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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

X-rays and electrons


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

X-rays and electrons


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

X-rays and electrons


_________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

__

X-rays and electrons


_________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

X-rays and electrons

Fluorescence spectrum (scale in keV)


Fe K, 7.11 - 0.71
Fe K, 7.11 - 0.05

Al K, 1.56 - 0.07

X-rays and electrons

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

X-rays and electrons

Absorption spectrum (scale in )


12400/15860
= 0.78

12400/13035
= 0.95

12400/15200
= 0.82

11

X-rays and electrons


_________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


X-rays and electrons
Essence of XPS
Instrumental aspects
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
Hemispherical electron
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
Hemispherical electron
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


X-rays and electrons
Essence of XPS
Instrumental aspects
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
Instrumental aspects
Features of a XPS spectrum
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

Peaks and background

Survey spectrum of collagen


(freeze-dried powder)

Intensity (103 counts/s)

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

Peaks and background

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

Intensity (103 counts/s)

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

Peaks and background

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

Peaks and background

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

Energy scale referencing

Polylactic acid

C-(C,H)
@ 284,8 eV

(Beamson 77
and Briggs, 1992)

Energy scale referencing

Polystyrene

C aromatic
@ 284,6 eV

C aliphatic
@ 284,8 eV

Accuracy of Eb

(Beamson78and Briggs, 1992)

Energy scale referencing

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

Energy scale referencing

Glass
SiO2
+ organic surface
contaminants

12

C 1s

Intensity (103 counts/s)

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
Instrumental aspects
Features of an XPS spectrum
core photoelectron peaks and background
Auger peaks
energy scale referencing
valence band
additional features

83

Additional features
Illustration: Streptococcus thermophilus

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

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.)

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


X-rays and electrons
Essence of XPS
Instrument
Features of a XPS spectrum
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

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

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

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

probability to leave the sample


Aa may vary along H

97

Complex reality

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

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

exp (- dH / Aa ) T' Aa DAa


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


X-rays and electrons
Essence of XPS
Instrumental aspects
Features of a XPS spectrum
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

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

XPS - Basic aspects


X-rays and electrons
Essence of XPS
Instrumental aspects
Features of a XPS spectrum
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

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