X-ray Photoelectron

Spectroscopy (XPS)
Surface Analysis
The Study of the Outer-Most Layers of Materials (<100 Α).

Electron Ion Spectroscopies

Spectroscopies SIMS: Secondary Ion
XPS: X-ray Mass Spectrometry
Photoelectron
Spectroscopy SNMS: Sputtered
Neutral Mass
AES: Auger Electron Spectrometry
Spectroscopy
ISS: Ion Scattering
EELS: Electron Energy Spectroscopy
Loss Spectroscopy
Introduction to
X-ray Photoelectron
Spectroscopy (XPS)
Introduction to X-ray Photoelectron
Spectroscopy (XPS)

What is XPS?- General

Theory
How can we identify elements
and compounds?
Instrumentation for XPS
Examples of materials analysis with
XPS
What is XPS?

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.
What is XPS?

X-ray Photoelectron spectroscopy,

based on the photoelectric effect,1,2 was
developed in the mid-1960’s by Kai
Siegbahn and his research group at the
University of Uppsala, Sweden.3

1. H. Hertz, Ann. Physik 31,983 (1887).

2. A. Einstein, Ann. Physik 17,132 (1905). 1921 Nobel Prize in Physics.
3. K. Siegbahn, Et. Al.,Nova Acta Regiae Soc.Sci., Ser. IV, Vol. 20 (1967).
1981 Nobel Prize in Physics.
XPS Background
XPS technique is based on Einstein’s idea about the
photoelectric effect, developed around 1905

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

electrons from a surface when photons were impinged upon it

During the mid 1960’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
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:

– MgKα photon with an energy of 1253.6 eV
– AlKα photon with an energy of 1486.6 eV

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

(MgKα or AlKα). This is known as a monoenergetic X-Ray beam.
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
AlKα and MgKα.
Valence e-

Core e- Atom
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 proton
p+ with certain binding
energy x
Energy Levels
Vacumm Level

Ø, which is the work function

Fermi Level At absolute 0 Kelvin the electrons fill

from the lowest energy states up.
When the electrons occupy up to this
BE
level the neutral solid is in its
“ground state.”

Lowest state of energy

X-ray Photoelectron Spectroscopy
Small Area Detection
Electrons are extracted
only from a narrow solid
X-ray Beam angle.

X-ray penetration
depth ~1µ m.
Electrons can be 10 nm
excited in this
entire volume. 1 mm2

X-ray excitation area ~1x1 cm2. Electrons

are emitted from this entire area
The Photoelectric Process
Ejected Photoelectron
Incident X-ray
Free XPS spectral lines are
Electron identified by the shell from
Conduction Band Level which the electron was
Fermi ejected (1s, 2s, 2p, etc.).
Level The ejected photoelectron has
Valence Band kinetic energy:
KE=hv-BE-Φ
2p L2,L3 Following this process, the
atom will release energy by
2s L1
the emission of an Auger
Electron.
1s K
Auger Relation of Core Hole
Emitted Auger Electron

Free L electron falls to fill core level

Electron vacancy (step 1).
Conduction Band Level
KLL Auger electron emitted to
Fermi conserve energy released in
Level step 1.
Valence Band The kinetic energy of the
emitted Auger electron is:
2p L2,L3
KE=E(K)-E(L2)-E(L3).
2s L1

1s K
Why Does XPS Need UHV?
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.
The Atom and the X-Ray
X-Ray
Free electron

Valence electrons

proton

neutron

electron
Core electrons

electron vacancy

The core electrons respond

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

Atoms layers
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.
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.
What e-s can the Cylindrical Mirror Analyzer
Detect?

The CMA not only can detect electrons from the

irradiation of X-Rays, it can also detect electrons from
irradiation by the e- gun.

The e- gun it is located inside the CMA while the X-Ray

source is located on top of the instrument.

The only electrons normally used in a spectrum from

irradiation by the e- gun are known as Auger e-s. Auger
electrons are also produced by X-ray irradiation.
XPS Energy Scale

The XPS instrument measures the

kinetic energy of all collected
electrons. The electron signal includes
contributions from both photoelectron
and Auger electron lines.
XPS Energy Scale- Kinetic energy
KE = hv - BE - Φspec

Where: BE= Electron Binding Energy

KE= Electron Kinetic Energy
Φspec= Spectrometer Work Function

If XPS spectra were presented on a kinetic energy scale,

one would need to know the X-ray source energy used to collect
the data in order to compare the chemical states in the sample
with data collected using another source.
XPS Energy Scale- Binding
energy
BE = hv - KE - Φspec

Where: BE= Electron Binding Energy

KE= Electron Kinetic Energy
Φspec= Spectrometer Work Function

The binding energy scale was derived to make uniform

comparisons of chemical states straight forward.
Fermi Level Referencing
Free electrons (those giving rise to conductivity) find
an equal potential which is constant throughout the material.

Fermi-Dirac Statistics: T=0 K

f(E) kT<<Ef
f(E) = 1 1.0
exp[(E-Ef)/kT] + 1
0.5

0
1. At T=0 K: f(E)=1 for E<Ef Ef
f(E)=0 for E>Ef

2. At kT<<Ef (at room temperature kT=0.025 eV)

f(E)=0.5 for E=Ef
Fermi Level Referencing

E f Fermi Edge of
TiN, room tem perture
N(E)/E

1.0 0.8 0.6 0.4 0.2 0.0 -0.2 -0.4 -0.6 -0.8 -1.0

Binding energy (eV)

Cylindrical Mirror Analyzer (CMA)

The electrons ejected will pass through a device called a

CMA.

The CMA has two concentric metal cylinders at different

voltages.

One of the metal cylinders will have a positive voltage and

the other will have a 0 voltage. This will create an electric
field between the two cylinders.

The voltages on the CMA for XPS and Auger e-s are
different.
Cylindrical Mirror Analyzer (CMA)
When the e-s pass through the metal cylinders, they will
collide with one of the cylinders or they will just pass
through.
– If the e-’s velocity is too high it will collide with the outer
cylinder
– If is going too slow then will collide with the inner cylinder.
– Only the e- with the right velocity will go through the cylinders
to reach the detector.

With a change in cylinder voltage the acceptable kinetic

energy will change and then you can count how many e -s
have that KE to reach the detector.
Cylindrical Mirror Analyzer (CMA)
Electron Pathway through the CMA
X-Rays
Source

Slit

0V 0V

+V +V

+V +V

Sample
Holder
0V 0V

Detector
 Sample/Spectrometer Energy Level
Diagram- Conducting Sample
e-

Sample Spectrometer
Free Electron Energy
KE(1s) KE(1s)
Vacuum Level, Ev
Φsample Φspec
hv
Fermi Level, Ef

BE(1s)
E1s

Because the Fermi levels of the sample and spectrometer are

aligned, we only need to know the spectrometer work function,
Φspec, to calculate BE(1s).
Sample/Spectrometer Energy
Level Diagram- Insulating
Sample
e-

Sample Spectrometer
Free Electron Energy
KE(1s)

Φspec
Vacuum Level, Ev
hv Ech
Fermi Level, Ef

BE(1s)
E1s
A relative build-up of electrons at the spectrometer
raises the Fermi level of the spectrometer relative to the
sample. A potential Ech will develop.
Binding Energy Referencing
BE = hv - KE - Φspec- Ech

Where: BE= Electron Binding Energy

KE= Electron Kinetic Energy
Φspec= Spectrometer Work Function
Ech= Surface Charge Energy

Ech can be determined by electrically calibrating the

instrument to a spectral feature.

C1s at 285.0 eV
Au4f7/2 at 84.0 eV
Where do Binding Energy Shifts
Come From?
-or How Can We Identify Elements and Compounds?
Fermi Level
Pure Element
Electron-electron Binding
Energy
repulsion
Look for changes here
Electron by observing electron
binding energies

Electron-nucleus
attraction Electron-
Nucleus
Separation

Nucleus
Elemental Shifts
Binding Energy (eV)
Element 2p3/2 3p ∆

Fe 707 53 654
Co 778 60 718
Ni 853 67 786
Cu 933 75 858
Zn 1022 89 933

Electron-nucleus attraction helps us identify the

elements
Elemental Shifts
Binding Energy Determination
The photoelectron’s binding energy will be
based on the element’s final-state configuration.

Initial State Free

Final State
Electon
Conduction Band Level Conduction Band
Fermi
Level
Valence Band Valence Band

2p
2s

1s
The Sudden Approximation
Assumes the remaining orbitals (often called the passive orbitals) are
the same in the final state as they were in the initial state (also called
the frozen-orbital approximation). Under this assumption, the XPS
experiment measures the negative Hartree-Fock orbital energy:

Koopman’s Binding Energy

EB,K ≅ -εB,K

Actual binding energy will represent the readjustment of the N-1

charges to minimize energy (relaxation):

EB = Ef N-1 - Ei N
Binding Energy Shifts
(Chemical Shifts)
Point Charge Model:

Ei = Ei0 + kqi + Σ q /ri ij

EB in atom i in given Weighted charge of i Potential at i due to

refernce state surrounding charges
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.
 XPS Spectrum
O 1s

O Auger

O because
of Mg source

C O 2s
Al
Al

Sample and graphic provided by William Durrer, Ph.D.

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

Characteristic of Auger graphs

The graph goes up as KE increases.

Sample and graphic provided by William Durrer, Ph.D.

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 you can look for the

designated value of the peak energy from the graph and
find the element present on the surface.
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.
Chemical Shifts-
Electronegativity Effects
Carbon-Oxygen Bond
Oxygen Atom

Electron-oxygen
atom attraction
Valence Level (Oxygen Electro-
C 2p C 1s
negativity)
Binding
Energy
Core Level
Shift to higher
C 1s binding energy
Electron-nucleus
attraction (Loss of
Electronic Screening)

Carbon Nucleus
Chemical Shifts-
Electronegativity Effects
Functional Binding Energy
Group (eV)
hydrocarbon C-H, C-C 285.0
amine C-N 286.0
alcohol, ether C-O-H, C-O-C 286.5
Cl bound to C C-Cl 286.5
F bound to C C-F 287.8
carbonyl C=O 288.0
Electronic Effects
Spin-Orbit Coupling

C 1s

O r b ita l= s
l= 0
s = + /-1 /2
ls = 1 /2

290 288 284 280 276

B in d in g E n e r g y ( e V )
Electronic Effects
Spin-Orbit Coupling
Cu 2p 2 p 3 /2

2 p 1 /2
O r b ita l= p
l= 1
s = + /-1 /2
ls = 1 /2 ,3 /2
1 9 .8
P e a k A re a 1 : 2

965 955 945 935 925

B in d in g E n e r g y ( e V )
Electronic Effects
Spin-Orbit Coupling
Ag 3d 3 d 5 /2
3 d 3 /2
O r b ita l= d
l= 2
s = + /-1 /2
6 .0 ls = 3 /2 ,5 /2
P e a k A re a 2 : 3
378 374 370 366 362
B in d in g E n e r g y ( e V )
Electronic Effects
Spin-OrbitCoupling
Au 4f 4 f7 /2
4 f5 /2
O r b ita l= f
l= 3
s = + /-1 /2
ls = 5 /2 ,7 /2
3 .6 5
P e a k A re a 3 : 4
91 87 83 79
B in d in g E n e r g y ( e V )
Electronic Effects- Spin-Orbit Coupling

Ti Metal Ti Oxide
Final State Effects-
Shake-up/ Shake-off
Results from energy made available in the relaxation of the final
state configuration (due to a loss of the screening effect of the
core level electron which underwent photoemission).
L(2p) -> Cu(3d)
Monopole transition: Only the principle
quantum number changes. Spin and
angular momentum cannot change.
Shake-up: Relaxation energy used to
excite electrons in valence levels to
bound states (monopole excitation).
Shake-off: Relaxation energy used to
excite electrons in valence levels to
unbound states (monopole ionization).
Final State Effects-
Shake-up/ Shake-off

Ni Metal Ni Oxide
Final State Effects- Multiplet Splitting

Following photoelectron emission, the

remaining unpaired electron may
couple with other unpaired electrons in
the atom, resulting in an ion with
several possible final state
configurations with as many different
energies. This produces a line which
is split asymmetrically into several
components.
Electron Scattering Effects
Energy Loss Peaks

eph + esolid e*ph + e**solid

Photoelectrons travelling through the

solid can interact with other electrons in
the material. These interactions can result
in the photoelectron exciting an electronic
transition, thus losing some of its energy
(inelastic scattering).
XPS of Copper-Nickel alloy
120
Peak R e l. A t o m ic
C u 2p
A re a S ens. C onc
100 M c t-e V /s e c %
Ni 2 .6 5 4 .0 4 4 49
Cu 3 .6 5 5 .3 2 1 51
80
T h o u sa n d s

Cu
N ( E ) /E

60 N i 2p LM M C u
N i LM M
Cu
LM M N i
LM M
40 LM M N i
LM M

N i 3p
20
C u 3p

0
-1 1 0 0 -9 0 0 -7 0 0 -5 0 0 -3 0 0 -1 0 0
B in d in g E n e r g y ( e V )
Comparison of Sensitivities
H Ne Co Zn Zr Sn Nd Yb Hg Th

A ES a n d X PS

1%

5E19
RBS

PP IX
I X EE

1ppm 5E16

S IM S

1ppb 5E13
0 20 40 60 80 100
A T O M IC N U M B E R
Instrumentation for X-ray
Photoelectron
Spectroscopy
Introduction to X-ray Photoelectron
Spectroscopy (XPS)

What is XPS?- General Theory

How can we identify elements and
compounds?
Instrumentation for XPS
Examples of materials analysis with
XPS
Instrumentation for XPS
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.
Why UHV for Surface Analysis?
Pressure
Degree of Vacuum Torr
Remove adsorbed gases from
102 the sample.
Low Vacuum
Eliminate adsorption of
10-1
contaminants on the sample.
Medium Vacuum
10-4 Prevent arcing and high voltage
High Vacuum breakdown.
10-8 Increase the mean free path for
Ultra-High Vacuum electrons, ions and photons.
10-11