Profiling via AES
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AES Depth Profiling: An Example
(cross section)
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AES Depth Profiling: An Example
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Imaging
Electron Beam in combination with
an SED detector allows for imaging
of the sample to select the area for analysis
Fracture surface of Carbon fibers in BN matrix - analysis area outlined in black
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Chemical Shift
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Chemical Shift
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Semiconductor Doping Shift in AES
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Doping Map by AES
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AES – A PERSPECTIVE
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Elements: Li and above.
•
Sensitivity: 0.1 – 1 atomic %
•
Destructive: No, some beam damage to sensitive materials.
•
Elemental Analysis: Yes, semi-quantitative without standards, quantitative with
standards, not a trace analysis technique.
•
Chemical State Information: Yes, for some elements, sometimes requires highresolution analyzer.
•
Depth Resolution: 0.5 – 5 nm.
•
Lateral Resolution: 500 nm.
•
Sample Types: Solid UHV-compatible, conducting, semiconducting.
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THANK YOU ALL
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