X-Ray Photoelectron
Spectroscopy (XPS)
Prof. Paul K. Chu
X-ray Photoelectron Spectroscopy
Introduction
Qualitative analysis
Quantitative analysis
Charging compensation
Small area analysis and XPS imaging
Instrumentation
Depth profiling
Application examples
Photoelectric Effect
Einstein, Nobel Prize 1921
Photoemission as an analytical
tool
Kai Siegbahn, Nobel Prize 1981
XPS is a widely used surface analysis technique because of its
relative simplicity in use and data interpretation.
KE = hn - BE - FSPECT BE = hn - KE - FSPECT
hu: Al Ka(1486.6eV)
P 2s P 2p1/2-3/2
Kinetic Energy
Peak Notations
L-S Coupling ( j = l s)
e- 1
s= 12 s= 2
j= l + 12 j= l 1
2
For p, d and f peaks, two peaks are observed.
Au
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 elemental identification
Relative binding
energies and
ionization cross-
section for U
General methods in assisting peak identification
(1) Check peak positions and relative peak intensities of 2 or more
peaks (photoemission lines and Auger lines) of an element
(1) Check spin orbital splitting and area ratios for p, d, f peaks
A marine sediment sample from Victoria Harbor
Si 2p
Si 2s
Al 2s The following
Al 2p
elements are found:
O, C, Cl, Si, F, N, S,
Al, Na, Fe, K, Cu,
Mn, Ca, Cr, Ni, Sn,
Zn, Ti, Pb, V
Analysis Depth
Inelastic mean free path () is the mean distance that
an electron travels without energy loss
x
3 -
0
e dx
x
-
0
e dx
1 - e -3
0.95
1
For XPS, is in the range of 0.5 to 3.5 nm
Only the photoelectrons in the near surface region can
escape the sample surface with identifiable energy
Measures top 3 or 5-10 nm
B.E. = Energy of Final state - Energy of initial state
+
B A B
(one additional Redistribution of
+ve charge) electron density
B A B
B.E. provides information on chemical environment
Example of Chemical Shift
Example of Chemical Shift
Chemical Shifts
Chemical Shifts
Factors Affecting Photoelectron Intensities
For a homogenous sample, the measured photoelectron intensity is given by
I i ,c f N i i ,c cos F T D A
Ii,c: Photoelectron intensity for core level c of element i Detector
f: X-ray flux in photons per unit area per unit time
Ni: Number of atoms of element i per unit volume d
i,c: Photoelectric cross-section for core level c of element i
: Inelastic mean free path of the photoelectron in the sample matrix
: Angle between the direction of photoelectron electron and the sample normal
F: Analyzer solid angle of acceptance
T: Analyzer transmission function
D: Detector efficiency
A: Area of sample from which photoelectrons are detected
Quantitative Analysis
Peak Area of element A
IA Sensitivity factor of
SA element A
Atomic % 100%
Ii
i S Peak Areas / Sensitivity
i
factors of all other elements
Au 4f
Peak Area measurement
Need background subtraction
Empirical Approach
k = constant
SA = sensitivity factor of a
I A k S AM A core level of element A
MA = No. of A in the empirical
formula
I A S AM A IA MF
SA Usually assume SF=1
I F SF M F IF M A
For example, Teflon (-CF2-)
IC 2
SC
IF 1
Examples of Sensitivity Factors
1s Li2CO3 C 1s 0.067 0.069
Li2SO4 S 2p 0.069 0.067
KBF4 K 2p 0.50 0.50
NH4BF4 N 1s 0.55 0.57
Na2SO3 S 2p 2.95
CuSO4 S 2p 3.25
K2SO4 S 2p 2.90 2.85
Ag(COCF3)3 F 1s 2.62 2.81
Na5P3O10 Na 2s 3.40
C6H2NS2K3O9 K 2p 2.89 3.05
N
1
SA
N
S
i 1
Ai N = number of compounds tested
X-ray damage
Some samples can be
damaged by x-rays
For sensitive samples,
repeat the
measurement to check
for x-ray damage.
Charging Compensation
For metal or other conducting
Electron loss and compensation samples that grounded to the
spectrometer
-
e e-
X-ray
- -
e e- e
sample Electrons move to the surface
continuously to compensate
the electron loss at the surface
region.
For resistive samples
+ + + + + + + + "current" net loss of electrons
from the surface
e -
V RI
Potential developed Resistance between the
at the surface surface and the ground
I 10nA 10nA 10nA Note: for conducting
samples, charging
R 1k 1M 1000M may also occur if
-5
V 10 V 0.01V 10V there is a high
resistance at the back
Important
Not important for accurate B.E. contact.
measurements
Shift in B.E.
of a polymer
surface
+ + + + + + + +
Differential (non-uniform) surface charging
B
r
o
ad
en
i
ngo
f
pe
ak
Sample
Effects of Surface Charging
Charge Compensation Techniques
Low Energy Electron Flood Gun
filament
~2eV-20eV
Electrons
optics
-
e
Electron source Low energy
with magnetic field electrons and Ar+
analyser
+
electrons Low energy Ar beam
-ve
filament e X-ray Low energy
electron beam
Sample
Sample
Magnet A single setting for all types
of samples
Small area analysis and XPS Imaging
Photoelectrons Aperture of Photoelectrons Aperture of
Analyzer lens Analyzer lens
X-ray X-ray
Sample Sample
Spot size determined by the analyser Spot size determined by the x-ray beam
Both monochromated and dual anode
x-ray sources can be used
Instrumentation
Electron energy analyzer
X-ray source
Ar ion gun
Neutralizer
Vacuum system
Electronic controls
Computer system
Ultrahigh vacuum
< 10-9 Torr (< 10-7 Pa)
Detection of electrons
Avoid surface reactions/
contamination
Dual Anode X-ray Source
X-ray monochromator
n=2dsin
For Al Ka
8.3
use (1010) planes
of quartz crystal
d = 4.25
= 78.5
o
Advantages of using x-ray monochromator
Narrow peak width
Reduced background
No satellite & ghost peaks
Commonly used
Cylindrical Mirror Analyzer
CMA: Relatively high signal and good resolution ~ 1 eV
Concentric Hemispherical Analyzer (CHA)
Resolution < 0.4 eV
o
Inside: Heating stage (max. 1200 C)
and filament for radical generation
5 keV
argon
Top View Dosing ion gun
Mg
x-ray gun
unit
UHV
STM Gate
valve
UV source
UHV e-beam evaporator for UPS
Ion beam
source XPS
Wien Filter Target
chamber Wobble Sample stage
stick with heating/
LEED cooling
QMS for TDS Magnet
Heating/cooling
stage for TDS
Detachable
nitrogen
CMA-QMS X-ray
Low energy ion beam system Entry glove box
monochromator
loadlock
XPS system suitable for industrial samples
Vacuum Chamber Control Electronics
Ion pump
Turbopump
Sample Introduction Chamber
X-ray induced secondary electron x-ray secondary
imaging for precise location of the electrons
analysis area
+1
+2
500 x 500mm
Focused X-ray Source
Ellipsoidal
Scanning Focused Monochromator
Electron Beam
Scanning Focused
X-ray Beam
Analyzer Input Lens
Aluminum Anode
Sample
Depth Profiling
Ar+ Sputtered
materials
Peak Area
Sputtering Time
Depth Scale Calibration
1. Sputtering rate determined from the time required to sputter
through a layer of the same material of known thickness
2. After the sputtering analysis, the crater depth is measured using
depth profilometry and a constant sputtering rate is assumed
Concentration
Peak Area
Sputtering Time Depth
Angle Resolved XPS
Plasma Treated Polystyrene
Angle-Resolved
XPS Analysis
High-resolution
C 1s spectra
Plasma Treated Polystyrene
O concentration is higher near the surface
(10 degrees take off angle)
C is bonded to oxygen in many forms near
the surface (10 degrees take off angle)
Plasma reactions are confined to the surface
Angle-resolved
XPS analysis
Oxide on silicon
nitride surface
Typical Applications
Silicon Wafer Discoloration
Depth Profiling Architectural Glass Coating
Architectural glass coating
~100nm thick coating
Sputtered crater
Sample platen 75 X 75mm
Depth profile of Architectural Glass Coating
100
80
O 1s O 1s
O 1s
60
Ti 2p
40 Nb 3d
Si 2p Ti 2p N 1s Si 2p
20 N 1s
Al 2p
0
0 Surface 200
Sputter Depth (nm)
Nickel (30.3 nm)
Depth profiling Chromium (31.7 nm)
of a multilayer Chromium Oxide (31.6 nm)
Nickel (29.9 nm)
structure Chromium (30.1 nm)
Silicon (substrate)
100
80
60 Ni 2p Cr 2p metal Cr 2p oxide Ni 2p Cr 2p metal Si 2p
40 O 1s
20
0
0 Sputter Depth (nm) 185
Depth Profiling with Sample Rotation
High energy ions
100
80
Ions: 4 keV
60 Ni 2p
Cr 2p
Si 2p
Sample still
Ni 2p Cr 2p
40 Sample
O 1s
20 Cr/Si interface width (80/20%) = 23.5nm
Atomic concentration (%)
00
185
100 High energy ions
Ions: 4 keV
80 Si 2p
Ni 2p Cr 2p With Zalar rotation
60 Ni 2p Cr 2p
40 O 1s
Sample rotates
20
00
185 Cr/Si interface width (80/20%) = 11.5nm
100
80 Si 2p Ions: 500 eV Low energy ions
Cr 2p Ni 2p Cr 2p With Zalar rotation
60 Ni 2p
40 O 1s
20
00
Sample rotates
Sputtering depth (nm) 185
Cr/Si interface width (80/20%) = 8.5nm
Multi-layered Drug Package
Optical photograph of SPS Photograph
encapsulated drug tablets Cross-section of Drug Package
Al foil
Polymer
Coating A
Polymer Coating B
Adhesion layer
at interface ?
100 X 100mm 1072 X 812m
Photograph of cross-section
Polymer coating A
10m x-ray beam
30 minutes
Al
foil
++ +
-Si 2p
-Si 2s
1000 Binding Energy (eV) 0
1072 X 812m
Polymer A / Al foil Interface Polymer coating B
10m x-ray beam 10m x-ray beam
30 minutes 30 minutes
1000 Binding Energy (eV) 0 1000 Binding Energy (eV) 0
Polymer coating A Photograph (1072 X 812um)
10m x-ray beam
C 1s
11.7eV pass energy
30 minutes
Al foil
Interface
C
H ++ +
O=C-O CCl
298 288 278
Binding Energy (eV) Polymer coating B
Atomic Concentration (%) 10m x-ray beam C 1s
11.7eV pass energy
30 minutes
Area C O N Si
A 82.6 12.2 ---- 0.7
Interface 83.2 12.2 ---- 1.3 CH
B 85.9 9.8 4.3 ---- CNO
O=C-O
A silicon (Si) rich layer is present at 298 288 278
the interface Binding Energy (eV)
XPS study of paint
Paint Cross Section
Polyethylene
Mapping Area
Substrate
Adhesion Layer
Base Coat
Clear Coat
695 x 320m
1072 x 812mm
Elemental ESCA Maps using C 1s,
O 1s, Cl 2p, and Si 2p signals
C O Cl Si
695 x 320mm
C 1s Chemical State Maps
C 1s CH CHCl O=C-O
695 x 320mm
Small Area Spectroscopy
High resolution C 1s spectra from each layer
Polyethylene Substrate Base Coat
Polyethylene Substrate
CHn
CHn
CN
C-O
Adhesion Layer
O-C=O
300 280 300 280
Adhesion Layer Clear Coat
Base Coat
CHn CHn
C-O
Clear Coat CN
CHCl O-C=O
300 280 300 280
Binding Energy (eV) Binding Energy (eV)
800 x 500m
Quantitative Analysis
Atomic Concentration* (%)
Analysis Area C O N Cl Si Al
Substrate 100.0 --- --- --- --- ---
Adhesion Layer 90.0 --- --- 10.0 --- ---
Base Coat 72.0 16.4 3.5 3.3 2.6 2.2
Clear Coat 70.6 22.2 7.2 --- --- ---
*excluding H
Summary of XPS Capabilities
Elemental analysis
Chemical state information
Quantification (sensitivity about 0.1 atomic %)
Small area analysis (5 mm spatial resolution)
Chemical mapping
Depth profiling
Ultrathin layer thickness
Suitable for insulating samples
Sample Tutorial Questions
What is the mechanism of XPS?
What are chemical shifts?
How is depth profiling performed?
What is angle-resolved XPS?
Is XPS a small-area or large-area analytical
technique compared to AES?
Is XPS suitable for insulators?
What kind of applications are most suitable
for XPS?
