Introduction to

X-ray Photoelectron Spectroscopy (XPS)

X
X
-
-
ray Photoelectron Spectroscopy (XPS), also
ray Photoelectron Spectroscopy (XPS), also
known as Electron Spectroscopy for Chemical
known as Electron Spectroscopy for Chemical
Analysis (ESCA) is a widely used technique to
Analysis (ESCA) is a widely used technique to
investigate the chemical composition of surfaces.
investigate the chemical composition of surfaces.

XPS which makes use of the photoelectric effect,

s by Kai
s by Kai
Siegbahn
Siegbahn
and his research group at the University of
and his research group at the University of
Uppsala, Sweden.
Uppsala, Sweden.
Photoemission of Electrons
Conduction Band Conduction Band
Valence Band Valence Band
L2,L3 L2,L3
L1 L1
K K
Fermi Level Fermi Level
Free Electron Level (vacuum) Free Electron Level (vacuum)
Incident X Incident X- -ray ray
Ejected Photoelectron Ejected Photoelectron
1s 1s
2s 2s
2p 2p
XPS spectral lines are identified by the
shell from which the electron was ejected
(1s, 2s, 2p, etc.).
The ejected photoelectron has kinetic
energy:
KE= hv BE -
Following this process, the atom will
release energy by the emission of a
photon or Auger Electron.
Auger Electron Emission
Conduction Band Conduction Band
Valence Band Valence Band
L2,L3 L2,L3
L1 L1
K K
Fermi Fermi
Level Level
Free Free
Electron Electron
Level Level
1s 1s
2s 2s
2p 2p
Conduction Band Conduction Band
Valence Band Valence Band
1s 1s
2s 2s
2p 2p
L electron falls to fill core level vacancy (step 1). L electron falls to fill core level vacancy (step 1).
KLL Auger electron emitted to conserve energy released in step 1 KLL Auger electron emitted to conserve energy released in step 1. .
The kinetic energy of the emitted Auger electron is: The kinetic energy of the emitted Auger electron is:
KE=E(K) KE=E(K)- -E(L2) E(L2)- -E(L3). E(L3).
XPS Energy Scale - Binding energy
BE =
BE =
hv
hv
-
-
KE
KE
-
-

spec spec
Where: Where: BE= Electron Binding Energy BE= Electron Binding Energy
KE= Electron Kinetic Energy KE= Electron Kinetic Energy

spec spec
= Spectrometer Work Function = Spectrometer Work Function
Photoelectron line energies: Photoelectron line energies: Not Dependent Not Dependent on photon energy. on photon energy.
Auger electron line energies: Auger electron line energies: Dependent Dependent on photon energy. on photon energy.
XPS spectrum of Vanadium
Auger electrons
Note the stepped background
Only electrons close to surface can escape elastically ( 63%, 3 95%))
Electrons from deeper in sample undergo inelastic collisions while
traveling to the surface giving rise to the stepped background
Empirical models can be used to subtract the backgorund
X-ray Photoelectron Spectrometer
X X- -ray ray
Source Source
Electron Electron
Optics Optics
Hemispherical Energy Analyzer Hemispherical Energy Analyzer
Position Sensitive Position Sensitive
Detector (PSD) Detector (PSD)
Magnetic Shield Shield
Outer Sphere Outer Sphere
Inner Sphere Inner Sphere
Sample Sample
Computer Computer
System System
Analyzer Control Analyzer Control
Multi Multi- -Channel Plate Channel Plate
Electron Multiplier Electron Multiplier
Resistive Anode Resistive Anode
Encoder Encoder
Lenses for Energy Lenses for Energy
Adjustment Adjustment
(Retardation) (Retardation)
Lenses for Analysis Lenses for Analysis
Area Definition Area Definition
Position Computer Position Computer
Position Address Position Address
Converter Converter
54.7
Hemispherical electron
energy analyzer
Cylindrical mirror
electron energy
analyzer
X-ray source
e-
X-rays
water
Tungsten Filament
~15,000 Volts
Mg(K) : h = 1253.6 eV
Al(Ka) : h = 1486.6 eV
Note that most XPS peaks
appear as doublets
965 955 945 935 925
19.8
Binding Energy (eV)
Cu 2p
2p
1/2
2p
3/2
Peak Area 1 : 2
965 955 945 935 925
19.8
Binding Energy (eV)
Cu 2p
2p
1/2
2p
3/2
Peak Area 1 : 2
Electron quantum numbers
orbital momentum: l = 0,1,2,3 (s, p, d, and f orbitals)
spin momentum: s = +, -
total momentum: j =l + s
Since s can be +or -, each level with l >0 is
split into two sublevels with an energy difference
known as the spin-orbit splitting. The degeneracy
of each of these levels is 2j+1
A little quantum mechanics is needed to
understand why this is the case
Orbital l j degeneracy Electron level
1s 0 1/2 1 1s
2s 0 1/2 1 2s
2p 1 1/2 2 2p
1/2
2p 1 3/2 4 2p
3/2
3d 2 3/2 4 3d
3/2
3d 2 5/2 6 3d
5/2
4f 3 5/2 6 4f
5/2
4f 3 7/2 8 4f
7/2
965 955 945 935 925
19.8
Binding Energy (eV)
Cu 2p
2p
1/2
2p
3/2
Peak Area 1 : 2
Orbital l j degeneracy Electron level
2p 1 1/2 2 2p
1/2
2p 1 3/2 4 2p
3/2
370 374 378 366 362
6.0
Binding Energy (eV)
Peak Area 2 : 3
Ag 3d
3d
3/2
3d
5/2
Orbital l j degeneracy Electron level
3d 2 3/2 4 3d
3/2
3d 2 5/2 6 3d
5/2
3.65
87 91 83 79
Binding Energy (eV)
Peak Area 3 : 4
Au 4f
4f
5/2
4f
7/2
Orbital l j degeneracy Electron level
4f 3 5/2 6 4f
5/2
4f 3 7/2 8 4f
7/2
What information can you obtain from XPS?
What information can you obtain from XPS?
Identification of elements near the surface and
surface composition
Local chemical environments
Oxidation states of transition metals
Valence band electronic structure
Morphology of thin films
The universal electron scattering curve
Sampling Depth
Electron mean free path is energy dependent
Sampling depth is materials dependent
XPS is surface sensitive but samples more than just
the surface
Electron Energy (eV)
M
e
a
n

F
r
e
e

P
a
t
h
,

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

Fe 707 53 654
Co 778 60 718
Ni 853 67 786
Cu 933 75 858
Zn 1022 89 933
Atomic Number
B
i
n
d
i
n
g

E
n
e
r
g
y
,

e
V
Electron Binding Energies
Chemical Shifts
Chemical Shifts
In addition to the identity of the element and the orbital
(s,p, d, f) electron binding energies depend on:
(1) the formal oxidation state of the atom
(2) the local chemical environment
Both (1) or (2) cause small binding energy shifts (< 5 eV)
An increase in oxidation state causes the binding energy to
increase due to a decrease in the screening of the bound
electron from the ion core. The ability of XPS to determine
oxidation states is used extensively in catalysis research.
Oxidation States Vanadium foil
V
0
V
2
O
5
V
5+
V(2p
3/2
)
V
0
V
+5
511.95 eV 517.45 eV
O
505 515 525 535
Binding energy, eV
O 1s
V 2p
3/2
V 2p
1/2
VO
x
/TiO
2
(110)
500 510 520 530 540
Binding energy, eV
d
c
b
a
V 2p
1/2
V 2p
3/2
O 1s
Binding energy, eV
10
-7
torr O
2
Just deposited
525 520 510 515
10
-3
torr O
2
V 2p
3/2
0.5 ML VO
x
- XPS
VO
x
/CeO
2
(111)
10
-3
torr O
2
400 K
10
-7
torr O
2
575 K
As deposited
Clean substrate
V
0
512.3 eV
V
+3
515.3 eV
V
+4
515.7 eV
V
+5
516.8 eV
V 2p
3/2
Chemical Shifts - Electronegativity Effects
Local chemical environment can also cause small
shifts in XPS peak positions
Functional
Group
C(1s)Binding Energy
(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
Electronegative substituents decrease the electron density on the carbon atom
causing a small in crease in the C(1s) binding energy
C-F
+ -
XPS of Polyethylene-terephthalate
O
O
C
O
C O CH
2
CH
2
n
Quantitative elemental analysis Chemical state analysis
1s 1s
2s 2s
2p 2p
3d 3d
h
Primary photoemission
Shake-up process
1s 1s
2s 2s
2p 2p
3d 3d
h
E
KE = KE = hv hv - - BE BE - -
KE = KE = hv hv - - BE BE - - - - E E
860 880 900 920 940
Binding energy, eV
Ce(3d) - Ce
+4
u'''
u
v''
v'
v'''
u''
u'
v
Peaks Initial State Final State
Ce
4+
v,u 3d
10
4f
0
3d
9
4f
2
V
n-2
Ce
4+
v'',u'' 3d
10
4f
0
3d
9
4f
1
V
n-1
Ce
4+
v''',u''' 3d
10
4f
0
3d
9
4f
0
V
n
Final State Effects - Shake-up features
Shake Shake- -up features occur when additional electron energy level transiti up features occur when additional electron energy level transitions occur ons occur
during the photoelectron emission process during the photoelectron emission process
Quantitative Analysis of XPS DATA
Quantitative Analysis of XPS DATA
For a homogenous sample:
Element sensitivity factors
Sensitivity factor = S = f D
f = x-ray flux
s = photoelectron cross-section
D = detector efficiency
=electron mean free path
n
1
n
2
I
1
/S
1
I
2
/S
2
=
n
i
= number of I atoms
I
i
= area of I photoemission peak
S = sensitivity factor for i
n
x
I
x
/S
x
n
i
I
i
/S
i
=
i i
C
x
= concentration of element x
C
x
=
Relative Sensitivities of the Elements
0
2
4
6
8
10
12
Elemental Symbol
R
e
l
a
t
i
v
e

S
e
n
s
i
t
i
v
i
t
y
Li
Be
B
C
N
O
F
Ne
Na
M
Al
Si
P
S
Cl
Ar
K
Ca
Sc
Ti
V
Cr
M
Fe
Co
Ni
Cu
Zn
G
G
As
Se
Br
Kr
Rb
Sr
Y
Zr
Nb
M
Tc
Ru
Rh
Pd
Ag
Cd
In
Sn
Sb
Te
I
Xe
Cs
Ba
La
Ce
Pr
Nd
P
S
Eu
G
Tb
Dy
Ho
Er
T
Yb
Lu
Hf
Ta
W
Re
Os
Ir
Pt
Au
Hg
Tl
Pb
Bi
1s
2p
3d
4d
4f
S(F
1s
) = 1.0
500 510 520 530 540
Binding energy, eV
0
20
40
60
80
0 2 4 6
C
e

3
d
/

V

2
p
3
/
2

i
n
t
e
n
s
i
t
y

ML of vanadium deposited
ML of V
5.5
0
0.25
0.5
1.0
O 1s
V 2p
1/2
V 2p
3/2
Vanadium Deposition on CeO
2
(111)
Layer-by-layer
film growth
V
+3
XPS
CeO
2
(111)
V 2p
3/2
= 515.7 eV
Thin Film Morphology
Thin Film Morphology
XPS Depth Profiling
Ar
+
ion source
S
p
u
t
t
e
r
i
n
g

t
i
m
e
XPS depth profile of SiO
2
layer
on silicon wafer
Si(2p) - 99.3 eV
Si
4+
(2p) - 103.3 eV
Scanning XPS
- Provides elemental and chemical state maps of surfaces
Use electrostatic lenses
to select which are of the
surface is analyzed
Raster the x-ray beam.
Requires the electron beam in
the x-ray source to be rastered
and a complex quartz crystal lens
to focus the x-rays .
XPS image of a patterned polymer film
image line scan
XPS of Supported Catalysts
XPS of Supported Catalysts
Issues:
Sample is not homogenous
Only analyze external surface
Sample charging
Beam damage
Valence Band Photoelectron Spectroscopy Valence Band Photoelectron Spectroscopy
Density of states near the Fermi level.
Electronic states in the band gap
Binding energies of valance electrons of adsorbates
Need very high energy resolution to obtain useful information. He discharge lamp or synchrotron
is typically used as the photon source
If ultraviolet photons (rather than x-rays) are used the technique is called Ultraviolet
Photoelectron Spectroscopy (UPS). Other than the photon source instrumentation is identical to
that of XPS
Sample
Ionized He,
Produce photons at 21.2
and 40.8 eV
UPS Spectra of Ag/Ru(001) and AuRu(001)
UPS Spectra of Ag/Ru(001) and AuRu(001)
UPS Spectra of Adsorbates
UPS Spectra of Adsorbates