Advance Instrumentation Technique

(BSK4153)
X-Ray Photoelectron Spectroscopy (XPS)

Kratos Axis Ultra-DLD XPS Spectrometer

Outlines

• Theory and Principles of XPS

• Advantages and disadvantages of
XPS
• Data analysis: an example
• Applications
 XPS Background
• XPS technique is based on Hertz (1887), Thomson (1897) and
Einstein’s (1905) idea about the photoelectric effect, (Nobel Prize,
1921)

– The concept of photons was used to describe the ejection of

electrons from a surface when photons were impinged upon it

• During the 1950’s Dr. Siegbahn and his research group developed the
XPS technique.

– In 1981, Dr. Siegbahn was awarded the Nobel Prize in Physics for
the development of the XPS technique
• Also known as Electron Spectroscopy for Chemical Analysis (ESCA),
Ultraviolet Photoelectron Spectroscopy (UPS), Photoemission
Spectroscopy (PES)
 Theory and Principles of XPS
✓ XPS is based on the photoelectric effect where a sample is irradiated with a
monochromatic beam of X-rays (MgK or AlK). The X-rays provide an
energy in term of photon with hitting the core electron of the atoms leading
to ionisation and emission of valence electrons with specific kinetic energy.
✓ 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.
X-Ray
Free electron

Valence electrons

proton

neutron

Core electrons electron

electron vacancy

The core electrons respond very well

to the X-Ray energy
This kinetic energy information from ionisation and emission of
valence electron was used to calculate the binding energy of
photoelectron using equation given:

Ek = hv − Eb −  Ernest Rutherford Eq:

Eb = hv − ( Ek +  )
Where,
Ek is the kinetic energy of the photoelectron
h is Planck’s constant
v is the frequency of the exciting radiation
Eb is the binding energy of the photoelectron with respect to the Fermi level of
the sample
φ is the work function of the spectrometer (the minimum thermodynamic
work (i.e. energy) needed to remove an electron from a solid to a point in
the vacuum immediately outside the solid surface. It is an adjustable
instrumental correction factor that accounts for the few eV of kinetic energy
given up by the photoelectron as it becomes absorbed by the instrument's
detector
 What is 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.

This is the point with 0

energy of attraction
between the electron and
the nucleus. At this point
the electron is free from the
atom.
0 B.E.

x
These electrons are
attracted to the
p+ proton with certain
binding energy x
 Ek versus Eb
KE can be plotted depending on
BE

Each peak represents the amount

# of electrons

of e-s at a certain energy that is

characteristic of some element.

Eb increase from right to left

1000 eV 0 eV

Ek increase from left to right

Binding energy
(eV)
XPS spectrum of an Rh/Al2O3 model catalyst
• The separation between the two
peaks are named spin orbital
splitting. The values of spin
orbital splitting of a core level of
an element in different
compounds are nearly the same.

• The peak area ratios of a core

level of an element in different
compounds are also nearly the
same.

• Spin orbital splitting and peak

area ratios assist in element
identifications.

XPS spectrum of organoplatinum complexes

Determine the Intensity ratio of the XPS peaks: 2j + 1

Where, j = ℓ + s

If ℓ (angular momentum quantum number) equal/bigger than 1 (p,d,f),

has two sublevels with energy difference

Example; Pt 4f, 4f7/2 (ℓ=3, j = 3 + ½) and 4f5/2 (ℓ=3, j = 3 - ½)

Pt 4d ?
 How Does XPS Technology Work?
• A monoenergetic x-ray beam emits
photoelectrons from the from the
surface of the sample.
• The X-Rays either of two energies:
– Al Ka (1486.6eV)
– Mg Ka (1253.6 eV)
• The x-ray photons The penetration
about a micrometer of the sample
• The XPS spectrum contains
information only about the top 10 -
100 Ǻ of the sample.
• Ultrahigh vacuum environment to
eliminate excessive surface
contamination.
• Cylindrical Mirror Analyzer (CMA)
measures the KE of emitted e-s.
• The spectrum plotted by the
computer from the analyzer signal.
• The binding energies can be
determined from the peak positions
and the elements present in the
sample identified.
 X-Ray Source

Ion Source

SIMS Analyzer

Sample introduction
Chamber

UHV Chamber
 Why Does XPS Need UHV?
• To count the number of electrons during the acquisition of a
spectrum with a minimum of error

• Contamination of surface
– XPS is a surface sensitive technique.
• Contaminates will produce an XPS signal and lead to incorrect
analysis of the surface of composition.

• The pressure of the vacuum system is < 10-9 Torr

• Removing contamination
– To remove the contamination the sample surface is bombarded
with argon ions (Ar+ = 3KeV).
– heat and oxygen can be used to remove hydrocarbons

• The XPS technique could cause damage to the surface, but it is

negligible.
What can XPS be used for?
X-ray photoelectron spectroscopy (XPS) is suitable for the qualitative
and quantitative determination of;
• Elemental composition (atomic %, Relative quantification) of
elements in the surface region (0 to 10 nm) of solid sample. (and
what other elements they are bonded to)
• Chemical or electronic state of each element in the surface
• Impurities/contaminant
• The thickness of one or more thin layers (1–8 nm) of different
materials within the top 12 nm of the surface
• Measure uniformity of elemental composition as a function of
depth by ion beam etching (or depth profiling)

XPS is sensitive to all elements except from hydrogen and helium. It

cannot detect hydrogen (Z = 1) or helium (Z = 2) because the
diameter of these orbitals is so small, reducing the catch probability
to almost zero.
• XPS is highly surface sensitive with information typically arising
from the top ca. 1-5 nm. Through measurement of the element
peak areas and correction with the appropriate sensitivity factors,
XPS has a sensitivity for most elements of ca. 0.1 at%. Detection
limit of part per thousand, if ppm, concentration at top surface or
very long collection time (overnight)

• Analysis of elemental oxidation states in XPS relies on the

determination of binding energies based on a suitable
reference. Most samples encountered are inherently insulating
and so a suitable internal reference is chosen to reference all
energies.

Typically the carbon core level for adventitious carbon, C(1s) is used
and assigned a value of 284.8 eV, although 285.0 eV is also
commonly used, especially in the XPS of polymers.
 Example of XPS Spectrum
XPS counts electrons ejected from
a sample surface when irradiated
by x-rays.

The peak intensities measure how

much of a material is at the
surface.

The peak positions indicate the

elemental and chemical
composition

Full width at half maximum

(FWHM) are useful indicators of
chemical state changes and
physical influences (e.g broadening
of a peak may indicate: a change in
the number of chemical bonds
contributing to a peak
Shape)
Detection limits:
Parts Per thousand

Parts per million*

(*possible with concentration at
top surface or very long collection
time)
 Pd (3d5/2) 2+
Pd

Pd (3d3/2)
Intensity (arb. units)

Au (4d)
0 (a)
Pd

(b)

(c)
Deconvulation of Pd (3d) spectra of 5wt%Au-
Pd/TiO2IW catalyst reduced in 5%H2/Ar for 3
360 355 350 345 340 335 330 325 320 hours at 400 oC
Binding energy (eV)
• The number of detected electrons in each
Pd (3d) and Au (4d) spectra of 5wt%Au-Pd/TiO2IW catalysts of the characteristic peaks is directly
with different pretreatment (a) 400 oC in static air, (b) 400 oC related to the amount of element within
in 5%H2/Ar flow, (c) 400 oC in static air and hydrogen the XPS sampling volume.
peroxide treatment
• % composition (% atomic composition) for
Why Pd2+ appear at high BE? each element can be completed by
performing the de-convolution (peak-
fitting) of each XPS peaks to get area
intensity represent each metal oxidation
state with consideration of sensitivity
factor.
(i) Combined Au (4d) and Pd (3d) spectra of fresh
5wt%AuPd1.0wt%Cu/TiO2IW uncalcined catalyst, (ii) Overlay Au (4f) spectra
of uncalcined and calcined 5wt%AuPd1.0wt%Cu/TiO2IW catalyst, (a) Calcined
in static air at 400 oC for 3 hours, (b) Uncalcined (dried in air at 110 oC)
 Surface elemental compositions derived from XPS for the 5wt%Au–
Pd/TiO2IW catalysts prepared by impregnation method followed by
different pretreatment

Entry Catalyst/treatment Composition (atom Atom ratio

%) (Pd/Au)
Au/Ti Pd/Ti Measured Theoritically
expecteda
1 Static air, 400 oC 0.0075 0.0518 6.91 1.86
2 Flow 5%H2/Ar,400 oC 0.0049 0.0217 4.43 1.86
3 Static air, 400 oC and H2O2 0.0049 0.0267 5.49 1.86
treatment
a Assuming a random solid solution
• Consider as non-destructive • Applications in the industry:
– because it produces soft x-rays to – Polymer surface
induce photoelectron emission – Catalyst
from the sample surface. (Some,
– Corrosion
but not all, polymers, catalysts,
certain highly oxygenated – Adhesion
compounds, various inorganic – Semiconductors
compounds and fine organics are – Dielectric materials
degraded). – Electronics packaging
– Magnetic media
– Thin film coatings
– Paper
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 Deteriorated hardened cement paste
structure by XPS
XPS Applications in the Metal/Steel Industry

• Measuring composition and thickness of protective oxide films on

metals.
• Diagnose failures in the passivation process.
• Detect any contaminants that may have been introduced during
the manufacturing process.
XPS Applications in biomaterial/biomedical

Poly(propylene
fumarate)
(PPF)/titania
nanowire composites,
Tissue engineering
technology for
orthopedic bone
cements.
✓ XPS Applications in Biomedical Industry

✓ XPS Applications in Textiles Industry

✓ XPS Applications in Semiconductor Industry

✓ XPS Applications in Polymer Industry

Upon completion, students should be able;

• To explain the theory of X-Ray Photoelectron Spectroscopy

(XPS) used in chemical-related industries and sectors.
• To relate the X-Ray Photoelectron Spectroscopy (XPS) to the
applications in chemical-related industries and sectors
• To interpret the results from X-Ray Photoelectron Spectroscopy
(XPS)

Good Luck !!