Surface Analysis

The Study of the Outer-Most Layers of Materials (<100 Å ).

• Electron • Ion Spectroscopies

Spectroscopies SIMS: Secondary Ion
XPS: X-ray Photoelectron Mass Spectrometry
Spectroscopy

AES: Auger Electron

Spectroscopy
X-ray Photoelectron Spectroscopy
XPS, ESCA

Photon inn – electron out

MEF 3100 Spring 2008
Introduction to X-ray Photoelectron
Spectroscopy (XPS)
• What is XPS?- General Theory
• How can we identify elements
and compounds?
• Instrumentation for XPS
• Examples of materials analysis with
XPS
 What is XPS?

X-ray Photoelectron Spectroscopy

(XPS), also known as Electron Spectroscopy
for Chemical Analysis (ESCA) is a widely
used technique to investigate the chemical
composition of surfaces.
 What is XPS?

X-ray Photoelectron spectroscopy,

based on the photoelectric effect,1,2 was
developed in the mid-1960’s by Kai
Siegbahn and his research group at the
University of Uppsala, Sweden.3

1. H. Hertz, Ann. Physik 31,983 (1887).

2. A. Einstein, Ann. Physik 17,132 (1905). 1921 Nobel Prize in Physics.
3. K. Siegbahn, Et. Al.,Nova Acta Regiae Soc.Sci., Ser. IV, Vol. 20 (1967).
1981 Nobel Prize in Physics.
 Introduction
X-ray Photoelectron Spectroscopy (XPS)
X-ray photoelectron spectroscopy works by irradiating a
sample material with mono energetic soft x-rays causing
electrons to be ejected.

Identification of the elements in the sample can be made

directly from the kinetic energies of these ejected
photoelectrons.

The relative concentrations of elements can be

determined from the photoelectron intensities.
MEF 3100 Spring 2008
 XPS - ESCA
• Surface sensitive analysis technique based on
photoelectric effect. Depth of analysis ~4-40 nm.
• All elements except Hydrogen.
• Wide range of materials: Polymers, Ceramics,
metals …. (vacuum compatible)
• Applications: corrosion, catalysis, thin films,
surface coatings, segregation …
• Gives information on chemical composition and
chemical state.

MEF 3100 Spring 2008

The Photoelectric Process
Ejected Photoelectron
Incident X-ray
Free  XPS spectral lines are
Electron identified by the shell from
Conduction Band Level which the electron was
Fermi ejected (1s, 2s, 2p, etc.).
Level  The ejected photoelectron has
Valence Band kinetic energy:
KE=hv-BE-
2p L2,L3  Following this process, the
atom will release energy by
2s L1
the emission of an Auger
Electron.
1s K
Auger Relation of Core Hole
Emitted Auger Electron

Free  L electron falls to fill core level

Electron vacancy (step 1).
Conduction Band Level
 KLL Auger electron emitted to
Fermi conserve energy released in
Level step 1.
Valence Band
 The kinetic energy of the
emitted Auger electron is:
2p L2,L3
KE=E(K)-E(L2)-E(L3).
2s L1

1s K
 X-ray Photoelectron
Spectroscopy Electrons are extracted
Small Area Detection only from a narrow solid
X-ray Beam angle.

X-ray penetration
depth ~1m.
Electrons can be 10 nm
excited in this
entire volume. 1 mm2

X-ray excitation area ~1x1 cm2. Electrons

are emitted from this entire area
 Surface Sensitivity

MEF 3100 Spring 2008

Surface sensitivity

MEF 3100 Spring 2008

 XPS – ESCA

MEF 3100 Spring 2008

XPS Energy Scale- Binding
energy
BE = hv - KE - spec

Where: BE= Electron Binding Energy

KE= Electron Kinetic Energy
spec= Spectrometer Work Function

Photoelectron line energies: Not Dependent on photon

energy.
Auger electron line energies: Dependent on photon energy.

The binding energy scale was derived to make uniform

comparisons of chemical states straight forward.
 Photo emission process is often envisaged as
three steps

•Absorption and ionisation - (initial state effect)

•Response from atom and creation of
photoelectron -(final state effect)
•Transport of electron to surface and
escape - (extrinsic loss)

MEF 3100 Spring 2008

Absorbing X-rays – emitting Photoelectrons

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A closer look

MEF 3100 Spring 2008

XPS Peaks

MEF 3100 Spring 2008

 XPS example: Gold

MEF 3100 Spring 2008

 Energy resolution ~1 eV

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 Electronic structure and spectroscopy

MEF 3100 Spring 2008

 Binding energies?

MEF 3100 Spring 2008

 Chemical shift
Functional Binding Energy
Group (eV)
hydrocarbon C-H, C-C 285.0
amine C-N 286.0
alcohol, ether C-O-H, C-O-C 286.5
Cl bound to C C-Cl 286.5
F bound to C C-F 287.8
carbonyl C=O 288.0

MEF 3100 Spring 2008

Chemical shift – binding energies in
C 1s peak

MEF 3100 Spring 2008

 Spin-Orbit Coupling

Cu 2p 2p3/2

2p1/2
Orbital=p
l=1
s=+/-1/2
ls=1/2,3/2
19.8
Peak Area 1 : 2

965 955 945 935 925

Binding Energy (eV)

MEF 3100 Spring 2008

MEF 3100 Spring 2008
MEF 3100 Spring 2008
 Instrumentation
Surface analysis by XPS requires irradiating
a solid in an Ultra-high Vacuum (UHV)
chamber with monoenergetic soft X-rays
and analysing the energies of the emitted
electrons.

MEF 3100 Spring 2008

 XPS instrument at UIO?

Kratos Axis Ultra – new in 2007

MEF 3100 Spring 2008

People at UiO/Sintef

Martin Spyros
 Instrument

1. Chambers
2. Vacuum and Pumps
3. Sources
4. Monochromator
5. Analysers

Specimen handling
Planning experiments

MEF 3100 Spring 2008

 Dual anode X-ray source

MEF 3100 Spring 2008

 Alternative X-ray sources

MEF 3100 Spring 2008