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characterization of Nanoparticles
(NPs): I. Dimensional effects
3
1.1 Size matters: surface in nanoparticles
•Impact of surface atoms in NPs: (1) The fraction of atoms at the surface is called dispersion
F; (2) Atoms at the surface have fewer direct neighbours than atoms in the bulk. Therefore, particles
with a large fraction of atoms at the surface have a low mean coordination number (which is the
number of nearest neighbours)
• Major components:
• X-ray Source
• High Vacuum Environment
• Electron Energy Analyzer
6
1.2.1 Basically principle
• XPS works by irradiating a sample material with soft
x-rays causing core level electrons to be ejected.
7
X-ray excite photoelectron and Auger electron processes
1.2.2 XPS information depth
9
1. 2.4 Surface chemistry
12
2.2 Possible nanostructures patterns
13
2.3 XPS: challenge issues in nanostructures
Conventional XPS
•Uniform surface layer
-Chemical states: related to charge
-Exchange between atoms
-Quantitative analysis can be carried by
relative sensitive factors I i Si
C=
∑Ij Sj
New Challenges
j
•Non-uniform surface
-Chemical states : Core level shift is not
-only related to charge exchange between
-atoms, but also to structural dimensions
-Quantitative analysis? 14
(size effects)
3. Photoelectron peak shape of thin
layer materials
• 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
a 50A b c
d 15
[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]
4. Photoelectron emission from
nanoparticles
4.1 Size dependent electronic states of nanoparticles
Size dependent electronic states
suggested that binding energy
may affected by dimension of
nanoparticles!
[P. P. Edwards, R. L. Johnston and C. N. R. Rao,
On the Size-Induced Metal-Insulator Transition in
Clusters and Small Particles, in Metal Clusters in
Chemistry, Vol. 3, ed. P. Braunstein, L. A. Oro, P.
R. Raithby, Wiley, Weinheim, 1999 ]
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4.2 Photoelectron emission intensity in NPs
λc
C
Ic: intensity
Θ: surface coverage of the nanoparticles
d: mean dimension of the nanoparticles,
λ: photoelectron mean escape depth in the nanoparticles
I C0 : photoelectron peak intensity from bulk materials
• Then the intensity ratio from a nanoparticle with different mean
escape depth λ, can be expressed into
d
1 − exp( − )
I c1 I c01 λc1
= 0
Ic2 I c 2 1 − exp( − d ) 17
λc 2
• For a sphere particles
{
I c = I c 0πλ3 (d / λ ) 2 + [(2(d / λ ) + 1]e −2 d / λ − 1] / 2}
κ ( r / λ )d + λ −d / λ 3
I (λ , d , r ) = e πλ {( r / λ ) 2 + [( 2 r / λ + 1)e −2 r / λ − 1] / 2}
d +λ
where d
R −d
ρ= r
β 1ρ 2 + β 2 ρ + 1 λ
κ (ρ ) =
β 1ρ 2 + β 3 ρ + 1 d
δ=
λ 18
[D.-Q. Yang, J.-N. Gillet, M. Meunier and E. Sacher, J. Appl. Phys. 97(2005)024303]
5. Dimensional estimation of nanoparticles
•Approach[D.-Q. Yang, M. Meunier and E. Sacher, Appl. Surf. Sci., 173 (2001) 134]
r 2 2r
I (λi , r ) = πλ {( ) + [( + 1)e − 2 r / λi − 1] / 2}
3
i
λi λi
I (λ1 , r )
and R=
I ( λ2 , r ) 28
24
R
related the ratio of two photoelectrons from 16
a nanoparticles. 12
8
0 5 10 15 20 25 30
19
35 40
1.3
Cu2p3/2 (a)
1.1
1.0
0.9
resolution of
8 Å, 0.007 Å/sec
0.6 8 Å, 0.2 Å/sec
8 Å, 0.15 Å/sec
0.5
8 Å, 0.008 Å/sec
nanoparticles No 0.4
0 10 20 30 40 50 60 70 80
1.3
32 Å, 0.25 Å/sec
1.1
0.8
0 10 20 30 40 50 60 70 80
θ 20
6.2 Monte Carlo simulation model
Straight line
approximation Straight Line Approximation
method has been SLA
used for the z
Exponential attenuation along the path d
d (θ )
simulation of in the direction of observation.
dv
photoelectron y dI = I 0 exp[−d (θ, x, y, z ) / λ] dV
emission x
I = I 0 ∫ dI
V
1
[ ]
I sphere = πλ2 1 −e −2 r / λ (1 +2r / λ) , for θ ∈[0,90]
2
[K.N. Piyakis, D.-Q. Yang, and E. Sacher, Surf. Sci., 536 (2003) 139 ] 21
Monte Carlo simulation results
1.7 0.1
1.9
Relative Intensity
1.5 1
1.7 0.1
1.3 10
1.1
1.5 1.0
0.9 1.3 10
0.7 1.1
0.5
0.9
0 10 20 30 40 50 60 70 80
0.7
Angle
0.5
0 10 20 30 40 50 60 70 80
Angle
D D
R1 R3
R2
D1 D2
Radius=5(3) Distance=2(0) R3
R1 R2
2.5
2.3
Radius=5(3) Distance=2(2)
2.1
1.9 R/λ 2.5
Relative Intensity
1.7 2.3
0.1
1.5 1.0 2.1 R/λ
10 1.9
Relative Intensity
1.3
1.1 1.7 0.1
1.5 1.0
0.9
1.3 10
0.7
1.1
0.5
0 10 20 30 40 50 60 70 80 0.9
Angle 0.7
0.5
0 10 20 30 40 50 60 70 80
Angle
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Size effects on the core level shifts: evaporated Cu nanoparticles on (a) HOPG and
(b) BCB after different surface treatment. Untreated HOPG and BCB surface gives
very weak interaction with Cu, resulting larger NPs formation, Ar plasma (or beam)
resulting in surface creates high density defects (free radicals) and N2 plasma
treatment results in –NHx groups formation.
Fig(b) suggested that there may have addition contribution from surface chemistry
besides size-dependent Cu NPs effects on core level binding shift.
[D.-Q. Yang and E.Sacher, Appl.Surf.Sci. 195(2002) 187 ] 25
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
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7.2. XPS Valence band spectra of
NPs
Experimental evidence:
(2) Valence electron peak shifts to low binding
energy side as NPs size increase
(3) Peak width decreases as NPs size decrease
Possible explanation:
Size-dependent surface electronic states induced
valence band changes
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7.3 Auger parameters
1851.5
1851.0
Auger parameter (eV)
1850.5
1850.0
evapotation,untreated HOPG
1849.5 +
evaporation, Ar -treated HOPG
sputtering, untreated HOPG
1849.0
0 5 10 15 20 25 30 35
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7. 5 Initial- and final-state effects of NPs in XPS
•XPS core level binding shift: •Core level binding shift is, in general, related to
atomic chemical change. However, it can be
∆E B = ∆ε i − ∆E f + ∆EC
affected by (i) surface charge, (ii) weak electron
exchange, et al.
∆ε is the change of core eigenvalue ε (initial •The Auger parameter has been used as an
state effects), ∆Ef is change of final state empirical, or “fingerprinting”, tool to
relaxation energy, and EC is Coulomb characterize the chemical states of the elements
energy, which originates from core-electron in cases where charging of the sample or small
emission, leaving a cluster with unit positive shifts in core binding energies present problems.
• Wagner plot is also called a chemical state
charge that, in a free spherical metallic
plot, which uses both photoelectron and x-ray
cluster, will appear as surface charge, excited Auger lines, increase the utility of XPS
resulting in Coulomb energy of e2/2r . for identifying chemical states.
•Auger parameter is defined as •We use evaporated Cu nanoparticles and
α ' = EB (Cu 2 p3 / 2 ) + EK ( L3 M 4,5 M 4,5 ) HOPG and BCB substrates to identify binding
energy shifts, Auger parameters and Wagner
•Wagner plot plots due to relatively weak interactions between
nanoparticle and substrate, to evaluate the size
EB ~ EK effects of nanoparticles on these parameters.
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Ek is photoelectron kinetic energy
Table. Initial- and final-state ratios
Cu NPs supported on HOPG after of ΔΕB (Cu 2p3/2) for Cu Clusters on
different surface treatment HOPG and Cyclotene
-0.02
-0.14
0.0
0.02 0.04 0.06 0.08 0.10 0.12 0.14 0.16 0.18
-1
1/d (A )
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8. Conclusions and future work
Experimental results, based on Cu, Au, Pt, Pd, Ni and Si nanoparticles on various treated HOPG,
BCB polymer, SiO2, Al2O3 and TiO2 surfaces, from ours and literatures data, combined with
simple theoretical analyses, demonstrate that
(ii) XPS is a very useful tool, giving not only chemical information on nanoparticles, but also
dimensional information.
(iii) We offer a simple method to estimate nanoparticle average size and surface number density.
(iv) We have found the following parameters are dependent on size of NPs in XPS
a. Binding energy shift and peak width (FWHM, full width at half maximum )
b. Valence band peak shape (peak position and width)
c. Auger parameter, Wagner plots
(v) Our study has, for the first time, indicated that initial-states, final-states, Auger parameters and
Wagner plots, are not only related chemical state, but also strongly depend on nanoparticle size
and substrate surface states.
(vi) Unexpected angle-resolved XPS data for nanoparticles have been successful reproduced by
Monte Carlo simulation.
Comparing with TEM and TEM techniques, 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
Future work
Mean escape depth of photoelectron in NPs. It should be varied with NPs size, and need to simulate
by MC 32
Acknowledgments
The authors thank the Natural Sciences and Engineering Research Council of
Canada for funding.
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