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DOI: 10.

2478/s11532-006-0015-3
Research article
CEJC 4(3) 2006 476488

Partially nanowire-structured TiO2 electrode for


dye-sensitized solar cells
Yoshikazu Suzuki , Supachai Ngamsinlapasathian, Ryuhei Yoshida,
Susumu Yoshikawa
Institute of Advanced Energy,
Kyoto University,
Uji, Kyoto 611-0011, Japan

Received 20 December 2005; accepted 13 March 2006


Abstract: Partially nanowire-structured TiO2 was prepared by a hydrothermal processing followed by
calcination in air. The hydrogen titanate powder as-synthesized was calcined at 300 C for 4 h to obtain
the partially nanowire-structured TiO2 . A dye-sensitized solar cell (DSC) with a lm thickness of 5.6
m, fabricated using the partially nanowire-structured TiO2 showed better performance than using a
fully nanowire-structured TiO2 or a conventional equi-axed TiO2 nanopowder. The short-circuit current
density (JSC ), the open-circuit voltage (VOC ), the ll factor (FF) and the overall eciency () are 11.9
mA/cm2 , 0.754 V, 0.673 and 6.01 %, respectively. The eects of one-dimensional nanostructure and
electron expressway concept are discussed.
c Versita Warsaw and Springer-Verlag Berlin Heidelberg. All rights reserved.

Keywords: TiO2 nanowire, partially nanowire-structured TiO2 , dye-sensitized solar cell, electron
expressway concept

Introduction

TiO2 powder is widely used for industrial applications, such as pigments, cosmetics,
electronic devises, photocatalysts, catalyst supports, dye-sensitized solar cells etc. In
order to improve various functions of TiO2 powder viz phase, size and morphology, the
various factors have been extensively studied. Since the innovative work by Kasuga et al.
in 1998-99 [1, 2], TiO2 -derived one-dimensional (1-D) nanomaterials synthesized by the
hydrothermal alkali treatment method, such as nanotubes [320], nanowires [2125], and
nanobers [2628], have attracted much attention because of their unique microstructure

E-mail: suzuki@iae.kyoto-u.ac.jp

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and promising energy-related applications.e.g., lithium ion batteries [23, 24, 29], hydrogen
storage [30, 31], and dye-sensitized solar cells (DSCs) [32].
Since ORegan and Gratzel rst reported DSCs made of nanocrystalline porous TiO2
electrode in 1991 [33], a variety of semiconductor electrodes have been investigated. With
the objective of preparing ecient electron transfer paths through the electrode of DSCs,
porous lm electrode composed of various 1-D nanomaterials have been fabricated [32, 34
39]. Addition of carbon nanotubes into porous TiO2 electrode [3436] and preparing the
electrode by titania (or titanate) nanotubes [32], electrospun TiO2 bers [37] or ZnO
nanowires [38, 39] are typical examples of these studies. Using 1-D TiO2 nanomaterials as
well as hydrogen titanates, H2 Tin O2n+1 , which transform into TiO2 at high temperatures
is a straightforward way to realize the electron expressway concept (Fig. 1).

Fig. 1 Electron expressway concept by the incorporation of 1-D nanomaterials for DSC
electrode. The arrows indicate the path of the electron transfer.
However, to date, 1-D nanostructured electrodes have not yet resulted in a remarkable improvement in solar-energy conversion eciency. For example, in an early study
by Uchida et al. [32], they applied the hydrothermally prepared titania nanotubes for
DSC, and reported that there was almost no improvement in the eciency by using titania nanotubes (3.0 % for the commercial nanopowder, and 2.9 % for the nanotubes).
Although the nanotube-structured TiO2 is fascinating due to its high surface area, its
thermal stability is generally poor and it easily fragments into nanoparticles at a temperature of 500-600 C [19, 4043], which is close to the sintering temperature of DSCs
porous electrode (500 C).
The nanowire-structured TiO2 therefore forms a promising alternative candidate to
the nanotube, for a DSC electrode. Solid TiO2 nanowires as opposed to the hollow 1-D
nanomaterials can be similarly synthesized by a hydrothermal process at temperatures
typically between 150-170 C followed by the appropriate calcination process. These are
expected to show better thermal stability. In our preliminary experiments, however, a
fully nanowire-structured anatase TiO2 that was prepared as stated in Reference 25 did
not show a high DSC performance as expected. It showed a conversion eciency of 2.1
% and we attribute it to its low specic surface area (14 m2 /g) [42].
In this study, to harmonize the 1-D nanostructure and the high surface area of the

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electrode, we attempted to fabricate a partially nanowire-structured TiO2 via a modifed hydrothemal process and to apply it for DSCs. The idea is an analogy with a road
network system where truck lines and narrow paths are combined for ecient mass transportation. There are several routes available to prepare the TiO2 1-D nanomaterial/TiO2
nanoparticle composite structure:
(i) Simple mixing of pure 1-D nanomaterial and pure nanoparticles as cited in the
literature [3436] for addition ofcarbon nanotubes to TiO2 powder
(ii) Preparing a 1-D nanomaterial/nanoparticle composite powder using chemical fragmentation of 1-D nanomaterials in acid solution at low pH (pH 0) [28]
(iii) Preparing 1-D nanomaterial/nanoparticle composite powder by using middle-stage
i.e., an incomplete hydrothermal treatment in a rather short period
(iv) Preparing nanowire/nanoparticle composite powder by using thermal fragmentation
of the thermally unstable 1-D nanomaterials as in titania nanotubes or by in situ
thermal fragmentation during the sintering process for preparation of DSC devices.
We chose the third approach of middle-stage hydrothermal treatment because it involved a short time and low cost process. In addition, compared to the other approaches
we expected a good connectivity between 1-D nanomaterials and nanoparticles.

Experimental

Commercial ne TiO2 anatase powder (Ishihara Sangyo Ltd., ST-01, 300 m2 /g) was
used as starting material. 0.5 g of TiO2 powder and 50 ml of 10 M NaOH aqueous
solution were put into a Teon-lined stainless autoclave. The autoclave was heated and
magnetically stirred (400 rpm) at 150 C for 24 h. It was then cooled down to room
temperature, the precipitate was washed by H2 O and ltered in vacuum. The precipitate
obtained was ion-exchanged with an aqueous solution of HCl at pH 2 for 6 h. After
the HCl treatment, the precipitate was washed with distilled water and ltered. The
powder of hydrogen titanate as-synthesized was calcined at 300 C for 4 h to obtain the
partially nanowire-structured TiO2 . The TiO2 powder was evaluated by scanning electron
microscopy (SEM, JEOL, JSM-6500F), transmission electron microscopy (TEM, JEOL,
JEM-2010F), nitrogen adsorption (Quantachrome, Autosorb-3) and X-ray diractometry
(XRD, Rigaku, RINT-2100) techniques.
DSCs were fabricated using the partially nanowire-structured TiO2 and the ne
anatase (ST-01) powders. TiO2 pastes containing TiO2 powder and organic binders
were coated on FTO conducting glass (15 /) using the squeegee technique. The TiO2
lm was prepared by repetitive coating and sintering at 400 C for 10 min for each layer.
Finally, the electrodes were sintered at 450 C for 1 h. For all samples used in this
study, lm-processing conditions viz. repetitive coating times, calcination and sintering
conditions, and etc were kept uniform as much as possible. The nal lm thickness therefore closely reects the characteristics of the source powders such as packing density and
sinterability.
The sintered electrodes were immersed for 24 h in a 0.3 mM solution of ruthenium

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(II) dye (N719, Solaronix) in 1:1 v/v tert-butanol:acetonitrile solvent mixture. The redox
electrolyte composed of 0.6 M dimethylpropylimidazolium iodide, 0.1 M LiI, 0.05 M I2 ,
and 0.5 M 4-tert-butylpyridine in acetonitrile [44]. Pt-coated FTO was used as a counter
electrode. Solar energy conversion eciency was measured under simulated solar light,
i.e., AM 1.5, 100 mW/cm2 . The light intensity of the illumination source was calibrated by
using a standard silicon photodiode (BS520, Bunkoh-Keiki Co. Ltd.). The photocurrent
voltage curves were measured by using CEP-2000 (Bunkoh-Keiki Co. Ltd). A 300 W
xenon lamp, a monochrometer (Jasco), a scanning controller (Jasco), and a multimeter
(Keithley) were used for IPCE measurement of the solar cell. The thickness of TiO2 lms
was measured by a Tencor Alpha-step proler. It is noteworthy that all the cells tested
in this study contained no apparent cracks and delamination and was so conrmed by
the Alpha-step proler, optical microscope and SEM.

Results

Figure 2 shows typical SEM images of the partially nanowire-structured TiO2 . The
sample was composed of ne nanowires and relatively large particles. XRD and TEMSAED analyses revealed that the nanowires were composed of anatase phase and the larger
particles consisted of rutile phase (Fig. 3). Recent study by Zhu et al. revealed that the
phase transition between nanostructures of titanate and titanium dioxides proceeds at
rather low temperature with the assistance of acid treatment [45] and the results of this
study is well explained by their phase-relation model. In addition, co-existence of a small
amount of rutile nuclei accelerates the rutile particle formation. Relatively large rutile
particles found in Fig. 2(a) and Fig. 3(a) are expected to act as light-scattering centers
in the DSCs.

Fig. 2 SEM micrographs of the partially-nanowire structured TiO2 , consisting of ne


anatase nanowires and relatively large rutile particles. (a) low magnication, (b) high
magnication for nanowires.
The specic surface area of the partially nanowire-structured TiO2 powder was 174
m /g, which was much higher than the fully nanowire-structured TiO2 powder in our
2

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Fig. 3 (a,b) TEM micrographs, showing the co-existence of ne nanowires, nanowirecoated rutile and rutile particles (c) SAED pattern for the nanowire area of the partially
nanowire-structured TiO2 (showing anatase pattern), and (d) XRD pattern for the whole
partially-nanowire structured TiO2 powder.

previous work [25]. The isotherms showed hysteresis behavior, demonstrating the existence of mesopores (Fig. 4(a)). The pore-size distribution calculated by the BJH method
for the desorption curve is plotted in Fig. 4 (b). The pores ranging from 10 nm to
more than 100 nm are mainly attributed to the interstitial spaces within the nanowire
aggregates [40]. Note that there might be some co-existing nanotubes (in general, typical
internal pore-size is ca. 5 nm), but they should be a minor portion judged from TEM
observation and Fig. 4(b).
Figure 5 shows photocurrent-voltage characteristics (I-V curves) of the solar cells
made from (a) the partially nanowire-structured TiO2 and (b) a commercial ne anatase
powder (ST-01) as a reference. The photovoltaic performance for partially and fully
nanowire-structured TiO2 as well as reference data, obtained from the I-V curves, are
summarized in Table 1. For the fully nanowire-structured TiO2 , the optimum sintering
temperature was slightly higher (500 C) due to its low surface area and less sinterability
[42]. Obviously, the cell made from the partially nanowire-structured TiO2 (henceforth
referred to as PNW cell) showed better photovoltaic performance than those from other
TiO2 powders, including the fully nanowire-structured TiO2 (FNW cell). Despite the
thin lm thickness (5.6 m), the PNW cell showed the best performance among similarly
fabricated cells; the short-circuit current density (JSC ), the open-circuit voltage (VOC ),
the ll factor (FF) and the overall eciency () are 11.9 mA/cm2 , 0.754 V, 0.673 and

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Fig. 4 (a) N2 adsorption/desorption isotherms and (b) BJH plot for desorption showing
pore-size distribution for the partially nanowire-structured TiO2 .
6.01 %, respectively.

Fig. 5 Photocurrent-voltage characteristics of DSCs prepared by using (a) partially


nanowire-structured TiO2 ( = 6.01 %), and (b) ST-01 powder ( = 4.13 %). Insert:
IPCE spectrum for (a).

Discussion

To elucidate the reason for the improved performance of the PNW cell, further microstructural evaluation was conducted. Figures 6(a) and (b) demonstrate the top and crosssection views of the PNW cell, respectively. Although a large part of TiO2 nanowires
converted into equi-axed nanoparticles after the sintering process as with the titanate
nanotubes in references [19, 40, 41] approximately 5-10 % of the 1-D nanowires still
remained and could be clearly observed. From the top views, it is observed that rela-

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Table 1 TiO2 powder characteristics and photovoltaic performances obtained from the
I-V curves of the fabricated dye-sensitized solar cells.
TiO2 powder characteristics
Hydrothermal
conditions

Calcination
conditions

Surface area
(m2 /g)

Description
of powder

150 C, 24 h

300 C, 4 h

174

anatase nanowires
+ rutile particles

300

anatase nanoparticles

Fully-nanowired
TiO2

150 C, 72 h

700 C, 2 h

14

anatase nanowires

Fully-nanowired
TiO2 (B)

150 C, 72 h

500 C, 2 h

20

TiO2 (B) nanowires

300

anatase nanoparticles

Partially-nanowired
TiO2
Equi-axed anatase
TiO2 (ST-01)

Equi-axed anatase
TiO2 (ST-01)

Photovoltaic performancesa
Final sintering
conditions for
DSC

Electrode
thickness
(m)

Current
density,JSC
(mA/cm2 )

Voltage,
VOC
(V)

Fill factor
FF

Adsorbed
dye
mol )
(108 cm
2

Eciency
(%)

Partially-nanowired
TiO2

450 C, 1 h

5.6

11.9

0.754

0.673

8.7

6.01

Equi-axed anatase
TiO2 (ST-01)

450 C, 1 h

12.8

8.16

0.714

0.710

13

4.13

Fully-nanowired
TiO2

500 C, 1 h

14

5.3

0.65

0.62

7.2

2.1

Fully-nanowired
TiO2 (B)

500 C, 1 h

12

2.0

0.59

0.43

8.1

0.57

Equi-axed anatase
TiO2 (ST-01)

500 C, 1 h

9.5

10.5

0.65

0.73

19

5.0

a Area:

0.25 cm2 , using FTO substrate of 15 /.

tively large nanowire-bundles bridged nanoparticles aggregates, which presumably oer


the electron conducting path as well as prevent the formation of relatively large open
pores or microcracking amongst aggregated particles. The cross-sectional views (Figs 6
(c) and (d)) show that some nanowires bridged coated layers to prevent the delamination
via anchor eect to provide the interconnections.
In a separate experiment, addition of 10 %-nanowire to a commercial nanopowder
(namely, route (i) as described in the introduction part) showed highest eciency among
0-100 % nanowire compositions [46], which is in good agreement with this study. In
addition, in situ thermal fragmentation (described as route (iv)) concurrently proceeded
after route (iii), and as a result, approximately 10 % nanowires remained in the nal DSC

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Fig. 6 (a, b) Top views and (c,d) cross sectional views of the partially nanowire-structured
dye-sensitized solar cell electrode.

device. This phenomena is due to the relatively high surface area as observed by the N2
adsorption result (Fig. 4) and thus implies some co-existing nanotubes. Although the
nanowires in this study are transformable to nanoparticles, their 1-D morphology is much
stabler than that of nanotubes.
In order to conrm the above, the thermal stability of the nanowire in this study
was examined. It may be noteworthy that the actual localized temperature during the
sintering is be higher than the set temperature of the furnace at 450 C, due to the burn
out of organic binders. To discuss the morphological change of the partially nanowirestructured TiO2 , the hydrogen titanate nanowires synthesized were heat-treated at 650

C for 4 h (Fig. 7). Although some fragmentation and sintering ocurred, a large portion of
nanowires still retained their one-dimensional morphology. In other words, the partially
nanowire-structured TiO2 in this study had a higher thermal stability compared with
titanate (or titania) nanotubes [19, 4043]. Thus, during the sintering process for DSC
devices, a portion of nanowires (10 %) remained in the porous lm.
Although the absolute eciency value of 6 % in this study was much lower than the
maximum recorded value of 11 % for DSCs the result in this study demonstrates the
usefulness and potential of the electron expressway concept.
Using the 1-D TiO2 such as electrospun technique [37] or the 2-D vertical alignment of
1-D nanomaterials [38, 39] are also promising for improving the eciency.The partially

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Fig. 7 SEM micrographs of the partially nanowire-structured TiO2 , heat-treated at 650

C for 4 h indicating the improved thermal stability of one-dimensional structure compared with the reported nanotube-structured TiO2 : (a) lower and (b) higher magnications.
nanowire-structured design will also be applicable for them.

Conclusions

A partially nanowire-structured TiO2 powder was prepared by the middle-stage (or incomplete) hydrothermal treatment and was applied for designing a DSC device. The
partially nanowire-structured TiO2 nally formed a nanowire / nanoparticle composite
electrode that was approximately 5-10 % nanowire in composition, and it showed higher
DSC performance than the fully nanowire-structured TiO2 . Since, neither long-time hydrothermal treatment nor mixing process with nanopowder is required for this process,
it is in principle cost-eective. However, microstructural control and optimization are
required, and these will be the subject of our forthcoming papers [46, 47].

Acknowledgment
This work was supported by Grant-in-Aid for Science Research, No. 16685019 (For Young
Scientist: Category A); the 21COE program for Sustainable Energy System by MEXT,
Japan and the high-performance dye-sensitized solar cell project by NEDO, Japan.

Endnote
It may be worthy of note that Adachi et al. reported high-eciency DSCs consisted of
titania nanotubes prepared by a modied sol-gel technique using the surfactant assisted
templating method, or SATM [48, 49]. However, in a later report the author stated that
the nanotube in his early study was actually not titania but the misconception due to
contaminated carbon nanotubes [50]. Currently, he modied his concept to oriented

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attachment crystal growth of nanoparticles by SATM. If this is true, it can be considered


as single crystal-like short nanowires or nanorods.
Hara et al. [51] recently pointed out some technical problems in I-V measurements
and the importance of reproducible characterization of DSC an informative note for researchers in the DSC eld.

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