Course I.A. XPS Basics

Course I
Fundamentals of surface and interface science

and use of XPS
Paul G. Rouxhet
Prof. emeritus, Universit catholique de Louvain
Louvain-la-Neuve, Belgium
Paul.rouxhet@uclouvain.be
1st Colombian Seminar on Surface Science

Bucamaranga, 23-27 November 2015
A. Surface analysis by XPS: basic
aspects
B. Colloids and surfaces
C. Surface analysis by XPS: advanced
1
aspects
The slides are readable on prints

of 6 or 9 slides per A4 sheet
Course I.A
Surface analysis by XPS
Basic aspects
Paul G. Rouxhet
Prof. emeritus, Universit catholique de Louvain
Louvain-la-Neuve, Belgium
Paul.rouxhet@uclouvain.be
1st Colombian Seminar on Surface Science

Bucamaranga, 23-27 November 2015
With acknowlegments of contributions from
Christine Dupont and Michel Genet
3
XPS - Basic aspects

Scope :
Physical process instrument

chemical information surface selectivity ;
global vision and critical mind
X-rays and electrons

Essence of XPS
Instrumental aspects
Features of a XPS spectrum
Quantification
Chemical shift
Time line
M.J. Genet, C.C. Dupont-Gillain, P.G. Rouxhet
XPS analysis of biosystems and biomaterials
in Medical applications of colloids (ed. E. Matijevic),
Springer, New-York 2008, p. 177-307
Practical reference: close to the course, can be forwarded on request
4

Incident
particle
Attenuation
Primary
emission
A+* + e
Secondary emission
Radiat. relaxation Auger effect
A+* A+ + h
A+* A++ + e
Absorption sp. Photoelectron sp. Fluorescence

Surface anal. Elemental anal.
X-Ray imaging
X-ray filter
Transmission
electron micr.
Electr. energy
loss spec.
Auger peaks
in XPS spec.
Electr. microprobe
Element anal.
+ space resolut.
imaging
Auger spec.
Surface anal.
+ space resolut.
imaging
X-ray source
Scanning
electron micr.
Morphology,
imaging

Electron orbitals
Shell
subshell //
n
l (0 to n-1) ml (- l 0 +l)
Spin -1/2, +1/2
orbital shape
angular moment
orientation
d 2
-2, -1, 0, +1, +2
d 1
-1, 0, +1
d 0
0
p 1
-1, 0, +1
p 0
0
s 0
0
p 1
-1, 0, +1
p 0
0
s 0
0
s 0
0
Spin orbit coupling
Resulting angular moment j = l- 1/2 or l+

mj = -j, -j+1, j-1, j
6

_________zero binding level_____________________________________
_
3d
3d
5/2 ____
3/2 _______
3p
3p
3/2 ______
1/2 _________
3s
1/2 _________
2p
2p
3/2 ______
1/2 _________
L series
2s
1/2 _________
_2s
1s
1/2 _________
K series
K
M series
_
_
Occupation
Name
in X-ray
spectroscopy
_2p3/2
_2p1/2
_LIII
_LII
K
_ 2
_
K1
_LI
_1s
_K
XPS peaks X-ray

absorption emission
7
edges
lines
X-ray
__

_________zero binding level_____________________________________ _
3d
3d
5/2 ____
3/2 _______
3p
3p
3/2 ______
1/2 _________
3s
1/2 _________
93
2p
2p
3/2 ______
1/2 _________
708 13035
73
721 15200
2s
1/2 _________
118
846
1s
1/2 _________ 1560
7112
88004
Fe
Pb
2484
2585
3066
54
Al
Position of
energy levels
3554
3850
15860
_ 2p3/2
_ K1
_2p1/2 _K2
_2s
_1s
XPS peaks
emission
lines
8
_ __
X-ray
Fluorescence spectrum (scale in keV)

Fe K, 7.11 - 0.71
Fe K, 7.11 - 0.05
Al K, 1.56 - 0.07
Conversion between energy and wavelength of photon

E = h = h c / = 6.6 10-34 3 108 / 10-10
in angstrm
E in joule
1 Faraday * 1 V = 96500 C.V = 96500 joule = N eV

E = h = (6.6 10-34 3 108 / 10-10) (6.023 1023 / 96500)
= 12400 /
E in eV
in
10
Absorption spectrum (scale in )

12400/15860
= 0.78
12400/13035
= 0.95
12400/15200
= 0.82
11

_________zero binding level_____________________________________ _
3d
3d
5/2 ____
3/2 _______
3p
3p
3/2 ______
1/2 _________
3s
1/2 _________
93
2p
2p
3/2 ______
1/2 _________
708 13035
73
721 15200
2s
1/2 _________
118
846
1s
1/2 _________ 1560
7112
2484
2585
3066
54
Al
Position of
energy levels
3554
Fe
3850
15860
88004
_LIII
_LII
_ K1
K
_2
_LI
_K
Pb
X-ray
absorption emission
edges
lines
12
X-ray
Essence of XPS
Principle
Photoemission
Photoelectron 1s
with kinetic energy Ek
13
Essence of XPS
hemispherical
Hemispherical electron
electron
energy analyzer
Electron multiplier
electron
multiplier
sample
Sample
Counts
X-rays
retardation
Retardation
stage
Ek = h Eb
Ek
Eb : electron binding energy

peak characteristic of a given element
elemental analysis
Koopmans approximation: binding energy = energy required to remove e
from energy level to assuming no rearrangement of other electrons
14
Essence of XPS
Survey spectrum of collagen

(freeze-dried powder)
Intensity (103 counts/s)
70
O 1s
60
C 1s
50
40
N 1s
30
20
10
1000
800
600
400
Binding Energy (eV)
200
15
Essence of XPS
Energy levels of selected elements
16
Essence of XPS
Global view of photoelectron spectroscopy
Information related to energy levels

- analytical aspects: elemental composition
atom environment chemical functions
- theoretical chemistry: electron energy levels
molecular orbitals
Energy levels - core, with X-ray : XPS, ESCA
- external, with UV : UPS
17
Essence of XPS
From principle to measurement
Ek = Ek sp Ec
= h Eb sp Ec
sp : spectrometer work function, work spent to bring e
from zero attraction by the sample to entrance of analyzer
Ec : case conductor = 0
case of insulator, sample charging
18
Essence of XPS
Elemental analysis with surface selectivity
X-ray
h
400
400
1-10 nm
Sample
600
600
800
800 1000
1000 1200
1200 1400
1400
Kinetic
Kinetic Energy
Energy (eV)
(eV)
Ground
c
Electrons contributing to the peaks: no energy loss
Electrons contributing to the background: energy loss
Electrons not ejected from the solid

19
Essence of XPS
Contribution of a layer of thickness dz at depth z
X-ray
h
P C dz Q
e
z
P C dz
dz
C concentration of photoelectron emitor in homogeneous solid

P constant for a given element and level (probability of electron emission)
and for a given explored area
Attenuation Q = exp (- z / cos )
20
Essence of XPS
Q = exp (- z / cos )
Attenuation
cfr Beer-Lambert law
Iin
dx
I I-dI
Iout
x
t
- dI /I = dx /
- ln Iout / Iin = - ln Q = t /
Q = exp (-t / )
: inelastic mean free path IMFP,

= - dx /(dI/I)
analogous to (absorption coefficient)-1

average distance such that dI/I= -1
average distance between inelastic collisions
21
Essence of XPS
Contributions of increasing depths

assuming that C is constant
% cumulated
63%
86%
95%
98%
P C exp(-z/ cos)
0
PC
PC
2
3
4
P C exp(-z/ cos)dz
P C cos
z/cos
22
Essence of XPS
Contributions of increasing depths
% cumulated
P C exp(-z / cos)
63%
86%
95%
98%
PC
PC
2
3
4
P C exp(-z / cos) dz
P C cos
z/ cos
If the solid has a homogeneous composition, things happen
as if the peak was due to a layer of thickness cos
and the photoelectron intensity was not attenuated
23
Essence of XPS
Illustration: oxidation of germanium
24
Essence of XPS
Analysis at different angles
= 0, cos = 1
= 80, cos = 0.17
Surface is depleted in PAA compared to 25

PS
XPS - Basic aspects

Essence of XPS
vacuum
X-ray source
energy analyzer
detection
surface charging
miscellaneous
26
Vacuum
27
Kratos Axis Ultra
Vacuum
High vacuum
to reduce
inelastic collisions between photoelectrons and gas molecules
detector, gauges degradation (electrical discharges)
surface contamination
(!!!!!)
Need of Ultra High Vacuum conditions

Aim : 10-7 Pa
Practice : ~10-6 Pa (10-11 atm ; 10-8 torr)
Introduction chamber
Analysis chamber
Pumps
28
Source
Coolidge tube
29
Source
Source without monochromator
1.486,6 eV
1.253,6 eV
N.B. Other less common anodes : Zr (151.4 eV); Si (1739.6 eV);

Ag (2984 eV); Ti (4510.9 eV); Cu(8047.8 eV)30
Source
X-ray emission spectrum from an aluminum source

K1,2
1.486,7 eV Int 2/3

K3,4 : due to
relaxation of Al++*
1.486,3 eV Int 1/3
Due to
slowing down of e in
the atom atmosphere
bremsstrahlung
K3,4
K
10000
1559
1487
E (eV)
1497
31
Source
Radiation filter
Emission spectrum of aluminum
Absorption spectrum of aluminum : absorption edge K
K1,2
1560 eV
bremsstrahlung
K3,4
K
10000
1559
1487
1497
E (eV)
32
Source
Satellites due to the source

Mg source
3
x 10
20
O 1s
18
due to K1,2
K 1,2
16
Ek= h- Eb
K3,4
14
due to
CPS
K3,4
12
K5,6
10
Real
Apparent
Esk = hs - Eb
Ebapp = h - Esk
= h - hs + Eb
= 10 eV
570
560
550
540
530
Binding Energy (eV)
520
510
Eb
etc
Ebapp
33
Source
Source with monochromator

Selection of wavelength through diffraction by a crystal
(Braggs law)
Al K1,2
removes K3,4
sharpens
K1,2
Al
34
Source
Effect of monochromatization
C 1s on Poly(ethylene terephthalate) - PET

VG ESCA 3 Mkll (1978)
Mg K, not monochrom., Ep 50 eV
SSI SSX 100/206 ( 1988)

Al K, monochrom., Ep 50 eV
Intensity (a.u.)
KRATOS Axis Ultra (1999)

Al K, monochrom., Ep 40 eV
300
296
292
288
Binding Energy (eV)
284
280
Monochromatisation reduces the width of K1,2 line,

K2 contribution is drastically reduced
35
Analyzer
Kinetic energy analysis
hemispherical
electron
energy analyzer
electron
Electron multiplier
multiplier
Sample
sample
Counts
X -rays
retardation
Retardation
stage
Ek
36
Ek
Analyzer
Concentric Hemispherical Analyzer (CHA-HSA)
Ep
Electrons of energy Ep injected tangentially in S :
circular orbits of radius R0 fall on F if
R1 R2
E p e(V 1 V 2) 2
R1 R22
Ep : pass energy
Spectrometer constant
37
Analyzer
Entrance and exit slit width: W
R
Ep
Electrons with lower or higher energy than Ep :
path radius smaller or larger than R0 , R
Possibility to sweep the Ek spectrum by sweeping Ep, i.e. V1-V2
38
Analyzer
Dispersion
R = (2 R0 / Ep) E
Entrance and exit slit width: W
R
Ep
Effective resolution : Eeff = (E/R) W

= (Ep/ 2 R0) W
energy resolution (Eeff) would change with electron energy
analyzer radius (R0) would be very high
to obtain a good energy resolution (Eeff)
39
Analyzer
Kinetic energy analysis

hemispherical
electron
energy analyzer
X -rays
retardation
Retardation
stage
Electron multiplier
electron
multiplier
Ekdet = Epass = Ek - Eret
Counts
Sample
sample
Constant analyzer energy mode
Ek
Epass constant; Ek swept by sweeping Eret

resolution constant in recorded spectrum
40
Ek
Analyzer
Effect of Epass on spectrum
Eeff = (Ep/ 2 R0) W

Peak width
Epass in eV
Peak intensity
Au 4f7/2
80
Au 4f7/2
70
counts/s)
3 10
150
Intensity (a.u.)
Intensity (
100
50
25
60
50
40
100
30
20
10
0
87 86 85 84 83 82
Binding Energy (eV)
150
50
25
87 86 85 84 83 82
Binding Energy (eV)
Constant spot size 600 m
FWHM : full width at half maximum
SSI SSX 100/206
41
Analyzer
Effect of Epass on spectrum resolution
PET
O 1s
O 1s
Pass energy 40eV

Pass energy 20 eV
Pass energy 40 eV
Pass energy 20 eV
C 1s
C 1s
Arbitrary units
Arbitrary units
Ep = 40 eV
Ep = 20 eV
544 542 540 538 536 534 532 530 528
Binding Energy (eV)
Ep = 40 eV
Ep = 20 eV
300
290
280
Binding Energy (eV)
Peaks height normalized

42
Analyzer
Electrostatic input lens
Transfer a magnified image of the

analysed area from the sample plane
to the entrance slit plane of the
analyzer
More free space around the sample
Reduce image distortion
Acts as a retardation stage
Ekdet = Ek - Eret
Retarding potential
43
Analyzer
Magnetic lens
Sample immersed in
a magnetic field
Sample to be supported at some distance

from the electrostatic lens
High collection efficiency (high collection angle)
High spatial resolution
Kratos Axis ultra
The current trough the lens is varied according to Ek
44
Analyzer
Comparison between lens modes

50
45
C 1s
40
counts/s)
3 10
Hybrid mode: combination of

electrostatic end magnetic lens
35
30
25
20
Intensity (
15
Electrostatic mode:
electrostatic lens only
10
5
296 292 288 284
Binding Energy (eV)
Oxygen plasma treated polystryrene

With magnetic lens: higher intensity and improved resolution
higher efficiency of charge stabilisation device
Kratos Axis Ultra
45
Analyzer
Analyzed area versus bombarded area

X-ray
Method
e-
Analyser
slit
Al or Mg
Non-mono
Bombarded Several
area
mm2
Analysed
Several
area
mm2
(smallest)
X-ray
Old generation
X-ray
X-ray
X-ray
e-
Focused Xray beam
Focused X-ray
beam + aperture
in the lens
Scanning X-ray
source
Al mono
Al mono
Al mono
15-100 m
10-100 m
same
10-100 m
SSI SSX 100/206 Kratos Axis Ultra

Thermo
VG ESCALAB46250
Theta/Sigma probe JEOL JPS-9010
PHI Quantera
Analyzer
Analysed area versus Bombarded area

Concern
- Analyzed spot size
- Variation of take off angle - change of zone analyzed
- Possibility to exploit focused X-ray
to avoid degradation of sensitive samples
(displacement of sample position during analysis)
47
Analyzer
Effect of spot size on spectrum

Focused X-ray beam
Spot size (m)
Peak width
Peak intensity
25
18
20
1000 m
counts/s)
3 10
counts/s)
2 10
600 m
15
300 m
10
5
0
14
12
10
8
Intensity (
Intensity (
150 m
16
6
4
2
0
87 86 85 84 83 82
Binding Energy (eV)
87 86 85 84 83 82
Binding Energy (eV)
Constant Ep = 40 eV
SSI
48 SSX 100/206
Analyzer
Effective resolution
Ep = 10eV
60
Ag 3d5/2
50
counts/s)
3 10
40
30
0.50 eV
Intensity (
20
10
Determined by measuring FWHM

on a clean metal (e.g. Ag)
no broadening due to
sample charging
Characterizes the performances
of the analyzer as set
Should be specified
in materials and methods
371 370 369 368 367 366

Binding Energy (eV)
Clean Silver
49
Kratos Axis Ultra
Analyzer
Kinetic energy scale

Ek= h - Eb - sp
sp work function of spectrometer
Determination = calibration of zero of Ek scale
ISO : Ag 3d5/2 = 368.27 0.025 eV
Linearity tested, adjusted by recording reference peaks
ISO : Cu 2p3/2 with Mg anode
Au 4f7/2 with Al anode
Difference = 1081.7 0.025 eV
To be checked by the operator using Ag, Cu and Au standard specimens
and adjusted by an XPS expert
Ek= h - Eb in principle !!!!
50
XPS - Basic aspects

Essence of XPS
vacuum
X-ray source
energy analyzer
detection
surface charging
miscellaneous
51
Surface charging
Sample charging
Ek= h Eb - sp - EC
h, photon energy
Ek, electron as measured
EC, charging term
X-rays
e-
Ek= h Eb - EC
Ek, electron as produced
sp, work function
e-
X-rays
++++++++
On conductors EC = 0
On insulators EC > 0
52
Charge stabilization
Flood gun : flooding the surface with low kinetic energy electrons (SSI)
Flood gun filament
X-rays
e-
Lens + analyser
+ detector
eNickel grid
EC < 0
Other devices according to manufacturer
SSI
53SSX 100/206
Surface charging
Charge stabilisation with Charge Balance device

eCharge balance plates
Focused photoelectrons
Entrance Slit
V
neg
Secondary
electrons
returning to
sample
Underfocused
photoelectrons
X-rays
Sample
Magnetic field lines
54
Kratos Axis Ultra
a, Adventitious carbon on stainless steel

Monochrom., charge stabilizer OFF
Conducting sample
EC 0
---------------------------------------------------------Poly(ethylene terephthalate) PET
Insulating sample
b, Not monochrom. without flood gun
EC +7.6 eV
C 1s
c, Monochrom. + charge stabilizer

EC - 9 eV
d, Monochrom. + charge stabilizer
EC - 1.4 eV
---------------------------------------------------------e, Monochrom. + charge stabilizer
Mixed sample Insulating + Conducting
Differ.charg. EC - 10 eV EC 0 eV
___________________________________
Eb = 284.8 eV
55
Surface charging
Sample charging
Ek= h Eb - EC
Problem : variation of EC - accross the sample

- as a function of time
peak broadening
distortion
shift
Cfr Course I,C
56
Miscellaneous
Powder in trough
Polyacetal Depth
cylinder 0.5 mm
Trough
(internal
diam. 4 mm)
57
Miscellaneous
Powder in trough
Polyacetal Depth
cylinder 0.5 mm
Trough
(internal
diam. 4 mm)
Powder sensitive to air exposure

isooctane
spectro
58
isooctane
Miscellaneous
Specimen on holder
Massive or Powdered
Double sided adhesive tape
(conductive or insulating)
Specimen holder
Other preparation methods:

cells
adsorbed biomolecules
freeze-drying
drying with a flux of nitrogen gas
59
Miscellaneous
Multi samples bar
Copper Stub
Kratos Axis Ultra
60
Miscellaneous
Sputtering with ion gun
Bombardment of sample with a beam of argon ions

sputtering - surface cleaning
- composition profile
Danger : alteration of analyzed zone
61
Miscellaneous
Removing organic contamination

Ion sputtering
before
C 1s
Intensity (a.u.)
! Carbide !
after
292 290 288 286 284 282 280
Binding Energy (eV)
Stainless steel cleaned by ion sputtering

62
Miscellaneous
Ion Gun
Heating/Cooling
device in FEL
(+150C/-175C)
Catalyst Cell
Camera on SAC
Catalyst Cell
Parking facility
63
XPS - Basic aspects

Photons and electrons
XPS : elemental analysis with surface selectivity
core photoelectron peaks and background
Auger peaks
energy scale referencing
valence band
addtional features
64
Peaks and background
Survey spectrum of polystyrene
40
x 10
C 1s
35
30
CPS
25
20
15
Name
C 1s
Pos.
283.00
FWHM
3.011
Area
37579.6
At%
100.00
Step due to photoelectrons

with same origin as the peak
but having undergone
inelastic collisions
10
background
0
1000
800
600
400
200
Binding Energy (eV)
Ek
Eb
65
Survey spectrum of collagen

(freeze-dried powder)
70
O 1s
60
C 1s
50
40
Auger peak
30 O KLL
N 1s
20
10
1000
800
600
400
Binding Energy (eV)
200
66
Background variation
70
25
O 1s
60
x 104
Name Pos. FWHM Area

O 1s 530.00 3.444 17425.3
20 N 1s 398.00 3.149 9790.5
C 1s 283.00 4.311 29887.9
C 1s
50
At%
14.86
13.65
71.49
15
40
30
Collagen adsorbed on polystyrene
N 1s
CPS
Collagen powder
O KLL
10
20
5
10
1000
800
600
400
200
Binding Energy (eV)
1000
800
C 1s: from substrate and adlayer

O 1s and N 1s: only from adlayer; from smaller depth
less subject to inelastic collisions
smaller background step
600
400
200
Binding Energy (eV)
67
Background variation
Sensitive to the element distribution
4
30 x 10
a
O 1s
25
20
Silica (SiO2)
15
O 2s
Si 2p
Si 2s
C 1s
O KLL
0i
18
VI i
14
16
4
x 10
O 1s
Intensity (counts/s)
10
12
8
C 1s
O KLL
**
1000
800
600
400
Binding Energy (eV)
200
**
O 2s
Si 2p
6
4
Silicon wafer
(Si + SiO2 layer)
Si 2s
10
68
Doublets
50
Glass
Ca 2p
Ca 2p3/2
45
counts/s)
2 10
Electron energy
levels
40
Ca 2p1/2
2p3/2
2p1/2
Intensity (
35
2s
30
1s
356
352
348
344
Binding Energy (eV)
69
Auger peaks
Relaxation by Auger emission
Photoemission
(XPS)
1s
or
Relaxation
X-ray
Fluorescence
70
Auger Electron
Emission
(XAES, AES)
KL1L2,3
Auger peaks
71
Auger peaks
Position of Auger peaks in XPS spectrum

measured
kinetic energy
energy consumed
Ek,KLL = Eb,K Eb,L1 Eb,L2 sp Ec + W

energy liberated
W : displacement of energy levels

upon formation of a doubly ionized atom
72
Auger peaks
Position of Auger peaks in XPS spectrum

does not depend on h
measured
kinetic energy
energy consumed
Ek,KLL = Eb,K Eb,L1 Eb,L2 sp Ec + W

energy liberated
Ek = h - Eb sp Ec
73
Illustration: Streptococcus thermophilus
Intensity (a.u.)
X-ray source Mg,

not monochromatized
1254 eV
Ek (eV)
(eV)
Ek (eV)
Eb (eV)(eV)
X-ray source Al,

monochromatized
1487 eV
Watch
Auger vs photoelectrons
Influence of source
Ek and Eb scales
peak position
background
74
Auger peaks
Auger parameter
= Ek,Auger(KLL) Ek,XPS(K)
Intensity (a.u.)
Modified Auger parameter

= + h
= Ek,Auger(KLL) + Eb,XPS(K)
Ek (eV)
As compared with Eb of
photoelectrons,
(eV)
Ek (eV)
Eb (eV)(eV)
- more sensitive to chemical state

- independent of calibration of
the zero of energy scale
75
Energy scale referencing

measured
Eb = h Ek = h Ek
sp Ec
known
Conducting sample: Ec = 0
Calibration of energy scale using a standard (Au, Cu)
Use of an identified peak Eb* determination of sp
zero of Ek scale
direct conversion of Ek to Eb
Use of several identified peaks check of energy scale linearity
Insulating sample: Ec 0 and particular to the sample
Calibration of Eb scale
Use of an identified peak of the sample Eb*
determination of sp + EC
conversion of Ek to Eb
Common practice: C 1s of aliphatic hydrocarbon
C-(C,H) set at 284.8 eV
76
Polylactic acid
C-(C,H)
@ 284,8 eV
(Beamson 77
and Briggs, 1992)
Polystyrene
C aromatic
@ 284,6 eV
C aliphatic
@ 284,8 eV
Accuracy of Eb
(Beamson78and Briggs, 1992)
Maltodextrin
C 1s
3
2
35 x 10
25
30
C1s
20
25
CPS
20
15
15
10
10
5
5
292
C-O
@ 286,3 eV
O-C-O
290
288
286
284
Binding Energy (eV)
79
C-(C,H)
282
Glass
SiO2
+ organic surface
contaminants
12
C 1s
10
C-(C,H)
@ 284,8 eV
8
6
4
K 2p
2
300
296
292
288
284
Binding Energy (eV)

80
280
Valence band
Valence band
Spectrum zone Eb = 0 eV to Eb = 20 eV
Weakly bound electrons (molecular orbitals)
Polyethylene
Polypropylene
Binding energy (eV)
81
Valence band
Polyethylene cross-linking
Polyethylene treated by plasma ischarge in nitrogen
Intensity (a.u.)
= 20
= 70
Influence of angle of
photoelectron collection
cross-linking
occurs at the outer surface
Binding energy (eV)
82
XPS - Basic aspects

Photons and electrons
XPS : elemental analysis with surface selectivity
Features of an XPS spectrum
core photoelectron peaks and background
Auger peaks
energy scale referencing
valence band
additional features
83
Additional features
Intensity (a.u.)
Source satellites K 3,4
X-ray source Al,

monochromatized
X-ray source Mg,

not monochromatized
Watch
Auger vs photoelectrons
Influence of source
Ek and Eb scales
peak position,
background
satellites
84
Additional features
Multiplet splitting
Spin coupling
between unpaired electron left in a core level
and
unpaired electron in the outer shell number
multiplication or broadening of XPS peaks of transition elements
possible information on coordination
85
Additional features
Shake-up peaks
Combination of
photoejection of electron from atom
and
excitation of valence electrons
discrete energy loss
satellite at higher Eb
Example: -* transition of aromatic polymers
86
Additional features
Shake-up peaks
C 1s of polystyrene
x 104
C-(C,H)
12
10
CPS
8
6
4
shake up
300
290
Binding Energy (eV)
280
Does not appear

if aromaticity is destroyed by oxidation
as produced by plasma surface oxidation
87
Additional features
Shake-up peaks
Poly(ethylene terephthalate) 3
3
x 10
25
x 10
O 1s
35
C 1s
30
20
25
20
15
CPS
CPS
15
10
10
542
540
538
536 534
532
Binding Energy (eV)
Binding Energy (eV)
530
528
300 298 296 294 292 290 288 286 284 282 280
Binding Energy
88 (eV)
Binding Energy (eV)
Additional features
*
Si 2p
i S
O 2s
Si 2s
Si 2p
Si 2s
C 1s
*
*
VI i
14
**
C 1s
b
O 1s
16
12
6
2
600
400
C 1s
200
*
*
*
800
600
400
Binding Energy (eV)
200
**
O 2s
0
1000
O 2s
Si 2p
Si 2s
10
O KLL
O 1s
O KLL
800
4
x 10
18
Silicon wafer
(Si + SiO2 layer)
4
Plasmon = quantum
of oscillation of
30 x 10
a in a metal or
the electron density
25
plasma (gas of positively charged ions
20
and electrons).
15
Conducting materials : excitation
10
may occur at the
expense of the
5
photoelectron energy
satellites on0 the high Eb side
O 1s
Plasmon peaks *
89
Additional features
Intensity (a.u.)
Energy loss peaks
X-ray source Mg,

not monochromatized
X-ray source Al,

monochromatized
Discrete features :
modulation
of the background step
affecting
all the peaks of the phase
90
Additional features
Peak tails
C 1s of graphite
Intensity (a.u.)
Intensity (a.u.)
Attributed to interactions
between positive core hole
and conduction electrons
297
294 291 288 285

Binding Energy (eV)
Intensi
C 1s of polymers containing saturated hydrocarbon chains

e.g. polyethylene
Vibrational fine structure: photoelectron energy loss
91
due to vibrational excitation
282
Illustrative summary
XPS spectrum of alumina

on which molybdenum
oxide was deposited
The intensity scale was
changed by a factor 3.5
at Eb = 450 eV
92
XPS - Basic aspects

Essence of XPS
Instrument
Quantification
from complex reality to practice
parameters
approaches
93
Complex reality
Schematic representation
94
Complex reality
General equation
Contribution of volume dx dy dz
regarding photoelectrons from level a for element A
dIAa = photoelectrons emitted in the adequate direction

x probability to leave the sample
x probability to be counted
J ' Aa L' Aa CA dx dy dz
exp (- dH / Aa ) T' Aa DAa

H
95
Complex reality


H
flux of photons
in direction X
factor of
anisotropy,
varies with
depends on orbital
cross section of photoionization:

probability of emission of an
electron when a photon hits the
element
amount of element A
96
Complex reality


H
probability to leave the sample

Aa may vary along H
97
Complex reality


H
transmission function
of analyzer ,
depends on Ep and Ek
efficiency factor
of detector
98
Complex reality
Intgration

H
I Aa
99
d I Aa
Complex reality common practice
Common simplification : model of homogeneous solid

Assumption n1
- surface planar and homogeneous along x and y
- average values of J, LAa, TAa (little variation according to x, y, X, G)
I Aa J S f Aa LAaTAa DAa RAa 0 CA exp (- z / Aa cos ) dz
irradiated
area
accounts for the difference

between irradiated area
and area of collecting
photoelectrons
roughness factor
For different elements of a given sample : J, S, f(), R, D are the same
use ratio of intensities IAa / IBb

100
Complex reality common practice
I Aa J S f Aa LAaTAa DAa RAa 0 CA exp (- z / Aa cos ) dz
same for A et B
Assumption n2 : homogeneity as a function of depth
Aa and CA constant
I Aa
I Bb
Aa
L Aa T Aa C
Bb
L Bb T Bb C B Bb cos
Aa cos
I Aa Aa L AaT Aa Aa C A i Aa C A
I Bb Bb LBbTBb Bb C B
i Bb C B
i = sensitivity factor
101
Parameters
Photoionisation cross section

J. H. Scofield
Hartree-Slater subshell photoionization cross-sections at 1254 and 1487 eV
J. Electron Spectrosc. Relat. Phenom. 8 (1976) 129-137
Anisotropy factor L
LAa = 1 + 0,5 Aa (1,5 sin2 1)
depends on h, atomic number , orbital a
For s orbitals, = 2
LAa = 1 if = 54,7 (angle magique)
102
Parameters
Transmission function of analyzer T

Depends on instrument, on Epass and on Ek
often considered of the form
T = k Ep [Ep / Ek]n with 0 < n < 1
Providing Epass is the same for all peak records :
TAa / TBb = [Ek Bb / Ek Aa]n
The value of n depends on the instrument.
The uncertainty on the value of n is lower if the peaks analyzed
correspond to close Ek values
Experimentally determined values T may be provided
by the spectrometer
manufacturer
103
Parameters
Inelastic mean free path

Depends on Ek and on the matrix
Evaluations of absolute values can be found or computed (literature)

104
Parameters
Inelastic mean free path
Aa / Bb = [Ek Aa / Ek Bb]m
Different values of m reported in the literature; frequently around 0.7.
Impact of uncertainty low
if the peaks analyzed correspond to close Ek values,
105
Approaches
Survey of approaches
Considering the analyzed zone as homogeneous
= most common practice, using sensitivity factors
Based on
assumption 1
assumption 2
intellectual contradiction
composition of the surface layer as seen by XPS
106
Approaches
Use of sensitivity factors

Two ways
Evaluated by first principles approach
Aa L Aa T Aa Aa
i Aa
i Bb
Bb LBbTBb Bb
Aa
Bb
mn
E k,Aa
k , Bb
Empirical values
Determined with standards
guarantee regarding surface composition

Tabulated values related to a given element
valid for one type of
spectrometer
Ex. Wagner, F 1s taken as reference; spectrometrer with n = 1
107
Approaches
Survey of approaches
Considering the analyzed zone as homogeneous
= most common practice, using sensitivity factors
Based on
assumption 1
assumption 2
intellectual contradiction
composition of the surface layer as seen by XPS
Simulating data
on the basis of hypothetical models of the complex solid
often using data collected with several take off angles
- Data = intensity ratios : need of absolute values for parameters
- Data = absolute intensities : additional need to take into account
details regarding X-ray beam, photelectron collection
as the sample is being tilted
See course II and I,C
108
Approaches
Analyzed area versus bombarded area
X-ray
Method
e-
Analyser
slit
Al or Mg
Non-mono
Bombarded Several
area
mm2
Analysed
Several
area
mm2
(smallest)
X-ray
Old generation
X-ray
X-ray
X-ray
e-
Focused Xray beam
Focused X-ray
beam + aperture
in the lens
Scanning X-ray
source
Al mono
Al mono
Al mono
15-100 m
10-100 m
same
10-100 m
SSI SSX 100/206 Kratos Axis Ultra

Thermo
VG ESCALAB109
250
Theta/Sigma probe JEOL JPS-9010
PHI Quantera
XPS - Basic aspects

Essence of XPS
Quantification
Chemical shift
110
Chemical shift
Effect of oxidation stage

Si 2p
= 0
Silicon wafer
= 80
Si+IV
106
104
Si0
102
100
98
Binding Energy (eV)
96
111
Chemical shift
Not just formal oxidation level, but electron density
Shift
+5-
00
+6
Oxidation number
Shift
+5-
0-1
+1
Charge
112
Chemical shift
Effect of electronegativity of surrounding atoms

poly(vinyl trifluoroactate)
Formal oxidation stage

C 1 : -2
C2 : 0
C3 : +3
C4 : +3
113
Chemical shift
Effect of first and second neighbour

poly(trifluorothylacrylate)
Formal oxidation stage

C 1 : -2
C2 : -1
C3 : -1
C4 : +3
C5 : +3
114
Chemical shift
Selectivity to chemical functions

Poly(thylne trphtalate)
3
x 10
3
x 10
O 1s
C 1s
25
C-(C,H) 6 x
35
O-C
O=C
30
20
25
20
15
CPS
CPS
C-O 2 x
15
C=O 2 x
10
10
542
540
538
536 534
532
Binding Energy (eV)
530
528
300 298 296 294 292 290 288 286 284 282 280
Binding Energy (eV)
115
60
x 10
Maltodextrin
50
Chemical shift
O 1s
CPS
CPS
30
x 10
O=C-N
C-OH
C-(C,H)
O-C-O
10
5
x 10
C-NH
8
6
4
2
C-NH2+
80 x 10
Collagen
10
x 10
CPS
CPS
15
16
14
12
10
Poly (L-serine)
20
C-NH
60
50
6
4
40
CPS
CPS
C-O
C-NH2+
30
20
2
x 10
x 10
O-C=O
C-O
C-N
O=C-N
x 10
C-O
C-N
534
532
530
Binding Energy (eV)
O=C-O
C-(C,H)
20
30
528
15
C-NH
28
26
406
C-(C,H)
O=C-N
O=C-O
10
C-O
C-N+
24
536
C-(C,H)
O=C-O
25
CPS
O=C-O-C
R4N+
32
P-O-C
30
34
P-OP=O
90
80
70
60
50
40
30
20
10
x 10
35 x 10
36
DPPC
CPS
538
18
16
14
12
10
8
6
4
2
70
O=C-N
110
100
90
80
70
60
50
40
30
10
N 1s
25
12
C-O
15
20
10
C 1s
20
Illustration
30
25
C-OH
C-O-C
40
x 10
404
402
400
398
Binding Energy (eV)
396
292
290
116
288
286
284
Binding Energy (eV)
282
XPS - Basic aspects

Essence of XPS
Quantification
Chemical shift
Time line
117
Time line
Historical survey of physical concepts
Source M. Genet
118
Time line
Time line for XPS
1951
Steinhardt RG, Serfass EJ. X-ray Photoelectron Spectrometer

for chemical analysis, Anal.Chem. 1951; 23: 1585-1590.
1954
K. Siegbahn K./ First iron-free double focussing magnetic

deflection spectrometer.
1957
K. Siegbahn: Chemical shift by XPS (copper).
1964
Hagstrom S, Nordling C, Siegbahn K. Electron

Spectroscopy for Chemical Analyses, Phys. Let. 1964; 9:
235-236.
2003
Kay Siegbahn
(Sweden, 20/07/1918 20/07/2007)
Nobel prize in 1981
(Karl Siegbahn Nobel prize in 1924)
Source M. Genet
119
Time line
1969
First commercial spectrometer (Hewlett Packard USA)
1970
Angle Resolved XPS (ARXPS), Gelius et al.
1971
1st XPS spectrometer in Belgium: UCL J.J. Fripiat
1972
First X-ray monochromator: U. Gelius & K. Siegbahn
1977
Multitechnique systems
1987
Focused X-ray beam and scanning imaging (~150m): R.L.

Chaney
1997
Parallel imaging (~5m): Thermo VG, Kratos
2003
Delay Line Detector (Kratos)
Source M. Genet
120

Course I.A. XPS Basics

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Course I.A. XPS Basics

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Course I

Fundamentals of surface and interface science

1st Colombian Seminar on Surface Science

The slides are readable on prints

1st Colombian Seminar on Surface Science

XPS - Basic aspects

Physical process instrument

X-rays and electrons

X-rays and electrons

Absorption sp. Photoelectron sp. Fluorescence

X-rays and electrons

Spin -1/2, +1/2

Spin orbit coupling

Resulting angular moment j = l- 1/2 or l+

X-rays and electrons

XPS peaks X-ray

X-rays and electrons

1/2 _________ 1560

X-rays and electrons

Fluorescence spectrum (scale in keV)

X-rays and electrons

Conversion between energy and wavelength of photon

1 Faraday * 1 V = 96500 C.V = 96500 joule = N eV

X-rays and electrons

Absorption spectrum (scale in )

X-rays and electrons

1/2 _________ 1560

Eb : electron binding energy

Survey spectrum of collagen

Intensity (103 counts/s)

Binding Energy (eV)

Energy levels of selected elements

Global view of photoelectron spectroscopy

Information related to energy levels

From principle to measurement

Elemental analysis with surface selectivity

Electrons contributing to the peaks: no energy loss

Electrons contributing to the background: energy loss

Electrons not ejected from the solid

Contribution of a layer of thickness dz at depth z

C concentration of photoelectron emitor in homogeneous solid

cfr Beer-Lambert law

: inelastic mean free path IMFP,

analogous to (absorption coefficient)-1

Contributions of increasing depths

Contributions of increasing depths

Illustration: oxidation of germanium

Analysis at different angles

Surface is depleted in PAA compared to 25

XPS - Basic aspects

Kratos Axis Ultra

Need of Ultra High Vacuum conditions

Source without monochromator

N.B. Other less common anodes : Zr (151.4 eV); Si (1739.6 eV);

X-ray emission spectrum from an aluminum source

1.486,7 eV Int 2/3

1.486,3 eV Int 1/3

Satellites due to the source

Source with monochromator

C 1s on Poly(ethylene terephthalate) - PET

SSI SSX 100/206 ( 1988)

KRATOS Axis Ultra (1999)

Monochromatisation reduces the width of K1,2 line,