X-ray

Photoelectron
Spectroscopy
(XPS)
Dr. Mohamad Azuwa Mohamed
Office: 2157, 2nd Floor, Department of Chemical
Sciences,
Faculty of Science and Technology,
Universiti Kebangsaan Malaysia
Email: [email protected]
 • 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.

• XPS is a surface-sensitive quantitative

technique based on the photoelectric effect
that can identify the elements that exist
within a material (elemental composition) or
1. Introduction to XPS are covering its surface, as well as their
chemical state, and the overall electronic
structure and density of the electronic states
in the material.

• XPS is a powerful measurement technique

because it not only shows what elements are
present, but also what other elements they
are bonded to.
Analytical Capabilities of XPS

It can:
• Identify elements or compounds (except H and He)
• Determine oxidation states (for example Ti3+ or Ti4+)
• Identify types of chemical bonds (like Si-O or Si-C)
• Semi-quantitative analysis (with about 10-15%
error)
• Determine film thickness
 History of XPS

• 1887: Heinrich Hertz /1888 - Wilhelm Hallwaches UV illuminating

metal surfaces resulted in (spark) - electronic emission

• 1900: Max Planck - Black body radiation

• 1905: Einstein - Light is quantized (Photon Energy, E = hv) * Nobel

Prize 1921.

• 1950: Kai Siegbahn - Studied photo-ejection of electrons with x-rays

* Nobel Prize 1981.

• 1950: Instrumentation (Photoemission as an analytical tool)

• 1960: Chemical Applications

Kai Siegbahn (b.1918): inventor of modern-day
XPS was working at Uppsala University in
1. H. Hertz, Ann. Physik 31,983 (1887). Sweden in the 1950s and 1960s.
2. A. Einstein, Ann. Physik 17,132 (1905).
3. K. Siegbahn, Et. Al.,Nova Acta Regiae Soc.Sci., Ser. IV, Vol. 20 (1967).
2. Basic Principle of XPS
X-ray Photoelectron
Spectroscopy
Small Area Detection
Photo-electric effect Kinetic Energy
Ev (KE)

Ef
Fermi Level

hv

Binding Energy
(BE)

• A photon (E =hv) is absorbed by an core

electron. Why core electron?
• The electron is emitted from the atom with
certain KE
XPS spectral lines are identified by the shell from which the
electron was ejected (1s, 2s, 2p, etc.).
 = minimum amount of energy The ejected photoelectron has kinetic energy:
needed to remove an electron to KE = hv – BE - 
vacuum level Following this process, the atom will release energy by the
emission of an Auger Electron.
 Binding Energy (BE)
❖The Binding Energy (BE) is characteristic of the core
electrons for each element.

❖The BE is determined by the attraction of the electrons to

the nucleus.

❖If an electron with energy x is pulled away from the

nucleus, the attraction between the electron and the
nucleus decreases and the BE decreases.

❖Eventually, there will be a point when the electron will be

free of the nucleus.
 Why the Core Electrons?
❑ An electron near the Fermi level is far from the nucleus, moving in
different directions all over the place, and will not carry information
about any single atom.

✓ Fermi level is the highest energy level occupied by an electron in a

neutral solid at absolute 0 temperature.
✓ Electron binding energy (BE) is calculated with respect to the
Fermi level.

❑ The core e-s are local close to the nucleus and have binding
energies characteristic of their particular element.

❑ The core e-s have a higher probability of matching the energies of

AlKa and MgKa X rays.
3. XPS
Instrumentation
 Energy of Light
Wavelength
106m 103m 1 m 10-3m 10-6m
()

Energy
10-6eV 10-3eV 1 eV 1 KeV 1 MeV
(E)

Short wave radio

Broad-cast

X-ray
 X-ray Sources
❑ Irradiate the sample surface, hitting the core electrons (e-) of the atoms.

❑ The X-Rays penetrate the sample to a depth on the order of a micrometer.

❑ Useful e- signal is obtained only from a depth of around 1 to 10 nm on the surface.

❑ Normally, the sample will be radiated with photons of a single energy (MgKa or
AlKa).

❑ This is known as a monoenergetic X-Ray beam.

❑ The X-Ray source produces photons with certain energies:
– MgKa photon with an energy: hn = 1253.6 eV
– AlKa photon with an energy :h n = 1486.6 eV

❑ The emitted photoelectrons will therefore have kinetic

energies in the range of ca. 0 - 1250 eV or 0 - 1480 eV
The X-ray source for XPS:
➢ In contrast to the electron source, the X-ray source energy depends on the choice of the
anode material, resulting in the availability of a number of discrete energies rather than a
continuous variation of the energy, as exists for electron and ion guns.

➢ The photon energy must be sufficiently high to excite intense photoelectron peaks from all
elements of the periodic table.

➢ For XPS analysis, it is very important to consider the energy resolution of the primary X-
rays.
X-rays vs. e- Beam:
• X-Rays:
Hit all sample area simultaneously permitting
data acquisition that will give an idea of the
average composition of the whole surface.
• Electron Beam:
It can be focused on a particular area of the
sample to determine the composition of selected
areas of the sample surface.
X-ray monochromator
n=2dsin

For Al Ka
 = 8.3Å
use (1010) planes
of quartz crystal
d = 4.25Å
 = 78.5
o

Advantages of using x-ray monochromator

• Narrow peak width
• Reduced background
• No satellite & ghost peaks
 X-ray generation

Standard lab X-ray

source is by very high
energy e- beam hitting
the anode.
Ultra-high Vacuum (UHV) chamber
Surface analysis by XPS requires irradiating a solid in an
Ultra-high Vacuum (UHV) chamber with monoenergetic soft
X-rays and analyzing the energies of the emitted electrons.

Pressure
Degree of Vacuum Torr Remove adsorbed gases from the sample.
102
Low Vacuum
10-1 Eliminate adsorption of contaminants on the sample.
Medium Vacuum
10-4
Prevent arcing and high voltage breakdown.
High Vacuum
10-8
Ultra-High Vacuum
Increase the mean free path for electrons, ions and
10-11
photons.
Ultra-high Vacuum (UHV) chamber
Electron Energy Analyzer EEA: most essential
part of any electron
spectroscopy, its
characteristic are:
energy range,
energy resolution,
sensitivity and
acceptance angle.

Normally its
functions involve:
retarding of the
incoming electron,
selection of the
electrons with right
kinetic energy (pass
energy), detecting of
the electrons
(channeltron)
Detector
✓ Electrons are detected using electron multipliers: a single channeltron for single
energy detection, or arrays of channeltrons and microchannel plates for parallel
acquisition.

✓ These devices consists of a glass channel with a resistive coating on the inside. A
high voltage is applied between the front and the end.

✓ An incoming electron is accelerated to the wall, where it removes more electrons, in

such a way that an electron avalanche is created, until a measurable current pulse
is obtained.

✓ An electron avalanche is a process in which a number of free electrons in a

transmission medium are subjected to strong acceleration by an electric field and
subsequently collide with other atoms of the medium, thereby ionizing them.
✓An electron multiplier is a vacuum-tube
structure that multiplies incident charges.
XPS Instrumentation Mechanism
Data Analysis
CasaXPS, Computer Aided
Surface Analysis for X-ray
Photoelectron Spectroscopy, is a
computer program that allows you
to process your XPS and UPS
data. It offers a powerful data
processing environment on a PC. It
can do angle resolved and depth
profile XPS.
Types of XPS spectra
Example of XPS spectra
4. Instrument Calibration
➢ Accurate energy calibration of the spectrometer is therefore essential to obtain
quantitative information from XPS spectra.

➢ Common to calibrate the spectrometer by the photoelectron peaks of Au 4f7/2, Ag 3d5/2

or Cu 2p3/2

➢ The National Physics Laboratory (NPL) in Teddington, England, set up the first traceable
reference calibration line energy positions for XPS as shown in Table below

. . . .
. . . .
. . . .
. . . .
. . . .
. . . .

➢ Many spectroscopists often use adventitious carbon (AC) as a binding energy (284.8 eV)
standard.

➢ As AC is present on all air exposed surfaces it is the simplest method of establishing a

standard for studies on non-conductive materials.
XPS Analysis of Pigment from Mummy
Artwork Pb3O4

Egyptian Mummy
2nd Century AD
World Heritage Museum
University of Illinois
PbO2

C
O
150 145 140 135 130
Binding Energy (eV)

Pb Pb
N
Ca
Na XPS analysis showed
Cl Pb that the pigment used
on the mummy
wrapping was Pb3O4
rather than Fe2O3
500 400 300 200 100 0
Binding Energy (eV)
Analysis of Carbon Fiber- Polymer
Composite Material by XPS
XPS analysis identifies the functional
groups present on composite surface.
Chemical nature of fiber-polymer
interface will influence its properties.

-C-C-

N(E)/E
Woven carbon
fiber composite
-C-O

-C=O

-300 -295 -290 -285 -280

Binding energy (eV)
Analysis of Materials for Solar Energy Collection
by XPS Depth Profiling-
The amorphous-SiC/SnO2 Interface
The profile indicates a reduction of the SnO2
Photo-voltaic Collector occurred at the interface during deposition.
Such a reduction would effect the collector’s
efficiency.
SnO2
Sn

Solar Energy

Conductive Oxide- SnO2

Depth
p-type a-SiC 500 496 492 488 484 480
a-Si Binding Energy, eV
Data courtesy A. Nurrudin and J. Abelson, University of Illinois
Thank you