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X-ray photoelectron spectroscopy

characterization of Nanoparticles
(NPs): I. Dimensional effects

D.-Q.Yang* and E.Sacher


Department of Engineering Physics
École Polytechnique of Montréal

* Correspondence email: derry.yang@gmail.com


Outline
1. Introduction
1. Nanoparticles (NPs)
• Size matters: surface of NPs
• Size-dependent properties
2. XPS
1. Basic principle
2. Information depth
3. Surface composition and chemistry
4. Depth profiling
2. New challenges of XPS in nanostructures
– Ideal nanostructured surface patterns
– Possible nanostructured surface patterns
– Challenges issues
3 Photoelectron peak shape of thin layer materials
4. Photoelectron emission from nanoparticles
– Size dependent electronic states of nanoparticles
– Photoelectron emission intensity in NPs
5. Dimensional estimation of nanoparticles
6. Angle-resolved XPS of nanoparticles
5 Issues
5 Monte Carlo simulation model
5 Simulation results
7. Binding energy and related shift of core level
– Binding energy shift
– Valence band spectra
– Auger parameters
– Wagner plots
– Initial- and final-states effects
• Conclusions and future work
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1. Introduction
• Nanoparticles
– A nanoparticle is a microscopic particle whose size is measured in nanometres
(nm). It is defined as a particle with at least one dimension <100nm. Nanoparticles
made of semiconducting material may also be labeled quantum dots if they are
small enough (typically sub 10nm) that quantization of electronic energy levels
occurs.
– Nanoparticles are of great scientific interest as they are effectively a bridge
between bulk materials and atomic or molecular structures. A bulk material should
have constant physical properties regardless of its size, but at the nano-scale this is
often not the case. Size-dependent properties are observed such as
quantum confinement in semiconductor particles, surface plasmon resonance in
some metal particles and superparamagnetism in magnetic materials. Semi-solid
and soft nanoparticles have been manufactured. A prototype nanoparticle of semi-
solid nature is the liposome
– nanoparticles have already been used for commercial purposes. Refrigerators and
washing machines that are able to release silver nanoparticles enable the
machines to kill micro-organisms, as the silver nanoparticles inhibit the respiration
of the micro-organisms and suffocate them. This ensures that food will stay fresh
for a very long time and clothes are cleaned thoroughly.
– Nanoparticle research is currently an area of intense scientific research, due to a
wide variety of potential applications in biomedical, optical, and electronic fields.
– All these macro-properties of the nanoparticles are dependent on the their size

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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)

Evolution of the dispersion Calculated mean coordination


F as a function of n for Potential of the surface oxide
number NN as a function of reduction peak Ed of glassy
cubic clusters up to n = inverse radius, represented by
100 (N = 106). The carbon-supported Pt
N–1/3, for magnesium clusters nanoparticles as a function of
structure of the first four of different symmetries
clusters is displayed particle size. [F. Maillard, S.
(triangles: icosahedra, squares: Schreier, M. Hanzlik, E. R.
[E. Roduner, Nanoscopic decahedra, diamonds:
Materials: Size-Dependent Savinova, S. Weinkauf and U.
Phenomena. The Royal
hexagonal close packing). (Ref. Stimming, Phys. Chem.
Society of Chemistry, 1, based on data in [A. Köhn, F. Chem. Phys., 2005, 7, 385 ]
Weigend and R. Ahlrichs, Phys.
Cambridge, 2006 ] 4
Chem. Chem. Phys., 2001, 3, 711 ]
1.2 Size-dependent properties

Calculated cohesive energies of various


size magnesium clusters in their most Left: Background-subtracted differential scanning
stable geometry as a function of N–1/3. calorimetry melting endotherms for indium confined in
controlled pore glass (a–c) and in Vycor samples (d)
with different pore diameters. Note that the melting
feature of the pore-confined material moves to lower
temperatures and broadens as the pores get narrower.
Right: Melting temperature as a function of pore
diameter and inverse diameter. The broken line
represents the bulk melting point

a) Fluorescence of CdSe–CdS core–shell nanoparticles with a diameter of 1.7 nm (blue)


up to 6 nm (red), giving evidence of the scaling of the semiconductor band gap with
particle size. (Figure courtesy of H. Weller, University of Hamburg). b) Schematic
representation of the size effect on the gap between the valence band (VB) and the 5
conduction band (CB) and the absorption (up arrow) and fluorescence (down arrow).
Smaller particles have a wider band gap. .
1.2 X-ray Photoelectron Spectroscopy
(XPS)
• X-ray Photoelectron Spectroscopy (XPS) , or ESCA -
Electron Spectroscopy for Chemical Analysis

• Major components:
• X-ray Source
• High Vacuum Environment
• Electron Energy Analyzer

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1.2.1 Basically principle
• XPS works by irradiating a sample material with soft
x-rays causing core level electrons to be ejected.

• Surface information offered by XPS


– elements
– chemical status
– elemental composition
– electronic state
– depth analysis

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X-ray excite photoelectron and Auger electron processes
1.2.2 XPS information depth

An XPS surface analysis is not like slicing off


a few nanometers of the sample surface and
counting the atoms in the slice. The Beer-
Lambert law

tells us that the signal intensity from a layer of


atoms buried a distance z beneath the
surface is less than the signal intensity one
would obtain from that layer had it been at the
surface by a factor

where λ is the photoelectron attenuation


length and θ the photoemission angle.

" 95% of the information


obtained by XPS comes from
within three attenuation lengths
of the surface " , say 1-10nm
[ Elastic Scattering corrections in AES and XPS. II, Estimating Attenuation Lengths and Conditions
Required for their Valid Use in Overlayer/Substrate Experiments, by P.J.Cumpson and M.P. Seah,
Quantitative Electron Spectroscopy of Surfaces:A standard Data Base for Electron Inelastic Mean Free 8
Paths in Solids. By M.P.Seah and W.A. Dench ]
1.2.3 Surface compositions and chemistry

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1. 2.4 Surface chemistry

Oxidation of Mo with different


chemical states

Spectra deconvolution may be needed in order to


10
quantitative estimate of chemical states in most case due
Oxidation of Pd
instrument resolution limitation
1.2.5 XPS depth profiling: composition depth
distribution

Angle resolved XPS 11


Ion etching XPS
2. New challenges of XPS in
nanostructures
• 2.1 General nanostructured surface patterns

(a) (b) (c) (d)


Thin layer Island-like Hemisphere Sphere

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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

• For rectangle or square shape,


photoelectron emission intensity
from a nanoparticles, with a
narrow size distribution, following
as
d
I C = ΘI [1 − exp( − )]
0

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}

[G.K. Wertheim and S.B. DiCenzo, Phys.Rev. B 37(1988) 844]

• For a sphere particles with shell

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]

The ratio of two photoelectron emission intensities from a spherical nanoparticle,


having different escape depths λ, can be deduced from

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

The dimension r of the nanoparticles is only 20

R
related the ratio of two photoelectrons from 16

a nanoparticles. 12

8
0 5 10 15 20 25 30
19
35 40

Nominal Cu thickness (A)


The ratio of Cu2p3 to Cu3d as Cu mass thickness
6 Angle-resolved XPS of nanoparticles
6.1 Current issues: 1.4

1.3
Cu2p3/2 (a)

Cu2p 3/2 peak intensity (normalized)


1.2

1.1

1.0

0.9

No model for angle 0.8


3 Å, 0.1 Å/sec
3 Å, 0.02 Å/sec
0.7

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

experimental data are


reported 1.8

1.7 3 Å, 0.1 Å/sec (b)


Cu3d
Our experimental 1.6
3 Å, 0.02 Å/sec
8 Å, 0.007 Å/sec

Cu 3d peak intensity (Normalized)


1.5 8 Å, 0.15 Å/sec

data are not 1.4

1.3
32 Å, 0.25 Å/sec

consistent for 1.2

1.1

different XPS peak; 1.0

see Figs. a and b


0.9

0.8
0 10 20 30 40 50 60 70 80

θ 20
6.2 Monte Carlo simulation model

•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

Effect of size distribution on the


Effect of λ on the photoelectron emission photoelectron emission
R D R D R
D D
R1 R3
R2

Radius=5(0) Distance=2(0) Radius=5(1) Distance=2(0)


2.5
2.3
2.5
2.1 2.3 R/λ
1.9 R/λ 2.1
Relative Intensity

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

The Monte Carlo simulations show that:


the unexpected photoelectron emission behavior can be explained
by different size distribution of the nanoparticles, separation and
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the ratio of the mean size to λ.
7. Binding energy and related core level shift
of NPs:
Binding energy shift of core level
• Experimental results

[M.G.Mason, Phys.Rev.B27(1983)748; G.K.Wertheim


and S.B. DiCenzo, Phys.Rev.B37(1988)844] 23
[H.G.Boyen et al,
Phys.Rev.Lett.,
94(2005)016804]

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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

•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.
α ' = E B (Cu 2 p3 / 2 ) + E K ( L3 M 4,5 M 4,5 )

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

Nominal Cu thickness (A)

Auger parameter as a function of initial thin film


deposition, which is used to evaluate initial thin film
growth. Figure shows that different substrate have
different contributions to the Auger parameters. There
is no any affects of surface charging in XPS using Auger 28
parameters
7.4 Wagner plots
Wagner plot is also called a chemical state plot, which uses both
photoelectron and x-ray excited Auger lines, increase the utility of XPS for
identifying chemical states
EB ~ EK

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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

0.00 HOPG Cyclotene


0.6

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


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

-0.02

0.5 surfac untreat Ar+- untreat untreat Ar+- N2-


-0.04
e ed treated ed ed treated treated
0.4 -0.06

metalli evapor evapor sputter evapor evapor evapor


0.3 -0.08 zation ated ated ed ated ated ated
-0.10
0.2

-0.12 ratio 1.8 1.8 1.8 0.02 0.09 0.25


0.1

-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.

The collaborations of Prof. L. Martinu, Drs. J. E. Klemberg-Sapieha, S. Poulin,


and O. Zabeida, from Ecole Polytechnique of Montreal, are also appreciated.

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