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?