Electrochimica Acta 74 (2012) 83–86

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Mesoporous TiO2 nanowires as bi-functional materials for dye-sensitized solar

cells
Sangwook Lee a , Gill Sang Han b , Ji-Hae Lee c , Jung-Kun Lee d , Hyun Suk Jung b,∗
a
Department of Material Science and Engineering, University of California at Berkeley, CA94709, USA
b
School of Advanced Materials Science and Engineering, Sungkyunkwan University, Suwon 440-746, Republic of Korea
c
Seoul Semiconductor, Ansan 425-851, Republic of Korea
d
Department of Mechanical Engineering & Material Science, University of Pittsburgh, Pittsburgh, PA 15261, USA

a r t i c l e i n f o a b s t r a c t

Article history: A bimodal structured TiO2 nanowire (NW) was synthesized via metal glycolate-mediated method. Each
Received 4 October 2011 large NW was comprised of a few nanometers-sized anatase particles, which led to a high specific surface
Received in revised form 31 March 2012 area, 50.4 m2 g−1 . When the bimodal TiO2 NWs were coated onto a spherical nanoparticle-based active
Accepted 2 April 2012
layer of the photoelectrode for a dye-sensitized solar cell, the reflectance of the photoelectrode increased
Available online 13 April 2012
by 4-times, compared to a bare active layer. The TiO2 NWs increased quantum efficiency of the dye-
sensitized solar cell, from 400 to 800 nm wavelengths, which was attributed to both the light-scattering
Keywords:
and charge generating effects due to the capability of reflecting incident light and adsorbing large amount
Dye-sensitized solar cell
TiO2
of dye molecules.
Nanowire © 2012 Elsevier Ltd. All rights reserved.
Scattering
Bimodal structure

1. Introduction that are micron-sized particles exhibiting high specific surface

During the last two decades, a great deal of scientific
and technical advances have been achieved in semiconductor
nanoparticle-based dye-sensitized solar cells (DSSCs) which are
regarded as a potential cost-effective alternative to currently dom-
inant silicon solar cells [1–3]. A traditional DSSC is composed of
a photoelectrode containing a nanoporous TiO2 active layer (AL),
transparent conducting oxide (TCO) layer, dye molecules, an iodide
electrolyte, and a Pt counter electrode [4–8]. Notably, the dye-
loaded porous TiO2 AL is one of the key components to this design,
because, in this film, electrons are photo-generated and trans-
ported to the TCO layer. As the light penetration depth of AL is
longer than the electron diffusion length, light scattering layers
have been employed in DSSCs [9–11]. Usually, the light scattering
layer is composed of a few hundred nanometers-sized spherical
TiO2 particles to confine the incident light via the Mie scattering
[12]. This light scattering effect is supposed to increase the pho-
tocurrent and thereby the overall conversion efficiency. However,
these bulky scattering particles cannot provide sufficient surface
area to load dye molecules for electron generation because of
their low specific surface area [13,14]. Recently, bimodal structures
∗ Corresponding author. Tel.: +82 31 290 7403; fax: +82 31 290 7410.
E-mail address: hsjung1@skku.edu (H.S. Jung).
areas, such as nano-embossed hollow spherical TiO2 particles [15]
and mesoporous TiO2 beads [16], have been exploited to yield
bi-functionality, i.e. light-scattering and charge-generating prop-
erties. The bi-functional layers in DSSCs demonstrated to boost
photocurrent densities.
In this report, we introduce a micrometer-sized wire comprised
of a few nanometers-sized TiO2 nanoparticles for application to
a functional layer of DSSC. By employing the bimodal-structured
nanowires (NWs), the external quantum efficiency (EQE) of the
DSSC was enhanced in the wavelength region of 550–800 nm due
to the light scattering of the large-sized wires, and even in the
400–550 nm region due to the high specific surface area of the TiO2
nanoparticles contained in the nanowires.
2. Experimental
Titanium tetrabutoxide (25 mM), urea (250 mM), and tetra-
butylammonium bromide (124 mM) were added to ethylene
glycol (180 mL). The solution was refluxed at 195 ◦ C for 6 h.
About 4 h later, a yellow precipitate began to appear. After a
further 2 h, the mixture had become completely dark brown.
The dark brown precipitate was collected by centrifugation, and
washed several times with ethanol. The synthesized NWs were
investigated using a field-emission scanning electron microscope
(FESEM, JSM-6330F, JEOL), high-resolution transmission electron

0013-4686/$ – see front matter © 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.electacta.2012.04.008
84 S. Lee et al. / Electrochimica Acta 74 (2012) 83–86

Fig. 1. FESEM image (a and b), XRD pattern (c) of the synthesized TiO2 NWs.

microscope (HRTEM, JEM-3000F, JEOL), and X-ray powder NWs was 50.4 m2 g−1 , which is comparable to the commercial TiO2
diffractometer (XRD, M18XHF, Mac-science Instruments). Opti- nanopowder, P25 (47.5 m2 g−1 ) [17].
cal reflectance spectra were measured by a UV–vis spectrometer The NWs were deposited onto nanoporous TiO2 ALs to fabricate
(Lamda 35, Perkin-Elmer). The specific surface areas were deter- photoelectrodes of DSSCs. The FESEM images (Fig. 3(a–c)) show that
mined via Brunauer–Emmett–Teller (BET) analysis. the NWs are homogeneously coated (∼10 ␮m) onto the AL (∼8 ␮m).
A sandwich-type DSSC was fabricated with N719 dye, AN-50 The reflectance of the photoelectrode was measured to check the
electrolyte (SOLARONIX), Pt counter-electrode, and the photoelec- light-scattering capability (Fig. 3(d)). For the comparison, a typi-
trode that was fabricated by screen printing the NWs on a spherical cal light-scattering layer/AL-based photoelectrode (10 ␮m/8.2 ␮m
TiO2 nanoparticle-based AL which was coated on a fluorine-doped as shown in Fig. S2 in Supplementary material) was also prepared
tin oxide electrode, which processes were demonstrated by a previ- using commercial scattering particles (CCIC, Japan). The CCIC layer-
ous report [17]. The photovoltaic properties were measured using based photoelectrode exhibited 1.5 times higher reflectance than
a potentiostat (CHI 608C, CH Instruments) and a solar simulator the NW layer-based one. Nevertheless, the NW/AL-based photo-
(AM 1.5, 100 mW cm−2 ). The EQE was measured using a spe- electrode exhibits about 4-times higher reflectance than the bare
cially designed incident photon-to-current efficiency (IPCE) system AL-based photoelectrode, which indicates that the NW can work as
(PV measurements) for dye-sensitized solar cells. The amount of an efficient light-scattering layer.
adsorbed dye molecules were determined by the desorbed dye Fig. 4 shows the photovoltaic J–V curves for bare ALs (8 ␮m
solutions from the dye loaded powders at 50 ◦ C for 2 h. and 18 ␮m)-, and NW/AL-based photoelectrodes. The average val-
ues of photovoltaic performances with standard deviations are
3. Results and discussion summarized in Table 1. We checked the reproducibility by five
times of repeated experiments. By employing the additional NW
As-collected dark brown precipitate was NWs with diameters
of 0.5–3 ␮m and lengths of 20–40 ␮m (Fig. S1 in Supplemen-
tary material). Recently, the Xia group reported that metal glycolate
NWs were obtained by refluxing metal alkoxide with ethylene gly-
col [18,19]. During the reflux, the ethylene glycol units gradually
replaced the alkoxide groups, and then the metal glycolates were
oligomerized, and eventually led to the formation of longer chains
which self-assembled into NWs. In the present study, therefore,
the precipitate was considered to be titanium glycolate. To obtain
anatase TiO2 NWs, the precipitate was annealed at 450 ◦ C for 1 h in
air. Fig. 1(a) shows a FESEM image of the annealed NWs, indicating
that no major change in dimension took place during the annealing
process. The edge of a NW (Fig. 1(b)) shows that the NW is com-
prised of tiny nanoparticles. The XRD (Fig. 1(c)) pattern shows that
the NW has an anatase phase.
HRTEM image for the TiO2 NW (Fig. 2(a)) shows that the size of
nanocrystals contained in the NW is less than 10 nm. The apparent
lattice images (Fig. 2(a)) and the ring-typed selective area diffrac-
tion pattern (Fig. 2(b)) show that the NW is composed of anatase
polycrystalline. The HRTEM micrograph (Fig. 2(c)) shows that the
TiO2 NW is an aggregate of nanoparticles with nanopores. The
nanoporous nature of the NWs synthesized by the metal-glycolate
mediated method was reported by several groups [18–20]. In the
case of SnO2 NWs, this nanoporous property makes them applica-
ble as gas sensor materials [18]. Likewise, this nanoporous structure
of the NW is favorable for dye adsorption in DSSCs because of Fig. 2. HRTEM image (a), SAD pattern (b), and TEM image (c) of the synthesized TiO2
the large surface area. The BET surface area of the synthesized NWs.
 S. Lee et al. / Electrochimica Acta 74 (2012) 83–86 85

Fig. 4. Photovoltaic J–V curves of the bare AL-, NW/AL-, and CCIC/AL-based DSSCs.

Approximately two-time increase in the bare AL thickness

improved  by only 9%.
Although the reflectance of the NW-based photoelectrode is
lower than that of the CCIC-based photoelectrode (Fig. 3), both
the NW-based and CCIC-based one exhibited similar cell efficiency.
To understand the main factor of the improved efficiency for the
NW-based DSSC, IPCE spectra from each cell were measured as
the function of the incident light wavelength. The IPCE spectra
(Fig. 5) show that both the NW and CCIC scattering layer-based
DSSCs exhibit more excellent IPCE than the bare AL-based DSSC,
demonstrating the enhanced light-harvesting capability. Although
the NW-based DSSC shows lower IPCE than the CCIC-based DSSC
in the range of 550–800 nm consistent with the aforementioned
reflection result shown in Fig. 3, the NW-based DSSC exhibits a
much higher IPCE than the bare AL-based DSSC in the same range
(Fig. 5). The normalized figure (inset of Fig. 5) clearly shows the
enhanced IPCE in this wavelength range. This demonstrates that the
NW layer contributes to improving the light-harvesting properties

Fig. 3. Cross-sectional FESEM image of the NW/AL (a), plain view of the NW layer
(b) and the AL (c), and UV–vis reflectance of the bare AL- and NW/AL-based photo-
electrodes (d).

layer, the energy conversion efficiencies () of the DSSCs were

increased significantly in comparison with the bare AL-based DSSC.
The improved  is ascribed to the significantly increased short cir-
cuit current density (Jsc ) from 9.0 to 12.4 mA cm−2 . On the other
hand, the open circuit voltage (Voc ) and fill factor (FF) did not con-
tribute to the improved . The NW layer enhanced the  by 23%
from 5.3% to 6.6%, which is comparable to  of the CCIC layer-based
DSSC, 6.8%. The increase in the thickness of the bare AL did not
remarkably improve the photovoltaic energy conversion efficiency.

Table 1
Photovoltaic parameters calculated from the J–V curves shown in Fig. 4.

Jsc (mA cm−2 ) Voc (V) FF (%)  (%)

Bare (8 ␮m) 9.0 ± 0.14 831 ± 2.1 71.1 ± 1.0 5.33 ± 0.04
Bare (18 ␮m) 10.3 ± 0.13 792 ± 1.7 71.2 ± 1.7 5.79 ± 0.08
NW/AL (10/8 ␮m) 12.4 ± 0.06 780 ± 4.7 68.1 ± 1.9 6.58 ± 0.21
Fig. 5. IPCE spectra of the bare AL-, NW/AL-, and CCIC/AL-based DSSCs. Inset shows
CCIC/AL (10/8 ␮m) 12.5 ± 0.09 800 ± 6.6 68.4 ± 1.6 6.82 ± 0.12
the normalized IPCE spectra.
86 S. Lee et al. / Electrochimica Acta 74 (2012) 83–86

properties of the bimodal NW, which led to significant increase of

Jsc of the DSSC and consequently enhancing the cell efficiency by
24% in comparison with the bare active layer-based DSSC.

Acknowledgements

This work was supported by the National Research Founda-

tion of Korea (NRF) grant funded by the Korea government (MEST)
(R11-2005-048-00000-0, 2011-0017210, and 2011-0031606). This
work was also supported by the New & Renewable Energy of the
KETEP grant funded by the Ministry of Knowledge Economy (2010-
T100100460).

Appendix A. Supplementary data

Supplementary data associated with this arti-

cle can be found, in the online version, at
http://dx.doi.org/10.1016/j.electacta.2012.04.008.

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