X-Ray Photoelectron Spectroscopy (XPS)

Abdul halim
MS Research Student
Department of Chemistry
Shahjalal University of Science and Technology, Sylhet-3114

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 OUTLINE
• XPS Background

• XPS Instrument

• How Does XPS Technology Work?

• Equation

• KE versus BE

• Spectrum Background

• Identification of XPS Peaks

• XPS Technology
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 XPS
• X-Ray Photoelectron Spectroscopy
• ESCA: electron spectroscopy for chemical
analysis

-elemental composition
-chemical formula
-chemical/electronic state of the element

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 XPS Background

• In 1905, Einstein, photoelectric effect

• In 1960, Dr. Siegbahn and his research group, developed the

XPS technique and produce the first commercial
monochromatic XPS

• 1981, Seighbahn, noble prize

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 Photoelectric Effecct

Electros
knock
away
from the
surface
with
definite
hν

Fig: photoelectric effect

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 The photoelectric process
• Ejected Photoelectron
• Incident X-ray
• Free
• Electron
• Conduction Band • Level
• Fermi
• Level
• Valence Band

• 2p • L2,L3
• 2s • L1

• 1s • K
 Following this process, the atom will
release energy by the emission of an
Auger Electron.
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 Auger Relation of Core Hole
Emitted Auger Electron

Free
Electron
Conduction Band Level
Fermi
Level
Valence Band

2p L2,L3
2s L1

1s K

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 X-Rays
• 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 10 to

100 Å on the surface.

• The X-Ray source produces photons with certain energies:

– MgK photon with an energy of 1253.6 eV
– AlK photon with an energy of 1486.6 eV

• Normally, the sample will be radiated with photons of a single

energy (MgK or AlK). This is known as a monoenergetic
X-Ray beam.
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 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.

• 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 AlK and MgK.

Valence e-

Core e-
Atom

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 Binding Energy (BE)

The Binding Energy (BE) is characteristic of the core electrons

for each element.
This is the point with 0
energy of attraction
between the electron
and the nucleus. At
this point the electron
0 B.E. is free from the atom.

x These electrons are

attracted to the
p+
proton with certain
binding energy x
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 XP SPECTROMETERS

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 COMPONENTS OF XPS

 A source of X-rays
 An ultra high vacuum (UHV)
 An electron energy analyzer
 magnetic field shielding
 An electron detector system
 A set of stage manipulators

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 XPS Instrument

X-Ray Source

Ion Source

SIMS Analyzer

Sample introduction
Chamber

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 X-ray Photoelectron Spectrometer
Computer
System
Hemispherical Energy Analyzer

Outer Sphere Magnetic Shield

Inner Sphere Analyzer Control

Electron Lenses for Energy Multi-Channel

Optics Adjustment Plate Electron
(Retardation) Multiplier
Resistive Anode
X-ray Encoder
Source Position Computer
Lenses for Analysis
Position Address
Area Definition
Converter
Position Sensitive
Detector (PSD)
Sample
5 4 .7

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 How Does XPS Technology Work?

• A monoenergetic x-ray beam • Ultrahigh vacuum environment to

emits photoelectrons from the eliminate excessive surface
surface of the sample. contamination.

• Cylindrical Mirror Analyzer

• The x-ray photons The (CMA) measures the KE of
emitted e-s.
penetration about a micrometer of
the sample
• The spectrum plotted by the
• The XPS spectrum contains computer from the analyzer
signal.
information only about the top 10
- 100 Ǻ of the sample.
• The binding energies can be
determined from the peak
positions and the elements present
in the sample identified.

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 Which materials are analazıed?

 XPS is routinely used to analyze inorganic

compounds,metals,semiconductors,polymers,
ceramics,etc.

 Organic chemicals are not routinely analyzed by XPS

because they are readily degraded by either the energy
of the X-rays or the heat from non-monochromatic X-
ray sources

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 ANALYSIS OF XPS

 XPS detects all elements with (Z) >3. It cannot detect H (Z =

1) or He (Z = 2) because the diameter of these orbitals is so
small, reducing the catch probability to almost zero

 Dedection unit: ppt and some conditions ppm

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 The Atom and the X-Ray
X-Ray
Free electron

Valence electrons
proton
neutron

Core electrons electron

electron vacancy

The core electrons

respond very well to
the X-Ray energy
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 X-Rays on the Surface
e- lower layer
e- top layer Outer surface
but no collisions
e- lower layer X-Rays Inner surface
with collisions

Atoms layers
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 X-Rays on the Surface
• The X-Rays will penetrate to the core e- of the atoms in the
sample.

• Some e-s are going to be released without any problem giving

the Kinetic Energies (KE) characteristic of their elements.

• Other e-s will come from inner layers and collide with other e-s
of upper layers
– These e- will be lower in lower energy.
– They will contribute to the noise signal of the spectrum.

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 Equation
KE=hv-BE-Ø

KE Kinetic Energy (measure in the XPS

spectrometer)

hv photon energy from the X-Ray source (controlled)

Ø spectrometer work function. It is a few eV, it gets

more complicated because the materials in the
instrument will affect it. Found by calibration.

BE is the unknown variable

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 Equation

KE=hv-BE-Ø

• The equation will calculate the energy needed to get

an e- out from the surface of the solid.

• Knowing KE, hv and Ø the BE can be calculated.

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 KE versus BE

KE can be plotted
depending on BE
# of electrons

Each peak represents the

amount of e-s at a certain
energy that is characteristic
of some element.

BE increase from right to left

E E E

Binding energy
1000 eV 0 eV
(eV) KE increase from left to right
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Interpreting XPS Spectrum: Background
• The X-Ray will hit the e-s in the bulk (inner e- layers) of the
sample
N = noise
• e- will collide with other e- from top layers, decreasing its
energy to contribute to the noise, at lower kinetic energy than

# of electrons
N4
the peak .
N3
• The background noise increases with BE because the N2 SUM of
all noise is taken from the beginning of the analysis.
N1

Binding energy

Ntot= N1 + N2 + N3 + N4

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 XPS Spectrum
• The XPS peaks are sharp.

• In a XPS graph it is possible to see Auger electron

peaks.

• The Auger peaks are usually wider peaks in a XPS

spectrum.

• Aluminum foil is used as an example on the next

slide.

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 XPS Spectrum

O 1s

O Auger

O because
of Mg source

C O 2s
Al
Al

08/14/2025 Sample and graphic provided by William Durrer, Ph.D. 26

Department of Physics at the Univertsity of Texas at El Paso
 Auger Spectrum

Characteristic of Auger graphs

The graph goes up as KE increases.

08/14/2025 Sample and graphic provided by William Durrer, Ph.D. 27

Department of Physics at the Univertsity of Texas at El Paso
 Identification of XPS Peaks
• The plot has characteristic peaks for each element
found in the surface of the sample.

• There are tables with the KE and BE already

assigned to each element.

• After the spectrum is plotted we can look for the

designated value of the peak energy from the graph
and find the element present on the surface.

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 XPS Technology
•• Applications in the industry:
Consider as non-destructive
– Polymer surface
– Catalyst
• Provide information about
– Corrosion
surface layers or thin film
– Adhesion
structures
– Semiconductors
– Dielectric materials
– Electronics packaging
– Magnetic media
– Thin film coatings

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 Thank you very much

Any Questions

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