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
