Article

pubs.acs.org/JPCC

Electrical and Optical Properties of Conductive and Transparent

ITO@PMMA Nanocomposites
Elen Poliani S. Arlindo,† Juliana A. Lucindo,† Carlos M. O. Bastos,‡ Paulo D. Emmel,‡
and Marcelo O. Orlandi*,†,§
†
Departament of Physics and Chemistry, São Paulo State University, CEP 15385-000, P.O. Box 31, Ilha Solteira, SP, Brazil
‡
Department of Physics, Federal University of São Carlos, CEP 13565-905, São Carlos, SP, Brazil
§
Department of Physical Chemistry, São Paulo State University, CEP 14801-970, P.O. Box 355, Araraquara, SP, Brazil

ABSTRACT: In this work, nanocomposite films of indium tin oxide

(ITO) nanowires in a PMMA matrix were obtained by tape casting. The
electrical, optical and morphological properties of films were studied as a
function of the amount of wires inserted in the composite, and it was
used 1, 2, 5, and 10 wt %. Results confirmed that films transmittance
decreases as the concentration of wires increases, attaining a minimum
transmittance of 55% for 10 wt % of filler. On the other hand, the
electrical resistance of composites was found to decrease by increasing
the filler amount and the dc characterization indicate that percolation
occurs for about 5 wt % of wires. The morphological studies carried out
by TEM were considered to be in good agreement with the electrical
results and confirm that for 5% of filler, the ITO nanostructures are in
contact with one another inside the polymer. Moreover, we made
computational simulation of 1D structures in a general matrix and it was
found that percolation should occur for about 12 wt %. Although computational results indicate higher amount of wires necessary
for percolation than we found experimentally, both results illustrate that using one-dimensional nanostructures as filler in
composites enables obtaining percolation for a smaller amount of filler than when using, for instance, nanoparticles. Therefore,
the simple processing technique employed here can be used to obtain transparent and conductive composites with several useful
applications.

1. INTRODUCTION PMMA is a widely used commercial polar polymer because

Nanomaterials are defined as materials that have at least one of
their dimensions in the nano scale. These materials have been
extensively studied in the past decade because of their
interesting properties and the opportunities opened to test
theories in the quantum range. In addition, the new or superior
properties presented by nanomaterials permit them to be used
technologically in almost all areas of knowledge.1−7
One interesting approach in the area of materials is the
possibility of combining two or more phases which are
immiscible at the microscopic level, but that result in a material
with better properties than its constituents. This type of
material is called a composite, and composites can have
polymer, ceramic or metallic matrix. Polymer matrix nano-
composites have attracted special attention because they can be,
for instance, lightweight and extremely strong depending on
their constituents. Furthermore, this class of materials may
possess antagonistic properties such as transparency in the
visible range and conductivity, which renders it to be
considered special. Usually, composites possess more than
one improved property for a special application, thus referred
to as multifunctional materials, and in order to have some
control over the desired property the matrix and fillers should
be carefully chosen.8−13
of its excellent transparence in the visible range of electro-
magnetic radiation; it is lightweight and possesses good
mechanical properties. Notwithstanding, the extremely low
conductivity of PMMA can be a drawback depending on its
application. In order to overcome this limitation conductive
filler can be inserted into the PMMA matrix. However, a
metallic or carbon based filler can induce opacity to the PMMA
and/or jeopardize the esthetical characteristic of the material.
Therefore, in the pursuit of transparent and conductive fillers
some ceramics with these desired characteristics, such as ATO,
ITO, and FTO, have been used, and composites with
nanoparticles of these materials have been widely studied.14−17
Among these ceramics, special attention has been given to ITO
because of its high conductivity and transparency values. In
addition, the use of nanostructures enables attaining
percolation threshold limits in composites for lower amounts
of filler when compared to macrocomposites, and studies on
high aspect ratio nanostructures such as carbon nanotubes
(CNTs) confirm attainment of percolation for less than 1 wt %
Received: April 2, 2012
Published: May 8, 2012

© 2012 American Chemical Society 12946 dx.doi.org/10.1021/jp3031418 | J. Phys. Chem. C 2012, 116, 12946−12952
The Journal of Physical Chemistry C
of filler. Hence, the use of high aspect ITO nanostructures to
obtain nanocomposites should be examined.18
The main goal of this work is to develop a method of
introducing different amounts of high aspect ratio ITO
nanostructures (nanowires) inside a polymeric matrix
(PMMA) followed by a study of its electrical, optical and
morphological properties. Composites studied were charac-
terized by UV−vis, dc (two and four probes) electrical
measurements and by scanning and transmission electron
microscopy (SEM and TEM, respectively). Moreover, a
computational simulation of 1D structures in a general matrix
was performed to know, theoretically, what is percolation
threshold of nanowires. Finally, results were discussed in detail.
2. EXPERIMENTAL SECTION
2.1. Growth of ITO Nanostructures. The ITO nanowires
were synthesized by a carbothermal reduction method using
the coevaporation of oxides.18 In this work, the starting
materials used were SnO2 (Sigma-Aldrich, 99.9% of purity) and
In2O3 (Sigma-Aldrich, 99.99% of purity) mixed in a molar
proportion of 1:1 with the reducing agent, which in the present
study was the carbon black (Union Carbide, > 99% of purity).
In a typical procedure both mixtures were placed in separate
alumina boats which were then inserted side by side in the hot
zone of a tube furnace (EDG, model FT-HI 40). The synthesis
was performed at 1150 °C for 1 h with the extremities of the
tube sealed with aluminum cover and PTHF o-rings. A N2 gas
flux of 80 sccm was kept throughout the synthesis to carry on
vapor to colder region of the tube. Details of the ITO
nanostructures synthesis are given in refs 18 and 19.
2.2. Preparation of Nanocomposites. To prepare the
nanocomposites, the material collected after the synthesis was
dispersed using an ultrasonic cleaner in an alcohol medium.
Then, the PMMA (Sigma-Aldrich, average molecular weight of
12000 g/mol) was dissolved in Tetrahydrofuran (THF) and a
known amount of ITO nanowires was inserted into the solution
at 1, 2, 5, and 10 wt % in relation to the amount of PMMA. The
suspension was kept under stirring for 15 min and then
deposited over a glass substrate using the tape casting process
at room temperature. After the removal of films from the glass,
no further processing was necessary to characterize the
nanocomposites.
2.3. Characterization of Nanowires and Nanocompo-
site. The wool-like material collected after the carbothermal
reduction synthesis was analyzed by X-ray diffraction
(Shimadzu, model XRD 6000) using the Cu Kα radiation in
the range of 20 to 60°.
The morphological characterization of the materials was then
performed using a field emission gun scanning electron
microscope (FEG-SEM; Jeol, models JSM 6330F and JSM
7500 F). The morphology, structure and chemical ratio of the
cations in the ITO nanowires were also analyzed by
transmission electron microscopy (TEM; Jeol JSM 3010
operated at 300 kV) equipped with energy dispersive X-ray
spectroscopy (EDS). The same technique (TEM, using a
Philips CM 200 microscope operated at 200 kV) was used to
study the percolation of wires inside the polymeric matrix. In
order to prepare the samples for SEM, some drops of a
suspension of ITO nanowires in an alcohol medium were
deposited on conductive and plane silicon substrate. For TEM
characterization of wires, one drop of the same suspension was
deposited on a carbon coated Cu grid, while for the composite
characterization, a composite film was produced on the Cu
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grids by inserting the grid into the suspension of ITO and
PMMA in THF which was dried at room temperature.
To carry out electrical measurements of the nanowires, a
quartz substrate with interdigitated gold electrodes made by
lithograph was used. A micromanipulator (Wentworth, model
MP1008) was then used to connect the substrate to a stabilized
voltage source (Keithley, model 237). For the two and four
probe electrical measurements in the composites, a resistivity
measurement system (Signatone, model Pro-4) and the
Keithley stabilized source were used simultaneously.
The optical characterization of the composite films (about 20
μm of thickness) was performed by UV−vis spectroscopy
(Varian, model Cary 50) in the range of 200 to 1000 nm. It
should be highlighted that the optical transmittance in the
visible range is an important parameter for the application of
these films.
2.4. Computational Simulation to Achieve Percola-
tion. To study, theoretically, the percolation threshold of fibers
in a general matrix, we developed a Fortran program which
calculates the intersection of random distributed fibers in a
matrix. In this program it is possible to change the box size,
which in this case is the matrix; and the number, size and
rotation angle of fibers. The program associates a number to
each fiber and has a subroutine to verify percolation,20,21 and
when different wires intersect they assume the same number,
which was chosen as the lower one. So, when two parallel sides
of the box have wires with the same number, percolation
occurred. In this study the box size was kept constant because
all films done by tape casting have the same size, and we
studied the percolation as a function of size and number of
fibers (the rotation angle of fibers was left between −180 to
+180 o for all simulations).
3. RESULTS AND DISCUSSION
3.1. ITO Nanostructures. After the synthesis of the ITO
structures, a wool-like material was collected inside the tube in
a region between 450 and 500 °C. Figure 1 presents the XRD
pattern of the collected material. All the peaks in the
diffractogram can be indexed by the Al, In0,2Sn0,8 (JCPDS
card #48-1547), and In2O3 (JCPDS card #6-416) phases. It is
Figure 1. XRD pattern of the collected material after the synthesis.
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The Journal of Physical Chemistry C
Figure 2. FEG-SEM images of typical ITO nanowires with square cross section and the width distribution of wires.
worth to mention that peaks of In1.875Sn0.125O3 phase (JCPDS
card #89-4597) superpose the In2O3 ones and the only way to
distinguish these phases is using data refinement or chemical
analysis or electrical measurements. In this work we used the
last two characterizations. The Al peaks are related to the
aluminum sample holder used in the XRD measurements and
have no correlation with the ITO sample. Moreover, the
relative intensities between the In2O3 and the In0,2Sn0,8 peaks
confirm that the former is present in greater amount. Regarding
the In2O3 phase, it is easy to recognize that the peak at 2θ =
35.5° is much higher than it should be for a nonoriented
powder, meaning that the sample has a preferential orientation
for the (400) planes with an interplanar distance of 2.5 Å. It is
important to notice that no peak was observed for tin oxide
phases. In fact, following the phase diagram of In2O3 and
SnO2,22 up to about 15 mol % of tin atoms can be in the solid
solution in the In2O3 matrix without any secondary phase.
According to the literature23−25 the tin rich metallic phase
should be related to particles which control the growth
mechanism of structures. Figure 2 illustrates the FEG-SEM
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characterization of the material obtained after the synthesis. It is
possible to observe that this material is composed of one-
dimensional structures with well-defined edges; its size is
homogeneous along their lengths and there are no apparent
superficial defects. Figure 2c shows a SEM image from which it
is possible to observe that the synthesized structures have
square cross section. This square cross section is expected for
the In2O3 phase, known to be cubic, if the growth occurs in
(h00) planes, and it is important to notice that the XRD result
showed preferential orientation for planes of this family.
Hereinafter, these square cross-section nanostructures will be
called nanowires. The SEM images also illustrated that most
nanowires have a metallic sphere at one extremity, thus
suggesting that the growth mechanism of wires follows a self-
catalytic vapor−liquid−solid (VLS) process. Figure 2d presents
the width distribution of wires. This figure clearly depicts a
single modal distribution and indicates that most of wires have
width between 51 to 100 nm. These findings are in good
agreement with previous reports about ITO nanostructures.5
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The Journal of Physical Chemistry C
Figure 3 presents TEM images of nanowires, confirming they
have a homogeneous width along their length. The high
Figure 3. (a) TEM and (b) HRTEM images of a typical ITO
nanowire. Inset in panel b is the Fourier-transform of the HRTEM
image.
resolution micrograph in Figure 3b and its Fourier-transformed
image show that each wire is single-crystalline and grows in the
In2O3 structure. Moreover, both the interplanar distance in the
HRTEM image and the electron diffraction indexation confirm
that wires grow in the (200) planes of the indium oxide phase.
This result agrees with the XRD analysis which showed
preferential orientation for this family of planes and also
explains the origin of square cross section obtained. In order to
ascertain that tin-doped In2O3 nanowires were synthesized, the
energy dispersive X-ray spectroscopy (EDS) technique was
used to examine the chemical composition of wires and
spheres. EDS spectra of both the wire and the sphere are given
in Figure 4. In this case, because the X-ray L lines of In and Sn
atoms are superposed, the X-ray K lines in a TEM microscope
were used. The EDS analysis showed that the wires are
constituted of indium, tin and oxygen atoms with a In:Sn
proportion of 89:11 at%, thus indicating this method was
successful in obtaining ITO nanostructures. Meanwhile, the
sphere chemical analysis showed the sphere is a Sn rich Sn−In
alloy with a In:Sn proportion of 22:78 at%. The EDS results for
the metallic spheres support those of the XRD, because the
proportion between cations obtained by EDS is close to that
Figure 4. EDS spectra: (a) ITO nanowire and (b) metallic sphere presents at the ITO wire extremity.
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obtained in the XRD metallic phase. The reason for obtaining
an Indium rich structure through a tin rich liquid sphere is
explained elsewhere.19
It is important to mention that these tin rich metallic spheres
must be in liquid phase at the wire formation temperature (450
°C), suggesting that the growth of nanowires follows a self-
catalytic VLS process.
Figure 5 presents the two probe electrical response for the
ITO nanowires. The electrical current is observed to vary
Figure 5. Two probe electrical response for ITO nanowires; the inset
shows a FEG-SEM image of the approach used to perform the
electrical measurements.
linearly with the applied voltage for both positive and negative
values of bias and the curve passes through the origin, which is
expected for an Ohmic material. The slope of the plot
represents the resistance of the wire which in this case is about
102 Ω. After carrying out geometric parameters correction, a
conductivity of about 1.1 × 106 S/m was obtained (resistivity of
about 90 μΩ cm). This value is found to be far higher than for
pure In2O3 nanowires, which is about 102 S/m,6 and similar to
ones obtained in other works6,26 for ITO nanowires. This
means that the doping of Sn atoms in the In2O3 matrix
increases the conductivity of nanowires, and this behavior
confers to ITO characteristics for special applications such as
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The Journal of Physical Chemistry C
transparent and conductive devices, which we will explored in
detail in the next section.
3.2. Nanocomposites. Nanocomposites filled with ITO
nanowires were produced using the quantities of filler already
described in the Experimental Section. Figure 6 shows typical
Figure 6. PMMA and ITO@PMMA photos of films with different
filler amounts.
photograph of composite films. It is easy to observe that films
present a good transparency although, as expected, the pure
PMMA film is found to be the most transparent one. As the
amount of filler increases, the transparency is found to decrease,
which is a characteristic behavior of composites.
The transmittance of films was measured quantitatively using
a UV−vis spectrometer and the resulting plot is given in Figure
7. The figure confirms that pure PMMA film transmits about
Figure 7. UV−vis spectra for pure PMMA and for nanocomposites;
the inset shows a zoom in the visible spectrum.
95% visible light and has a characteristic absorption at 275 nm,
attributed to carbonyl groups in the polymer macromolecule.27
For a wavelength below 257 nm, the transmittance is observed
to drop abruptly. This absorption is known as the optical
window of the PMMA, where the light energy is high enough
to excite electrons. Three changes are noticed in the UV−vis
results when ITO nanowires are inserted in the composite.
First, the absorption at 275 was found to increase as the
amount of nanowires was increased. This was attributed to the
interaction effect of the polymer with the wires; second, as
already observed qualitatively in Figure 6, the transmittance of
visible light was found to decrease as the amount of nanowires
in the composite increases, with the minimum transmittance
reaching about 55%, which is considered a good value for
several practical applications. Finally, composite samples were
found to present a small absorption band at 780 nm. This
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observation should be related to the spheres at nanowires
extremities since ITO does not have any absorption at this
wavelength,28,29 and this effect is more noticeable for
composites with higher amounts of filler.
Table 1 presents the two-probe electrical results for
nanowires and composites. The values clearly show that the
Table 1. Two Probe Electrical Results for Nanowires and
Composites
films R (2 probe)
PMMA 3.5 × 1010 Ω
PMMA/ITO 1% 4.0 × 1010 Ω
PMMA/ITO 2% 3.6 × 1010 Ω
PMMA/ITO 5% 2.5 × 104 Ω
PMMA/ITO 10% 5.3 × 103 Ω
ITO nanowire 2.2 × 102 Ω
insertion of 1 and 2 wt % of filler does not alter the electrical
resistance of pure PMMA. However, an abrupt fall in the
resistance is observed for 5 wt % of filler thus indicating the
start of percolation. On increasing the filler amount to 10 wt %
the electrical resistance of the composite was found to be only 1
order of magnitude greater than the nanowire one, and at this
point good percolation was reached for the composite. Figure 8
Figure 8. Plots of the transmittance at 550 nm and the electrical
resistance of composites as function of the amount of nanowires.
summarizes these findings and also shows the UV−vis average
transmittance at 550 nm. While the UV−vis data presents an
almost linear decreasing of transmittance as the amount of
nanowires increased, the electrical response has an abrupt drop
at 5 wt % of filler. So, Figure 8 shows that the effect of
nanowires insertion is more pronounced in the electrical
response than in the optical one, and this is a good result in
order to obtain transparent and conductive materials.
For those samples that presented percolation, it was possible
to measure the electrical resistance using the four probe
approach which represents a more accurate method. Values
obtained from this method are given in Table 2. From the four
probe method results, it was observed that the composite with
10 wt % of filler has about the same electrical resistance of
nanowires, confirming the occurrence of good percolation. The
electrical resistance corrected by the geometric parameters
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The Journal of Physical Chemistry C Article

Table 2. Four Probe Electrical Results and Conductivity for

Composites
films R (4 probe) σ
PMMA/ITO 5% 9.4 × 103 Ω 10.7 S/m
PMMA/ITO 10% 5.3 × 102 Ω 23.8 S/m

enabled calculating the conductivity of composites. While the

wires were observed to show a metallic-like behavior and high
conductivity, the composites present only reasonable con-
ductivity. This observed difference is due to the method used to
calculate the conductivity; for nanowires the two probe
measurement was used, while for the composites, the four-
probe measurement was employed.
To estimate the amount of filler theoretically necessary to
achieve percolation, a Fortran routine was developed. For
calculations, it was assumed a fixed size square box, with 1000
pixels in length, and we vary the size and the amount of filler.
Figure 9 shows a plot of average amount of filler necessary to
achieve percolation as function of wire length (wire width was
set as 1 pixel). In the same way which other reports,30 this plot
clearly shows that it is easier to achieve percolation using high
aspect ratio materials (like 1D nanowires), and the average of
percolation goes asymptotically to a limit value (20 wt %) as
the wire size increases. This value is higher than the one we
found experimentally to achieve percolation, and some errors
source are the average value obtained and the fixed wire length
used in the program: it is distributed in the obtained sample.
So, using the wire length of 400 pixels (average percolation at
23 wt %) we simulate the insertion of different amount of wires
in the matrix. Figure 9b shows a typical simulation with 20
wires (12.4 wt %) where is possible to see that percolation was
achieved in the horizontal direction. This value is much closer
to the experimental one to get percolation of filler in the
polymer matrix.
Figure 10 presents low magnification TEM images of the
composites for different amount of filler. In all images the
typical structure of PMMA can be clearly seen,31 while for
composites with 1 and 2 wt %, some isolated nanowires can
also be observed. This result is in good agreement with the
electrical ones since isolated wires could not decrease the
Figure 10. TEM images for the nanocomposite films: (a) 1 wt %, (b)
2 wt %, (c) 5 wt % ,and (d) 10 wt % of ITO nanowires.
electrical resistance of the composites. Furthermore, it is
important mentioning that although for 1 and 2 wt % filler
systems only isolated wires were observed, these wires were
more commonly found to occur in 2 wt % filler systems than in
1 wt % filler systems, as expected. For the composite with 5 wt
% of ITO, the TEM image clearly illustrates that percolation
was reached in some parts of the composite. This result also
supports the electrical results, which indicate the percolation
initiated for this amount of filler. For the sample with greater
amount of ITO percolation was also observed as shown in
Figure 10d. This kind of image is easily obtained during the
TEM analysis thus explaining the reason for the smaller
resistance obtained for this composite.
On the basis of the exposed analyses and observations, it can
be concluded that it is possible to produce transparent and
conductive composites by inserting conductive ITO nanowires
in a polymeric matrix. This result is important because
transparent and conductive films have a wide range of potential

Figure 9. (a) Plot of average number of wires to achieve percolation as function of the wire length and (b) typical simulation of wires with horizontal
percolation.

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The Journal of Physical Chemistry C Article

applications, and practical tests can be performed with this
system in order to examine its technological viability.
4. CONCLUSION
ITO nanowires were successfully synthesized by a carbothermal
reduction process with the coevaporation of oxides, and these
wires were used as filler in PMMA polymer. The electrical
response showed that ITO wires have a high conductivity (106
S/m), but incorporation of filler up to 2% does not change the
composite electrical resistance, and percolation began at 5 wt %
of filler. The optical response of the composite showed that the
transmittance decreases as the amount of filler increases, but
this effect is almost linear. It means that the filler insertion has a
greater influence on the electrical than on the optical response
of the composite. The TEM analysis supported the electrical
results showing that the beginning of percolation occurs for 5
wt % of filler and increasing the filler amount to 10 wt % does
not significantly alter the morphology of the composite. The
results presented here show that the insertion of a low
concentration of ITO nanowires in PMMA polymer enables
obtaining transparent and conductive composites.
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Corresponding Author (29) Lee, J. Y.; Yang, J. W.; Chae, J. H.; Park, J. H.; Choi, J. I.; Park,
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(31) Yeh, J. M.; Chang, K. C.; Peng, C. W.; Lai, M. C.; Hung, C. B.;
ACKNOWLEDGMENTS Hsu, S. C.; Hwang, S. S.; Lin, H. R. Mater. Chem. Phys. 2009, 115 (2−
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We would like to thank the financial support of Brazilian
funding agencies FAPESP and CNPq. TEM facilities were by
LME-LNLS and IQ-UNESP. SEM facilities were provided by
LMA-IQ-UNESP.

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