X-RAY PHOTOELECTRON SPECTROSCOPY

1
 Contents
➢ Introduction

➢ Instrumentation

➢ Working Principle

➢ XPS Spectra Analysis

➢ Chemical Shifting in XPS

➢ Case Study

2
3
4
5
6
 XPS Instrument
• The XPS is controlled by
using a computer system.

• The computer system will

control the X-Ray type and
prepare the instrument for
analysis.

7
XPS Instrument
• The instrument uses
different pump systems to
reach the goal of an Ultra
High Vacuum (UHV)
environment.

• The Ultra High Vacuum

environment will prevent
contamination of the
surface and aid an
accurate analysis of the
sample.

8
 XPS Instrument

X-Ray Source

Ion Source

SIMS Analyzer

Sample
introduction
Chamber
9
 Diagram of the Side View
of XPS System
X-Ray source

Ion source
Detector
SIMS
Analyz Axial Electron Gun
er
Sample
introduction
Chamber

Sample
Holder
sample
CM
A
Roughing Pump Sli
Ion Pump ts

10
SCHEMATIC OF XPS

11
 WORKING PRINCIPLE OF X-RAY PHOTOELECTRON
SPECTROSCOPY (XPS)
• XPS technique is based on Einstein’s idea about Ejected Photoelectron
the photoelectric effect, developed around 1905
– The concept of photons was used to describe Incident X-ray
Free
the ejection of electrons from a surface when Electron
photons were impinged upon it Level
• The sample surface is irradiated with photons, Conduction Band
hitting the core electrons (e-) of the atoms Fermi
Level
• The X-Ray source produces photons with certain Valence Band
energies:
– MgK photon with an energy of 1253.6 eV 2p L2,L3
– AlK photon with an energy of 1486.6 eV
• Normally, the sample will be radiated with 2s L1
photons of a single energy (MgK or AlK),
known as a monoenergetic X-Ray beam
1s K

12
 WHY CORE ELECTRONS ?

Ejected Photoelectron
• An electron near the Fermi level is far from the
nucleus, moving in different directions and
does not carry information about any single Incident X-ray
atom. Free
Electron
– Fermi level is the highest energy level Level
occupied by an electron in a neutral solid
at absolute 0 temperature. Conduction Band
– Electron binding energy (BE) is calculated Fermi
with respect to the Fermi level. Level
Valence Band
• The core e-s are local close to the nucleus and
have binding energies characteristic of their
particular element. 2p L2,L3

• The core e-s have a higher probability of 2s L1

matching the energies of AlK MgK.
1s K

13
 EQUATION

KE = hv – BE – Ø

• The equation will calculate the energy needed to get an e- out from the
surface of the solid.
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 Binding Energy (unknown variable)

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

14
 X-RAYS ON THE SURFACE
• The X-Rays will penetrate to the core
e- of the atoms in the sample.
e- lower layer
e- top layer Outer surface
but no collisions
e- lower layer
• Some e-s are going to be released with collisions X-Rays Inner surface
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. Atoms layers
– They will contribute to the noise
signal of the spectrum.

15
 X-RAYS AND THE ELECTRONS
Electron without collision X-Ray

Electron with collision

• The noise signal comes from

the electrons that collide with
other electrons of different
layers
• The collisions cause a
decrease in energy of the
electron and it no longer will
contribute to the
characteristic energy of the
element

16
 XPS SPECTRUM

• 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

1000 eV 0 eV

E E E KE increase from left to right

Binding energy
(eV)

17
 INTERPRETING XPS SPECTRUM

• The X-Ray will hit the e-s in the bulk N = noise

(inner e- layers) of the sample

# of electrons
• e- will collide with other e- from top
layers, decreasing its energy to N4
contribute to the noise, at lower kinetic
energy than the peak
N3
• The background noise increases with BE N2
because the sum of all noise is taken
from the beginning of the analysis. N1

Binding energy

Ntot= N1 + N2 + N3 + N4

18
 WHY DOES XPS NEED UHV?
• Ultra High Vacuum (10−9 mbar) is required
– To ensure the longest possible mean path of the photoelectrons
– To avoid the contamination of the sample surface.

• The ambient atmosphere that a sample is exposed to can change its properties.
– XPS is a surface sensitive technique
– Contaminates will produce an XPS signal and lead to incorrect analysis of the surface
of composition
– For example, at a pressure of 10-6 mbar, background gas constituents (O2, H2O, etc.)
can react with the surface of a sample in several seconds

• 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.
19
THANK YOU
Any Queries?

20