571 XPS Lecture1

X-Ray Photoelectron
Spectroscopy (XPS)
Louis Scudiero
http://www.wsu.edu/~scudiero; 5-2669
Electron Spectroscopy for

Chemical Analysis (ESCA)
• The basic principle of the photoelectric effect was enunciated by Einstein
[1] in 1905
E = hν
There is a threshold in frequency below which light, regardless of intensity, fails
to eject electrons from a metallic surface. hνc > eFm
Where h - Planck constant ( 6.62 x 10-34 J s ), ν– frequency (Hz) of the radiation
• In photoelectron spectroscopy such XPS, Auger and UPS, the photon

energies range from 20 -1500 eV (even higher in the case of Auger, up to
10,000eV) much greater than any typical work function values (2-5 eV).
• In these techniques, the kinetic energy distribution of the emitted

photoelectrons (i.e. the number of emitted electrons as a function of their
kinetic energy) can be measured using any appropriate electron energy
analyzer and a photoelectron spectrum can thus be recorded.
[1] Eintein A. Ann. Physik 1905, 17, 132 .
• By using photo-ionization and energy-dispersive analysis of the emitted
photoelectrons the composition and electronic state of the surface region
of a sample can be studied.
• Traditionally, these techniques have been subdivided according to the

source of exciting radiation into :
• X-ray Photoelectron Spectroscopy (XPS or ESCA) - using soft x-ray
(200 - 1500 eV) radiation to examine core-levels.
• Ultraviolet Photoelectron Spectroscopy (UPS) - using vacuum UV (10 -
45 eV) radiation to examine valence levels.
• Auger Electron Spectroscopy (AES or SAM) – using energetic electron
(1000 – 10,000 eV) to examine core-levels.
• Synchrotron radiation sources have 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 will remain, a very small
minority of all photoelectron studies due to the expense, complexity and
limited availability of such sources.
One way to look at the overall photoelectron process is as follows :
A + hv = A+ + e-
1. Conservation of energy then requires that :

E(A) + hv = E(A+ ) + E(e-) (energy is conserved)
2. Since the energy of the electron is present solely as kinetic energy

(KE) this can be rearranged to give the following expression for the KE
of the photoelectron :
E(e-) = KE(e-) = hν – [E(A+ ) - E(A)]
3. The final term in brackets represents the difference in energy

between the ionized and neutral atoms, and is generally called the
binding energy (BE) of the electron - this then leads to the following
commonly quoted equation :
KE = hv - BE
XPS Basic Principle
Photoelectrons
Vacuum
0 eV or Φs Fermi Surface
X-rays Valence Levels
or
2p
2s
Core Levels
E
1s
Photoelectron: BE = hν - KE -Φs
Energy Diagram
• Eb is below the conduction band

edge.
• Fermi energies of the metal and
the spectrometer coincide
EF (electrons transfer between metal and
spectrometer until the EF are aligned).
• Contact potential is e(φ - φsp).

•E’k is the energy measured.
• Eb = h ν - E’k – eφsp (no need to know
the work function of the sample
X-ray Sources
• Their choice is determined by the energy resolution. Typical materials
are Mg and Al.
•A heated filament (cathode) emits electrons which are accelerated
toward a solid anode (water cooled) over a potential of the order of 5 -20
kV.
•Holes are formed in the inner levels of the anode atoms by the electron
bombardment and are then radioactively filled by transitions from higher-
lying levels:
2p 3/2 1s
2p 1/2 1s
Resulting in the emission of X-rays

Mg Kα 1, 2 at 1253.6 eV
Al Kα1, 2 at 1486.6 eV
X-Rays Generation
Typical geometry of an X-ray gun Incident beam
E = hν
Escaped Si Kα X-ray
(~1.74 keV)
Aluminum windows of 10-30 μm thick

separate the excitation region from the
specimen.
Additional x-ray lines (Kα3 and Kα4 ) and
a continuous spectrum (Bremsstrahlung)
are produced. Peaks 10 eV above the Kα
1, 2 with intensities of 8 % and 4 % of Kα
1, 2 and a continuous spectrum contribute
to the BG.
X-ray Sources Available
X-rays Energy (eV) Natural Width (eV)
Cu Kα 8048 2.5
Ti Kα 4511 1.4
Ag Lα 2984 2.6
Al Kα 1487 0.9
Mg Kα 1254 0.8
Na Kα 1041 0.7
Kratos and PHI commonly use AlKα and MgKα

• To remove the unwanted radiation and increase the energy resolution the
AlKα is often monochromatized (cut a “slice” from the x-ray energy
spectrum, removing both satellites and Bremstrahlung (which increases the
BG level).
• Crystal used = quartz because can be obtained in near perfect form and can
be elastically bent (bending does not affect resolution or reflectivity).
θ θ
θ
Parallel Atomic Planes
d
λ = 2dsin(θ)
dsinθ
For first order (n =1) diffraction and Al Kα X-rays, λ = 8.3 Å and the Bragg angle, θ is 78.5°
Rowland circle
The crystal must lie along the circumference of the Rowland circle
(focusing circle), Johann focusing geometry.
Analyzers
Dispersive analysis of the kinetic energy spectrum n(KE)
A field is applied between 2 The parallel plate electrostatic analyzer

parallel plates, distance s apart. The
lower plate has slits a distance r
apart (entrance and exit slits). The
photoelectrons with kinetic energy
KE are transmitted to the detector.
By varying Vd the spectrum of
electron kinetic energies can thus
be obtained. KE is proportional to
Vd therefore the plot of electron
flux at the detector against V is the
2 sKE
photoemission spectrum. Vd =
er
Spherical mirror analyzer
www.Kratos.com
The alternative to dispersive analysis is to discriminate the electron KE by a

retarding electric field applied between the target region and the detector.
Electrons with KE > eVr will reach the detector (a kind of filtration process).
Spectrometer
Photo ionization process has a rather low absolute probability (104 electrons per
second, or 10-15 A) therefore electron multiplier (gain of 10 6) are used to obtain an
accurately measurable current. Newer instruments use channel plates.
3
Components:
2 4 1. Source of radiation
5
2. Ionization Chamber
3. Electron energy analyzer
1
4. Electron detector
5. High vacuum system
software and computer
Typical Wide Energy Scan
3
x 10
90
O 1s
Name Pos. FWHM Area At%
O 1s 533.50 1.633 139182.9 64.047
80
C 1s 285.50 2.019 3470.7 3.696
Si 2p 104.50 1.692 35335.2 32.257
70
Immediate identification of 60
the chemical composition of 50
the surface.
CPS
40
Si 2p
O (Auger)
30
20
C 1s
10
1000 800 600 400 200 0

Binding Energy (eV)
Washington State University--Pullman, WA
The core electron binding energies (BE) of the elements are distinctive
Typical High Resolution Spectra 2
x 10
14
Carbon Peaks
12
High-resolution acquisition scans

10
yield information such as
•Chemical shifts (covalent or ionic bonds) 8
CPS
•Multiplet structure
•Satellites
C 1s (HDPE)
6
C 1s (PTFE)
•Chemical bonding 4
296 294 292 290 288 286 284 282 280

Binding Energy (eV)
Surface Sensitive Technique
• XPS is very surface sensitive

because only electrons from the
top few atomic layers (mean free
path ~1.5 nm) can escape without
loss of energy.
• The absorption length of the X-

rays is about 100 nm to 1000 nm.
Universal Curve
AXIS-165 multi-electron spectrometer
From Kratos analytical Inc.
Summary
A sample placed in ultra-high vacuum is irradiated with photons of energy
(hν); soft x-rays. Atoms on the surface emit electrons (photoelectrons) after
direct transfer of energy from the photons to the core-level electron.
This process can be summarized as follows:

1. A bound electron adsorbs the photon, converting some of its energy into
kinetic energy.
2. As the electron leaves the atom some of its energy is used to overcome
the Coulomb attraction of the nucleus, reducing its KE by its initial state
BE.
3. At the same time the outer orbitals readjust, lowering the energy of the
final state that is being created and giving this additional energy to the
outgoing electron.
References
• Surface Analysis, The Principal Techniques Edited by John C.
Vickerman, John Wiley &Sons (1997).
•Handbook X-ray and ultraviolet photoelectron spectroscopy,
Briggs, Heyden &Son Ltd (1977).
•Solid State Chemistry: Techniques, A. K. Cheetham and Peter Day,
Oxford Science Publication (1987).
• Practical Surface Analysis by D. Briggs and M. P. Seah.
Websites:
http://srdata.nist.gov/xps,
http://www.xpsdata.com,
http://www.lasurface.com,
http://www.eaglabs.com

571 XPS Lecture1

Uploaded by

Copyright:

Available Formats

571 XPS Lecture1

Uploaded by

Document Information

Original Description:

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

571 XPS Lecture1

Uploaded by

Copyright:

Available Formats

X-Ray Photoelectron

Electron Spectroscopy for

• In photoelectron spectroscopy such XPS, Auger and UPS, the photon

• In these techniques, the kinetic energy distribution of the emitted

• Traditionally, these techniques have been subdivided according to the

• Synchrotron radiation sources have enabled high resolution studies to be

1. Conservation of energy then requires that :

2. Since the energy of the electron is present solely as kinetic energy

3. The final term in brackets represents the difference in energy

• Eb is below the conduction band

• Contact potential is e(φ - φsp).

Resulting in the emission of X-rays

Aluminum windows of 10-30 μm thick

Kratos and PHI commonly use AlKα and MgKα

A field is applied between 2 The parallel plate electrostatic analyzer

The alternative to dispersive analysis is to discriminate the electron KE by a

the chemical composition of 50

1000 800 600 400 200 0

Washington State University--Pullman, WA

High-resolution acquisition scans

296 294 292 290 288 286 284 282 280

• XPS is very surface sensitive

• The absorption length of the X-

This process can be summarized as follows:

You might also like

Pfad - The Proxy pFad of © 2024 Garber Painting. All rights reserved.