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A first report on the fabrication of vertically aligned anatase TiO2 nanowires

by electrospinning: Preferred architecture for nanostructured solar cells
Thirumal Krishnamoorthy,ab Velmurugan Thavasi,*c Mhaisalkar Subodh Gd and Seeram Ramakrishna*ef
Received 18th March 2011, Accepted 9th May 2011
DOI: 10.1039/c1ee01315g

Higher performance is expected in electronic devices that utilize

metal oxide semiconductors in vertical architecture owing to the
direct and effective electron transport. Producing anatase phase
vertical TiO2 nanowires on conductive substrate has been challenging. Herein we demonstrate for the first time not only the facile
fabrication of vertical arrays of anatase TiO2 nanowires, but also
fabricating the wires by using electrospinning method. Firstly
aligned nanofiberous TiO2 ribbons were produced by electrospinning
and then erected to vertical nanowires after the post-treatment. Asproduced vertical ceramic TiO2 nanowires possessed the area of 0.2
cm2 with wire diameter of 90 30 nm, and height up to 27 mm. This
approach can be a better alternative to the currently available
methods like hydrothermal synthesis and template assisted fabrication as the diameter, height of the wires, and spacing between the
wires can be effectively controlled by this method. With vertical
nanowires of anatase phase TiO2 as photoelectrode in dye sensitized
solar cells (DSSC), the solar-to-current conversion efficiency (h),
a
NUS Nanoscience and Nanotechnology Initiative (NUSNNI)-NanoCore,
National University of Singapore, Singapore 117576
b
School of Materials Science and Engineering, Nanyang Technological
University, 50 Nanyang Avenue, Singapore 639798
c
NUS Nanoscience and Nanotechnology Initiative (NUSNNI)-NanoCore,
National University of Singapore, Singapore 117576. E-mail:
velnanotech@gmail.com
d
School of Materials Science and Engineering, Nanyang Technological
University, 50 Nanyang Avenue, Singapore 639798
e
National University of Singapore, Singapore 117576. E-mail: seeram@
nus.edu.sg
f
King Suad University, Riyadh 11451, King Saudi Arabia

short circuit current (Jsc), open circuit voltage (Voc), and fill factor
(FF) were measured as 2.87% and 5.71 mA cm
2, 0.782 V, 64.2%
respectively.

Introduction
Several approaches to prepare vertically aligned one dimensional
nanostructured (ODNS) ceramic material have been developed in last
decade.110 Vertical ODNS ceramic material has been prepared either
by the synthesis or the fabrication method. The synthesis method
basically allows the anisotropic growth of different facets with
different energies of the crystals and produces single crystalline
materials, whereas fabrication methods such as anodic oxidation and
the template assisted method depend on the external bias/templates
and mainly yield polycrystalline materials. In the case of TiO2, it was
reported that synthesis method formed only single crystalline rutile
phase nanowires on fluorine doped tin oxide (FTO) substrate.6,10 This
was mainly because the lattice of rutile phase TiO2 closely matched
with the FTO lattice i.e. greater than 98% compared to 71% with
anatase phase which facilitates the nucleation of stable rutile TiO2.
Anatase phase TiO2 is preferred for electronic applications because of
its crystal plane (1 0 1) that exhibits better electron transport, lower
charge carrier recombination rate, better optical transparency and
higher surface area.11 Fabrication methods produce facile vertical
anatase phase polycrystalline TiO2 nanotubes. Despite the drawback
that they cannot produce single-crystalline phase materials, the
resultant polycrystalline vertical TiO2 nanotubes should eliminate
random grain networks compared to nanoparticulate film, and also

Broader context
It is prefereed for metal oxide semiconductors to be in a vertical architecture for applications in solar cells (dye sensitized solar cells,
DSSC) and other electronic devices owing to high electron mobility. Growing of dense vertical arrays of anatase phase TiO2 directly
on conductive substrate by currently available methods such as chemical synthesis or other fabrication methods is not possible. In
this report, we demonstrate the fabrication of nanowires of anatase TiO2 in vertical arrays for the first time using electrospinning
followed by a top-down process. As-produced high quality anatase TiO2 vertical nanowires of diameter 100 nm, height up to 27 mm,
and with an area of 0.2 cm2 yielded a power conversion efficiency of 2.89%. These vertically aligned electrospun TiO2 nanowires can
facilitate for better light harvesting and charge collection, and even better efficiency can be expected upon fine tuning of the diameter,
height and surface area of the wires and also the interspacing between the wires, which are very much feasible by our proposed
method in this report.
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increase contact points for electrical connection, both of which have

been vital for improving the efficiency of solar cells,8,12 batteries,13 and
water splitting.14 In principle, poor surface roughness (and surface
area) is found in vertical tube architectures compared to vertical wire
arrays. The surface roughness of a material is one of the major
properties that enhance the electronic device efficiency. In particular,
nanomaterials with a higher surface area per unit volume support
better dye loading, light absorption and charge separation in Dye
Sensitized Solar Cell (DSSC) devices. Berlinguette et al.15 prepared
anatase TiO2 nanowires directly on fluorine doped tin oxide (FTO),
a conductive substrate by molecular self-assembly method, but the
resulting nanowire arrays were found to be loosely packed and
randomly oriented. No literature to date is available on the method of
producing anatase TiO2 in vertical nanowires architecture. Furthermore, synthesis methods are limited in tuning the vertical nanowires
diameter, height, porosity and packing density concurrently. Hence,
there has been growing demand for new methods which can create
vertical nanoarrays and also allow tuning of the materials features
such as packing density, height and diameter of the vertical
nanowires.
Electrospinning, a fabrication method, produces one dimensional
anatase TiO2 nanofibers by passing the solgel solution through an
electrically conductive nozzle tip where a solution droplet is formed.
Upon applying a high voltage, the droplet gets charged and changes
its shape into a cone, which is then elongated into a fiber of micron or
nano-size depending on the surface tension/molecular weight/
viscosity of the solution. These fibers were collected on a metal
collector. The electrospinning method has been explored for
producing anatase one dimensional TiO2 in hollow,16 porous,17 and
core-shell nanostructures in random architectures.18 Despite its great
potential for scalability and cost effectiveness, the use of electrospinning in the domain of nanoelectronics has remained less explored
until now, owing to its inability to produce vertically aligned nanomaterials on any conductive substrate. Electrospinning, due to its
nature, cannot create vertically aligned nanowires directly because the
nanofibers are influenced by gravitational forces during the deposition on a collector. Hence, there has been a great demand for
a method to fabricate vertically aligned nanowires on a transparent
conductive oxide (TCO) substrate from electrospun nanofibers.
In this communication, we not only demonstrate for the first time
the vertical alignment of anatase phase TiO2 nanowires on conductive substrate but also propose electrospinning as the method of
fabrication. Horizontally aligned TiO2 nanofibers were produced by
using the modified electrospinning set-up and then erected to vertical
nanowires on a TCO substrate after a post-treatment process. The
vertically aligned nanoarray architectures were analyzed using scanning electron microscopy (SEM). The improvement of this method
with high-throughput electrospinning should open new doors to
potential applications such as nanostructured solar cells, batteries and
water splitting.

Experimental section
The solgel solution for electrospinning was prepared by blending 0.2
g of polyvinylpyrolidone (PVP) polymer (Mw 1 300 000, Sigma
Aldrich), 0.5 g of titanium(IV) isopropoxide (Sigma Aldrich), 1 mL
acetic acid (99.7%, ACS. reagent) and 3.5 mL ethanol. The solution
was stirred for about 0.5 h and then immediately loaded in two plastic
syringes equipped with a 27 G stainless steel needle which has an
2808 | Energy Environ. Sci., 2011, 4, 28072812

Fig. 1 Schematic of the modified electrospinning setup with the airshield to generate horizontally aligned nanofiberous ribbon directly on
the copper strip.

inner diameter of 250 mm. As shown in Fig. 1, the two needles were
connected (with a gap of 1 cm between them) by a 1.5 cm  1.0 cm
size aluminium disc and the disc was connected to a high voltage
supply (Gauss High Voltage Research Inc. model RR50-1). The
solution feed rate was set to 0.2 mL h
1 using a syringe pump (KDS
200). The needle voltage was held at 15 kV dc voltage between needle
and ground. A copper strip with a width of 2 cm was rolled over the
rotating disc of diameter of 20 cm, which was then set at a distance of
10 cm from the needles to collect the electrospun fiber. The rotating
disc was placed with the air-shield at a distance 5 cm from the needle.
The speed of the rotating disc was set at 750 rpm to collect the aligned
nanofibers on copper strips. Fibers were collected for 4 h and the
fiberous ribbon was peeled off from the copper strip without any
damage.

Results and discussion

Aligning the fibers to a higher thickness and larger area are the key
factors to achieve the vertical wires. Xia et al.19 used two pieces of
conductive collector placed several centimetre apart to uniaxially
align the nanofibers. Chase et al.20 used a slower speed copper wireframed drum for producing the aligned nanofibers. However, both
methods were unable to produce nanofiberous film of micron-level
thickness and large area. We modified the electrospinning set up with
an air-shield, and used a copper strip rolled around a rotating disc as
the collector. The schematic of the instrument setup is shown in Fig. 1.
Disc rotation above 750 rpm facilitated for the better alignment of
nanofibers initially. However, during electrospinning over the period
of time, it was observed that the majority of the TiO2 composite
nanofibers were found to have flown away instead of being deposited
on the copper strip-collector. This was due to the air turbulence
generated by the high speed rotating disc that affected the lightweight and non-sticky TiO2 composite nanofibers. Furthermore, air
turbulence also caused poor alignment of the fibers. A non-conductive block with a gap of size 14 cm  3.5 cm at the centre was
designed and it allowed the collection of aligned nanofibers with
a higher degree of alignment onto the copper strip without much air
disturbance. The design also reduced the collection time. At high
voltage, the charged TiO2 composite fibers were quickly attracted
towards the collector which in turn, reduced the time required to align
the fibers. Therefore, the sol gel composition was optimized in this
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study such that the voltage applied and the flow rate of the solgel
solution was as low as possible.
The fiberous ribbon (Fig. 2A) was peeled off from the copper
strip without any damage after continuously collecting for 4 h.
The fiberous film was sintered in a muffle furnace at 500  C for 4 h.
The samples of the aligned nanofibers were prepared by sticking the
fiberous film on a carbon tape then sputter coating with gold for 2
min to reduce the charging effect for the scanning electron microscope (FE-SEM, Quanta 200 FEG System, FEI Company, USA).
The SEM analysis was used to examine the alignment and to measure
diameter and thickness. The cross sectional analysis using SEM
shows that the thickness is 25 mm and that the alignment is uniform
throughout its height (Fig. 2). SEM images in Fig. 2B confirm that
better alignment of ceramic TiO2 nanofibers was achieved and that
the alignment was also continuous over a minimum of a centimetre in
length after sintering. Fig. 2A shows the image of the as-spun TiO2
ribbon of size 60 cm  2 cm containing horizontally aligned nanofibers. This composite ribbon was cut into small pieces with dimension of 1 cm  2 cm (Fig. 2C), after sintering the size was reduced to
0.6 cm  1.2 cm (Fig. 2D). There is a 40% size reduction along the
fiber length, which is a crucial parameter in producing the approx.
30 mm height vertical nanowires. The resultant nanofiberous ribbon
with 60 cm length and 2 cm width was folded along its aligned
direction to get a width of 1 cm. A metal strip of size 2 cm  0.2 cm
was placed on one edge of the ribbon as shown in Fig. 3A. It was
rolled up together with the fiberous ribbon tightly against the fibers
aligned direction such that it forms a compact ribbon-roll, and finally
it was removed from the ribbon-roll. Similarly, five such ribbon-rolls
were prepared by repeating the electrospinning experiment and above
mentioned process. The purpose of making fibers in ribbon-rolls
using the plate as a roller was to retain the fibers integrity and
alignment upon rolling.
The as-prepared six ribbon-rolls were stacked one over one
another and hot pressed at 110  C for 15 min to form a single ribbon
sheet, then the sheet was transferred to a paraffin-wax bath of 110  C
and soaked for 1 h. This process enabled the wax to penetrate to the
entire portion of the sheet, which helped the fibers to maintain
smoothness during the cutting and filing processes. Furthermore, as
the paraffin wax is chemically inert, it neither affected the fiber
composition nor the morphology. It was observed that processing the
TiO2 fiberous sheet beyond 110  C introduced hardness to the
fiberous sheet that made the fiberous sheet brittle during the cutting
process. The wax coated fiberous sheet was cut using a very fine
bandsaw blade in a direction perpendicular to the fibers alignment.
The cut-fiberous sheet was affixed in a vice such that the aligned fibers

Fig. 2 (A) photo image of horizontally aligned electrospun TiO2

nanofiberous ribbon; (B) top view indicates the good alignment; (C) &
(D) photo images of the aligned nanofiberous film indicate size reduction
after sintering.

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were standing upright, the top surface of cut-side of the sheet was
levelled using a sharp-edge knife, and then vertically erected on a glass
plate (Fig. 3E) using polyacrylic glue.
The aligned fiberous sheet was transformed into vertically erected
fibers of height more than 5 mm because of this inventive step. It is
known that most of the micro/nanoelectronic devices require the
active semiconductor film thickness (or height) of the vertical 1D
nanostructure to be about a few tens of microns. We have therefore
introduced a top-down approach on the vertically erected TiO2/PVP
composite fibers to give sizes down to a height of 30 mm.
It was expected that the sintering of TiO2/PVP composite fibers
would cause ca. 40% size reduction along the fiber length upon
removal of the organic matrix due to the solgel composition. A
metal spacer with a thickness of 60 mm was chosen for this top-down
process and placed on the plate as shown in Fig. 3F. The fibers
protruding above the spacer (beyond 60 mm) were trimmed using
a penknife to the level of the fibers leveled uniformly throughout the
film. This process produced the overall film of thickness of 60 mm
(Fig. 4A). The vertically erected nanofibers were of 45 50 mm height
initially, and the acrylic glue layer covered the thickness up to 1015
mm. The fiberous sheet should therefore be pressed such that the
polyacrylic glue occupies minimum thickness (10 mm) in between
the glass plate and the fiberous sheet during the erection process. This
also played a crucial role in producing the ceramic vertical TiO2
nanowires film of desired thickness in the later stage.
The vertical-composite-fiber-based glass plate was placed in an
oven for sintering at 500  C at a ramp rate of 2  C min
1 and dwell
period of 4 h. The organic matrix that contains PVP, paraffin wax,
and polyacrylic glue was removed upon sintering, and resulted in the
formation of a free-standing vertically aligned ceramic TiO2 nanofiberous film to a total thickness of 27 mm (Fig. 4B) and area size of
0.5 cm  0.4 cm. Such a thickness range is more preferable for solar
cells where the electron diffusion is limited. For example, it was
reported in the literature that for the high performance dye solar cells
(DSC), the effective electron diffusion length in TiO2 nanotubes could
be up to 100 mm.21
The SEM images of vertically aligned ceramic TiO2 nanofibers
indicated that the average diameter of the ceramic fibers was 90  30
nm (Fig. 4C). The side view of SEM images showed that the fibers
were a little wavy, which is also advantageous for applications in solar
cells as such an architecture should enhance the internal reflection of
sunlight. In the perfectly straight vertical fibers obtained by hydrothermal growth process, the photons from the sunlight could possibly
fall between adjacent nanowires without being able to be absorbed by
the light harvester.22 The fiberous film was found to be continuous as
well as free from cracks and damage, which is due to the intrinsic
entanglement of the fibers and better mechanical strength of the
fibers. Vertically aligned fibers processed without wax treatment
induced the amalgamation at the top surface of the film during the
levelling process, which can be clearly seen in SEM Fig. 5.
The thickness of the sintered vertical TiO2 nanowires film was
measured to be 27 mm, and was uniform throughout the film. This
was confirmed by measuring the thickness at different places of the
film. Wax usually decomposes below 300  C which is lower than the
crystallization temperature of the TiO2. This was also confirmed by
TEM analysis. Fig. 6A shows the bright-field image TEM images of
the nanowires made of crystalline titania nanoparticles with a diameter of 12 nm. The selected-area electron-diffraction (SAED) ring
patterns the debye-Scherrer concentric rings of (101), (004), (200),
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Fig. 3 Process sequences for the preparation of vertical nanowires. A) Roll up of nanofiberous ribbon along its length, Inset is photo image of the
nanofiberous ribbon; B) Stacking and hot pressing of nanofiberous roll at 110  C for 10 min; C) Soaking of the fiberous sheet in wax melt; D) Cutting at
the centre position of the fiber sheet; E) Gluing the cut side of the fiber sheet on glass plate, Inset is 60 mm thick spacer; F) Placing the spacer surrounding
the vertical fiber sheet; G) Top-down process to bring down the height to 60 mm by trimming the protruding fibers above the spacer; H) Vertically aligned
TiO2 composite wires on the acrylic glue layer; The inset is the real photo image of free-standing ceramic anatase TiO2 vertical nanowire film obtained
after sintering at 500  C.

(105) and (204) confirmed that the nanofibers were composed of

polycrystalline and indexed for anatase phase of TiO2. Fig. 6B shows
that the width of neighbouring lattice fringes is 0.35 nm, which
corresponds to the (101) plane of anatase TiO2, suggesting that wax
treatment did not affect the TiO2 crystalline phase evolution. It also
served to avoid the clumping of the fibers during the cutting process.
This vertical TiO2 nanowires film with the area of 0.15cm2 was then
attached on a FTO substrate by using TiO2 nanoparticles adhesion
layer as reported in the literature,23,24 shown in Fig. 7.
It was decided to construct a DSSC to investigate the significance
of vertically aligned TiO2 nanowires for energy/electronic device
applications. As such, 27 mm thick vertically aligned TiO2 nanowires
with nanoparticle adhesive layer on FTOs were soaked for 24 h in
a 1 : 1 volume mixture of acetonitrile and tert-butanol of N-719,
a light harvesting dye. The dye-adsorbed vertical TiO2 nanowires/
FTO was then washed in ethanol, dried and used as the photoelectrode in a DSSC. Platinum (Pt) was sputtered on another FTO
which was used as the counter electrode. The photo electrode and the
2810 | Energy Environ. Sci., 2011, 4, 28072812

counter electrode (FTO/Pt) were sandwiched together using paraffin

film spacer to make the solar cell. The electrolyte containing 0.1 M
LiI, 0.03 M iodine, 0.5 M 4-tert-butylpyridine, and 0.6 M 1-propyl2,3-dimethyl imidazolium iodide in acetonitrile was injected between
photo and counter electrodes. Vertically aligned nanowires based
DSSC was illuminated at 100 mW cm
2 by using a solar simulator
(San Ei, Japan equipped with an AM1.5 filter). The photocurrent
density and photocurrent voltage (JV) characteristics of the device is
shown in Fig. 8. As-fabricated DSSC exhibited a short-circuit current
(Jsc) of 5.71 mA cm
2, open-circuit voltage (Voc) of 0.782 V, fill
factor (FF) of 64.2%, and with an overall conversion efficiency of
2.87%. Kumar et al.25 grew a vertical array of rutile TiO2 nanowires
on FTO using hydrothermal method and demonstrated an efficiency
of 2.9% after optimization. Feng et al.26 obtained a photoconversion
efficiency of 3.39% for TiO2 vertical nanowire arrays grown by solvohydrothermal method, with an open circuit voltage (Voc) of 0.769 V,
short circuit current density (Jsc) of 7.29 mA cm
2, and fill factor (FF)
of 0.62. Better device performance can be achieved by attaching more
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Fig. 5 SEM images of vertically aligned electrospun TiO2 nanowires,

top-view shows nanowires without clumping, processed with wax.

Fig. 6 (A) TEM image of sintered electrospun TiO2 nanowires processed with wax and glue; (B) HRTEM image; (C) selected-area electrondiffraction (SAED) pattern.

Fig. 4 SEM images of vertically aligned electrospun TiO2 nanowires,

side view: (A) shows 60 mm height of composite nanofibers with wax and
glue; (B) shows height of the vertical nanowires 27 mm; (C) vertical
nanowires under high magnification view.

dye molecules to the facets of the nanowire by making them porous,

obtaining lower diameter (<50 nm) wires. Such investigations are
underway and will be communicated soon for publication. While
hydro-thermal and solvo-thermal synthetic methods are also effective
in obtaining vertical nanowires, the safety concern due to high
pressure and high temperature conditions, especially during scaling
up as industrial processes, empower our method as a good
alternative.
This journal is The Royal Society of Chemistry 2011

Fig. 7 (A) SEM image of vertically erected electrospun TiO2 nanowires

on an FTO plate for solar cell applications.

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conversion efficiency is very likely possible by using this method upon

optimizing the height of the vertical nanowires, improving the
porosity, and reducing the diameter, which are currently under
investigation. We strongly believe that the method developed here
will offer benefits to the researchers who work in the alternative
energy and electronic domains where the semiconducting materials
cannot be grown vertically and directly on conductive substrates.

Acknowledgements
This work was supported by Singapore NRF-CRP grant on
Nanonets for harnessing solar energy and storage and also NUS
and NTU for providing facilities to carry out the research. Dr Thavasi acknowledges NUSNNI-NanoCore for the support.

Fig. 8 Photocurrent density vs. voltage of a vertical anatase TiO2

nanowires array electrode under AM 1.5 illumination.

It is also to be noted that so far only rutile phase TiO2 nanowires

were demonstrated in vertical architecture by the researchers. This is
the first report on fabrication of the anatase phase TiO2 as vertical
nanowires and also their demonstration in DSSC that resulted in an
efficiency of 2.87%. The device results clearly show that vertically
erected TiO2 nanowires are electrically connected with FTO, indicating a facile and an expeditious route towards the fabrication of
vertically-standing TiO2 nanowires. Using our method, it can be
expected that TiO2 nanowires arrays longer than 10 mm can be
fabricated, which would enable greater light absorption and effective
charge transfer capabilities.

Conclusions
In summary, we have developed a facile and effective approach for
the fabrication of vertically aligned anatase TiO2 nanowires by the
electrospinning method. To the best of our knowledge, this is the first
report of anatase phase TiO2 nanowires in a vertical architecture, and
also the first demonstration of fabricating the vertical nanowires on
FTO substrate using electrospinning. Aligned nanofiberous TiO2
ribbons with a thickness of 25 mm and area of 60 cm  2 cm were
produced by using a modified electrospinning set-up and then erected
to vertical nanowires on a TCO substrate after the post-treatment.
As-produced vertical ceramic TiO2 nanowires possessed an area of
0.2 cm2 with wire diameter 90  30 nm, and wire height up to 27 mm.
This is the only possible method by which the height of the vertical
nanowires can be easily varied from 10 to 100 mm. Although the
present work was demonstrated for preparing vertical anatase TiO2
nanowires, this method could be extended to provide a generic route
to vertical nanowires of other metal oxides. Moreover porous, hollow
and core-shell vertical nanowires can also be prepared. Conversion
efficiency of 2.87% with photocurrent density of 5.71 mA cm
2 and
open circuit voltage of 0.782 V was achieved using vertical anatase
TiO2 nanowires as the photoelectrode in a DSSC. Enhanced photo

2812 | Energy Environ. Sci., 2011, 4, 28072812

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This journal is The Royal Society of Chemistry 2011