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Course I.A. XPS Basics
Course I.A. XPS Basics
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
Attenuation
Primary
emission
A+* + e
Secondary emission
Radiat. relaxation Auger effect
A+* A+ + h
A+* A++ + e
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
subshell //
n
l (0 to n-1) ml (- l 0 +l)
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
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
X-ray
__
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
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
Al K, 1.56 - 0.07
E in joule
E in eV
in
10
12400/13035
= 0.95
12400/15200
= 0.82
11
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
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
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
70
O 1s
60
C 1s
50
40
N 1s
30
20
10
1000
800
600
400
200
15
Essence of XPS
16
Essence of XPS
17
Essence of XPS
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
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
Essence of XPS
X-ray
h
P C dz Q
e
z
P C dz
dz
Essence of XPS
Q = exp (- z / cos )
Attenuation
Iin
dx
I I-dI
Iout
x
t
- dI /I = dx /
- ln Iout / Iin = - ln Q = t /
Q = exp (-t / )
Essence of XPS
% 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
% 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
24
Essence of XPS
= 0, cos = 1
= 80, cos = 0.17
26
Vacuum
27
Vacuum
High vacuum
to reduce
inelastic collisions between photoelectrons and gas molecules
detector, gauges degradation (electrical discharges)
surface contamination
(!!!!!)
Introduction chamber
Analysis chamber
Pumps
28
Source
Coolidge tube
29
Source
1.486,6 eV
1.253,6 eV
Source
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
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
Al K1,2
removes K3,4
sharpens
K1,2
Al
34
Source
Effect of monochromatization
Intensity (a.u.)
300
296
292
288
Binding Energy (eV)
284
280
Analyzer
hemispherical
Hemispherical electron
electron
energy analyzer
electron
Electron multiplier
multiplier
Sample
sample
Counts
X -rays
retardation
Retardation
stage
Ek
36
Ek
Analyzer
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
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
R
Ep
Analyzer
X -rays
retardation
Retardation
stage
Electron multiplier
electron
multiplier
Counts
Sample
sample
Ek
40
Ek
Analyzer
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)
41
Analyzer
PET
O 1s
O 1s
Pass energy 40 eV
Pass energy 20 eV
C 1s
C 1s
Arbitrary units
Arbitrary units
Ep = 40 eV
Ep = 20 eV
Ep = 40 eV
Ep = 20 eV
300
290
280
Analyzer
Ekdet = Ek - Eret
Retarding potential
43
Analyzer
Magnetic lens
Sample immersed in
a magnetic field
44
Analyzer
C 1s
40
counts/s)
3 10
35
30
25
20
Intensity (
15
Electrostatic mode:
electrostatic lens only
10
5
296 292 288 284
Binding Energy (eV)
45
Analyzer
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 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
PHI Quantera
Analyzer
47
Analyzer
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
Clean Silver
49
Analyzer
50
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
SSI
53SSX 100/206
Surface charging
Focused photoelectrons
Entrance Slit
V
neg
Secondary
electrons
returning to
sample
Underfocused
photoelectrons
X-rays
Sample
Magnetic field lines
54
Kratos Axis Ultra
C 1s
Differ.charg. EC - 10 eV EC 0 eV
___________________________________
Eb = 284.8 eV
55
Surface charging
Sample charging
Ek= h Eb - EC
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)
58
isooctane
Miscellaneous
Specimen on holder
Massive or Powdered
Double sided adhesive tape
(conductive or insulating)
Specimen holder
freeze-drying
drying with a flux of nitrogen gas
59
Miscellaneous
Copper Stub
60
Miscellaneous
61
Miscellaneous
C 1s
Intensity (a.u.)
! Carbide !
after
292 290 288 286 284 282 280
Binding Energy (eV)
Miscellaneous
Ion Gun
Heating/Cooling
device in FEL
(+150C/-175C)
Catalyst Cell
Camera on SAC
Catalyst Cell
Parking facility
63
64
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
10
background
0
1000
800
600
400
200
Ek
Eb
65
70
O 1s
60
C 1s
50
40
Auger peak
30 O KLL
N 1s
20
10
1000
800
600
400
200
66
Background variation
70
25
O 1s
60
x 104
C 1s
50
At%
14.86
13.65
71.49
15
40
30
N 1s
CPS
Collagen powder
O KLL
10
20
5
10
1000
800
600
400
200
1000
800
600
400
200
67
Background variation
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
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
Photoemission
(XPS)
1s
or
Relaxation
X-ray
Fluorescence
70
Auger Electron
Emission
(XAES, AES)
KL1L2,3
Auger peaks
71
Auger peaks
energy consumed
72
Auger peaks
energy consumed
Ek = h - Eb sp Ec
73
Intensity (a.u.)
Ek (eV)
(eV)
Ek (eV)
Eb (eV)(eV)
Auger peaks
Auger parameter
= Ek,Auger(KLL) Ek,XPS(K)
Intensity (a.u.)
Ek (eV)
As compared with Eb of
photoelectrons,
(eV)
Ek (eV)
Eb (eV)(eV)
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
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
280
Valence band
Valence band
Spectrum zone Eb = 0 eV to Eb = 20 eV
Weakly bound electrons (molecular orbitals)
Polyethylene
Polypropylene
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
83
Additional features
Illustration: Streptococcus thermophilus
Intensity (a.u.)
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
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
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
280
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)
530
528
300 298 296 294 292 290 288 286 284 282 280
Binding Energy
88 (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
200
**
O 2s
0
1000
O 2s
Si 2p
Si 2s
10
O KLL
Intensity (counts/s)
Intensity (counts/s)
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
Illustration: Streptococcus thermophilus
Intensity (a.u.)
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
Intensi
282
Illustrative summary
92
93
Complex reality
Schematic representation
94
Complex reality
General equation
Contribution of volume dx dy dz
regarding photoelectrons from level a for element A
J ' Aa L' Aa CA dx dy dz
95
Complex reality
J ' Aa L' Aa CA dx dy dz
flux of photons
in direction X
factor of
anisotropy,
varies with
depends on orbital
amount of element A
96
Complex reality
J ' Aa L' Aa CA dx dy dz
97
Complex reality
J ' Aa L' Aa CA dx dy dz
transmission function
of analyzer ,
depends on Ep and Ek
efficiency factor
of detector
98
Complex reality
Intgration
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
I Aa
99
d I Aa
irradiated
area
roughness factor
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
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
Parameters
Parameters
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
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
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
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 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
PHI Quantera
110
Chemical shift
= 0
Silicon wafer
= 80
Si+IV
106
104
Si0
102
100
98
Binding Energy (eV)
96
111
Chemical shift
Shift
+5-
00
+6
Oxidation number
Shift
+5-
0-1
+1
Charge
112
Chemical shift
Chemical shift
Chemical shift
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
Intensity (counts/s)
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
117
Time line
Source M. Genet
118
Time line
1951
1954
1957
1964
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
1970
1971
1972
1977
Multitechnique systems
1987
1997
2003
Source M. Genet
120