New York State Center for Advanced Thin FilmTechnology

Auger Electron Spectroscopy (AES)

(pronounced ! j"y)
Fundamentals and Applications
New York State Center for Advanced Thin FilmTechnology
Important events in Auger Spectroscopy
Phenomenon discovered by Pierre Auger and reported
in the journal Radium in 1925.
1953 -- J. Lander uses electron-excited Auger electrons to study surface impurities.
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-80s 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.
New York State Center for Advanced Thin FilmTechnology
Auger emission principle (see following slide).
I An incident electron emitted by the gun is colliding with a 1s-shell
electron. Ejecting this electron generates a loss of energy that will be
compensated by an electron transition from 2s-shell toward 1s shell.
This generates a radiation which causes an Auger electron to be
ejected.
I Each emitted Auger electron is resulting from well-defined and
identified transitions. In the case above, we talk about KLL transition
because of the shells involved in the different transition mechanisms.
I To be complete, we must also say that ejecting an electron does not
lead to the final state: this phenomenon goes on until the atom recovers
a balanced energy state.
I For a given element, several lines of Auger emissions can be observed.
The complexity of the spectra scales with atomic number.
New York State Center for Advanced Thin FilmTechnology
http://www.cea.com/tutorial.htm
The process
New York State Center for Advanced Thin FilmTechnology
- Surface sensitive (0.5-5.0 nm
- Sensitive to light elements
- High spatial resolution (20 nm)
allows nanoscale elemental
mapping
- Chemical state information
- Analytical volume confined to
top 10 atomic layers.
Beam-solid interaction
New York State Center for Advanced Thin FilmTechnology
Analyzer configurations
Two general types
1. Cylindrical Mirror Analyzer (CMA)
2. Hemispherical Sector Analyzer (HSA)
New York State Center for Advanced Thin FilmTechnology
University of Arizona website
Salient points
1. Resolution
scales with Ep
2. Coaxial design
eliminates topography
shadowing
3. Better transmission
than an HSA
4. Relatively short working
distance.
New York State Center for Advanced Thin FilmTechnology
University of Arizona website
Salient points
1. Better energy
resolution
2. Longer working
distance possible
3. Angle-dependent
measurements possible
New York State Center for Advanced Thin FilmTechnology
Plasmonexcitation, occurs with high probability as the free electron gas
between ionic cores absorbs energy. Typical plasmonexcitations involve
transfer of around 15 eV to the solid. (A)
Conduction band excitation ejects loosely bound conduction electrons as
secondary electrons. The majority leave with 0 to 50 eV kinetic energies.
(B)
Bremsstrahlung(from the German for "braking radiation") occurs when a
primary electron undergoes deceleration in the Coulombicfield of an atom.
The bremsstralungconsists of X-ray photons with energies spread between
zero and the primary beam energy. (C)
Excitation of lattice oscillations (phonons) transfers a substantial portion
of beam energy to the sample as heat.
Inner shell ionization leaves the atom in an a highly energeticstate while
absorbing a large amount of primary electron energy. Decay of this excited
state produces characteristic Auger electrons and X-rays. (D)
Sources of features in Auger spectra
(see following slide)
New York State Center for Advanced Thin FilmTechnology
http://www.cea.com/tutorial.htm
A
B
C
D
New York State Center for Advanced Thin FilmTechnology
What about...
buried layers,
structures?
Sputter Depth Profiling
S. Hofmann, et al., Thin Solid Films, 1998
New York State Center for Advanced Thin FilmTechnology
What about...
buried layers,
structures?
Sputter Depth Profiling using
Zalar (sample) rotation to
improve depth resolution
Without sample rotation
With sample rotation
New York State Center for Advanced Thin FilmTechnology
Some caveats regarding sputter depth profiling
Sources of artifacts
Sample charging
Topographical features resulting in non-uniform sputtering
Non-homogeneous material (preferential sputtering)
Beam effects
Backscattered sample atoms
Ion beam mixing
New York State Center for Advanced Thin FilmTechnology
I Chemical information in Auger spectroscopy
MRL Website
New York State Center for Advanced Thin FilmTechnology
Quantification using first principles is theoretically possible but rarely done
due to the variance in coupling schemes governing the transition from a
singly-ionized state to a doubly-ionized state. Assumptions for planarity, 2-D
homogeneity and tool parametrical stability must also be made using these
equations.
Quantification in Auger Electron Spectroscopy
Quantification in Auger Electron Spectroscopy
The convention is to use relative sensitivity factors derived
from pure materials, referenced to some other material.
Originally this was silver, but more recently, copper.
A.W. Czanderna, Ed., 1975
New York State Center for Advanced Thin FilmTechnology
Auger relative sensitivity
10 kV primary beam
KLL LMM
MNN
PHI Auger Handbook
New York State Center for Advanced Thin FilmTechnology
AES Applications
-Easily characterized
Metals, semiconductors, thin films
-Difficult to impossible
Glasses/ceramics, polymers
Some composites
Biological materials (bone, hair, etc.)
Sample size
Maximum - 300 mm (state of the art systems), 25 mm (PHI 600 system)
Minimum - <100 microns (handling and mounting limiting factor)
Analytical area
<200 (field-emission/MCD systems, >1500, PHI 600 system
Requirements
Vacuum-compatible, conducting, semiconductor, or thin film on conducting substrate
Materials
Sputter depth profiling routinely used
See following examples
New York State Center for Advanced Thin FilmTechnology
An example of necking that occurs during the
sintering step, adding strength to offset porosity
1 mm
Surface Heterogeneity in ASTM
F-75 Alloy Prepared for
Biomedical Implantation
1
1 R. Moore, G. L. Grobe, J . Gardella, J VST, A9 (3), May-J une 1991, 1323-1328.
New York State Center for Advanced Thin FilmTechnology
Auger spectra from two areas on a passivated ball
surface exhibiting different morphologies. Note
chromium enrichment in area 1
1 um
New York State Center for Advanced Thin FilmTechnology
Auger elemental maps illustrating the distribution of the
chromium+carbon+nitrogen phase
New York State Center for Advanced Thin FilmTechnology
Platinum elemental map of halo region around Pt line. Note lack of
topographical features, confirming the lack of topographical artifacts.
Distribution of platinum deposited in FIB
10 um