Applications of XPS

Determine surface contamination of wire bonding

fingers of TBGA
Contaminated bond finger

Uncontaminated
bond finger

XPS Au 4f 7/2 image of bond fingers

with and without contamination

Information from secondary features in XPS spectra

Co 2 p

Energy Loss Spectra

HAO-5

Satellite

22000

Intensity (a.u.)

HAO-4

Counts / s

20000
18000
16000
14000
12000
810

HAO-3

800

HAO-2

Co 2p

8 10 12 14 16 18 20

Energy loss (eV)

Counts / s

770

Co/Si at room temperature

Plasmon

8000

780

B in d in g En e r g y ( e V )

HAO-1

790

6000
4000
2000
0

XPS O 1s energy loss spectra

to obtain Energy gap (Eg)

81 0

80 0

7 90

780

770

B indin g Ener gy ( eV )

Co/H-Si(111) after annealing

New challenges of XPS in nanostructures

General nanostructured surface patterns

Thin layer

Island-like

Conventional XPS

Sphere

New Challenges

Uniform surface layer:

1. Chemical states: related
to charge exchange
between atoms
2. Quantitative analysis can
be carried by relative
sensitive factors
C=

Hemisphere

Non-uniform surface:
1. Chemical states : Core level shift is not
only related to charge exchange between
atoms, but also to structural dimensions
2. Quantitative analysis? (size effect)
I i Si
Ij Sj
j

Growth mode study by XPS: intensity vs adsorbate

coverage
Co on Si
1 .0

(a )

0 .9

C o 2 p 3 /2

XPS intensity (normalized)

0 .8
0 .7
0 .6
0 .5
0 .4

Si 2s
0 .3

Smooth
morpholog
y

0 .2
0 .1
0 .0
0

20

40

60

80

1 00

T im e (m in )

Co on HOPG
1.0

(b)

0.9

XPS Intensity (normalized)

0.8

Co 2p3/2

0.7
0.6
0.5

C 1s

0.4
0.3

Island
growth

0.2
0.1
0.0
0

10

20

30

40

50

60

70

80

Time (mins)

n
s

0
s

nd a

The decay of XPS signal from substrate

I = I exp(

The intensity of the adsorbate signal

I an = I a [1 exp(

Surf. Sci. 600(2006)1308, 532(2003)639

nd a

)]

Nanostructure (2D) from background signals

Thin layer position can causes
different photoelectron scattering
(peak shape), as found by D.R.Penn
30 years ago, and confirmed by
S.Tougaard, as showing in Figures.
Tougaard et al have shown that the
inelastic scattering background near
the peak can be used to reliable
obtain detailed information about
the surface under investigation

1.1A
20A
50A

30A

50A

[D.R.Penn, Phys.Rev.Lett., 40(1978)568; S. Tougaard, Surf.Interf.Anal. 26(1996)249;

J.Vac.Sci.Technol., A14(1996)1415; J.Vac.Sci.Technol., B13(1995)949]

Determine the thickness of ultrathin SiO2 layers on Si

Tox = SiO2Sin ln[(ISi / ISiO2)(ISiO2exp/ISiexp) + 1]

SiO2 is the attenuation length of

the Si 2p photoelectron in SiO2
is take-off angle

This method is only suitable for an

oxide on its own elemental substrate
(e.g. SiO2 on Si)

Si 2p spectra

Surf. Interface Anal. 36(2004)1269

Determination of the heterojunction band offsets by a combination of core level and

valence band photoemission

Valence band offset:

E = (ECLY - EY) (ECLx - Ex) (ECLY(i) ECLx(i))
Conduction band offset:
Ec = Egx - EgY - E
Band alignments at ZrO2/Si, SiGe and Ge interfaces

Schematic flat-band diagram

Valence and Ge 2p spectra of Ge

with and without ZrO2 overlayer

Schematic flat-band diagram at

ZrO2/Si, SiGe and Ge interfaces

APL 98(2010)113510, 96(2010)072111, 95(2009)192109, 95(2009)162104, 94(2009)142903,

94(2009)062101, 93(2008)222907, 93(2008)052104, 92(2008)032107, 91(2007)042102,
89(2006)022105, 89(2006)202107, 88(2006)192103, 86(2005)112910, 85(2004)6166

Determination of nanoparticle size from XPS signal intensity

For rectangle or square shape

I C = I C0 [1 exp(

)]

[F. Kerkhof and J.A. Moulijn, J. Phys. Chem. 83(1979)1612]

For a sphere particles

I c = I c 03 (d / ) 2 + [(2(d / ) + 1]e 2 d / 1] / 2}
[G.K. Wertheim and S.B. DiCenzo, Phys.Rev. B 37(1988) 844]

For a sphere particles with shell

( r / )d + d / 3
I ( , d , r ) =
e {( r / ) 2 + [( 2 r / + 1)e 2 r / 1] / 2}
d +

d
r

[D.-Q. Yang, J.-N. Gillet, M. Meunier and E. Sacher, J. Appl. Phys. 97(2005)024303]
28

Peak intensity method:

24

The ratio of two photoelectron

emission intensities from a
nanoparticle is used to obtain its size.

I (1 , r )
R=
I (2 , r )

20

Modeling of XPS signals is required

16

12

8
0

10

15

20

25

30

35

40

Nominal Cu thickness (A)

The ratio of Cu2p3 to Cu3d as Cu mass thickness

Core-level binding energy shifts of nanoparticles

[H.G.Boyen et al, Phys.Rev.Lett., 94(2005)016804]

Core-level and velance binding energy shifts of Ni clusters

Ni 2p3/2

Ni Auger

2.5

Valence band

2.0

Energy shift (eV)

7.5 ML

Normalized intensity (a.u.)

5.0 ML

2.5 ML

1.5
1.0
0.5

2.0 ML

0.0

1.5 ML

0
1.0 ML

Ni thickness (Monolayer)

0.5 ML

850

852

854

856

835 840 845 850-2

-1

Binding energy (eV) Kinetic energy (eV) Binding energy (eV)

The Ni 2p3/2 core-level, Ni L3M4,5 M4,5

Auger transitions and valence band
spectra as a function of Ni coverage on
rutile TiO2(001) surface

[J. G. Tao et al. Surf. Sci. 602(2008)2769]

The BE shifts of Ni 2p3/2 core-level (solid

squares) and L3M4,5 M4,5 Auger transitions
(solid circles) as a function of Ni coverage

AFM images of Ni
clusters on TiO2

Major explanation of NPs binding

energy shifting in XPS
1. Initial effects proposed by Mason,
due to surface atomic coordination
number reducing in NPs surface
2. Charging effects (final-state effects)
of residing positive charge on a NP,
proposed by Wertheim et al, due to
photoelectron emission from a NP
and leaving a positive charge,
causing core level shifts to high
binding energy side.
3. Both theoretical models indicate
the binding energy shifting is
proportional to 1/d, d is NPs size
4. Peak width of core level is
increasing with NPs size decreasing,
and it is difficult to understanding by
charge residing model

Dependence of the binding energy

on cluster size
Initial state effect

Changes in the valence

shell configuration

Changes in the valence

electron density (atomic
renormalization)

Differences in extraatomic screening

energies

Final state screening effect

e

Coulomb
interaction
+
E~ e2/r

Semiconductor/Insulator
Poor electrical contact hinders the
electron flow to screen the holes
(hole delocalization).

Auger parameters and Wagner plots

The Auger parameter has been used as an empirical, or fingerprinting, tool to
characterize the chemical states of the elements in cases where charging of the
sample or small shifts in core binding energies present problems.

The Wagner Auger parameter

for the ith core-level, (i), and its shifts,
(i), are:
(i) =BE(i) + KE(klm)
(i) = BE(i) + KE(klm)
where i, k, l, and m are core levels. With
several approximations, the (i) can be
related to (i, Initial) and R (i, final )
By:

R (finial) = (i)/2
BE (BE shift) = -(initial) - R (finial)

Initial- and final-state contributions to binding energy shift of NPS

Table. Initial- and final-state ratios

of B (Cu 2p3/2) for Cu Clusters on
HOPG and Cyclotene

Cu NPs supported on HOPG after

different surface treatment

0.6
-0.02
0.5

-0.04

0.4

-0.06

0.3

-0.08
-0.10

0.2

-0.12
0.1
-0.14
0.0
0.02

0.04

0.06

0.08

0.10
-1

1/d (A )

0.12

0.14

0.16

0.18

Final-state contribution to EB(Cu 2p3/2) ) (eV)

Initial-state contribution to EB(Cu 2p3/2) (eV)

0.00

HOPG

Cyclotene

surfac
e

untreat
ed

Ar+treated

untreat
ed

untreat
ed

Ar+treated

N2treated

metalli
zation

evapor
ated

evapor
ated

sputter
ed

evapor
ated

evapor
ated

evapor
ated

1.8

1.8

1.8

0.02

0.09

0.25

ratio

The Auger Parameter analysis

BE (BE shift) = - (initial state) - R (finial state)
0.5

(a)

(001)
(110)

0.3
0.2

(001)
(110)

-0.4

0.1

-0.6

0.0

-0.8

-0.1

(b)

-0.2
R (eV)

(eV)

0.4

0.0

Ni thickness (Monolayer)

-1.0

Ni thickness (Monolayer)

The initial (a) and final (b) state effects contributions to the total shifts as a function of Ni
coverage obtained by A.P. analysis for both TiO2(001) and (110) surfaces.

Charge transfer between clusters and substrate

Determination of cluster size

[J. G. Tao et al. Surf. Sci. 602(2008)2769]

Determination of cluster size using R

0.0

(b)
(001)
(110)

R (eV)

-0.2
-0.4

e 2
R =
4 0 r

-0.6
-0.8
-1.0

10 nm

Ni thickness (Monolayer)

R - determination of cluster size (0.85 nm on (001)

and 1.38 on (110)). It has good agreement with TEM
results that the size distribution of particles is quite
narrow, with majority ranged from 1.5 -1.9 nm.

TEM images show Ni cluster

size

Comparing with TEM, XPS estimated dimension information of NPs has following
advantages and disadvantages:
Average size information, it is better for relative narrow size distribution of NPs
It can be used for very small size, such as less than 1nm