Synthesis of nanobranched TiO

2
nanotubes and their application to dye-sensitized
solar cells
Soon Hyung Kang
a,
*
, Wonjoo Lee
b
, Yoon-Chae Nah
c
, Kug-Seung Lee
d
, Hyun Sik Kim
e
a
Department of Chemistry Education, Chonnam National University, Gwangju 500-757, Republic of Korea
b
Advanced Material Research Lab, Samsung Advanced Institute of Technology, Samsung Electronics, Yongin-si, Gyeonggi-do 449-712, Republic of Korea
c
School of Energy, Materials, and Chemical Engineering, Korea University of Technology and Education, Cheonan-si, Chungnam 330-708, Republic of Korea
d
Texas Materials Institute, University of Texas at Austin, Austin TX 78712, United States
e
Honam Petrochemical Corporation, Daejeon 305-726, Republic of Korea
a r t i c l e i n f o
Article history:
Received 23 May 2012
Received in revised form
25 June 2012
Accepted 18 July 2012
Available online 7 August 2012
Keywords:
TiO
2
nanotube
Nanobranches
Dye-sensitized solar cells
Rutile TiO
2
Electron transport
a b s t r a c t
Nanobranched TiO
2
nanotubes (TONTs) were synthesized by a solegel dipping method for the formation
of seed layer, followed by a solution-phase deposition process. The different concentrations of seed
solution inuence the density of nanobranches on the top surface of TONT, achieving complete surface
coverage of nanobranches in 10 mM TiCl
4
seed solution relative to 5 mM TiCl
4
seed solution. With
a control sample of bare TONT, the nanobranched TONTs were explored as a photoanode for dye-
sensitized solar cells (DSSCs). In the 5 mM TiCl
4
seed solution, the nanotree-shaped branches were
sporadically formed on the top surface of TONT, with little effect on the photocurrent-voltage (JeV)
properties, while in the 10 mM TiCl
4
seed solution, J
sc
and ll factor increased, which may have been
on account of the increased surface area and light scattering effect from rutile nanobranches, whereas
the ll factor may be also increased by the electron transport property, leading to the degraded charge
recombination. Accordingly, the nanobranched TONT showed 33% improved efciency compared to bare
TONT.
2012 Elsevier B.V. All rights reserved.
1. Introduction
Since 7% efcient dye-sensitized solar cells (DSSCs) consist-
ing of approximately 20 nm-sized TiO
2
nanoparticles was re-
ported [1], considerable effort have been devoted to develop
suitable photoanode materials and to design their nanostructure
to suppress the charge recombination, which is regarded as
a main obstacle for achieving efciency above 15%. Up to now,
early efforts have been mainly focused on studying the metal
oxide nanoparticles (NP) lms on account of offering vast
surface area for dye adsorption, leading to efciency of above
12% [2]. However, one of the barriers to produce more efcient
DSSCs has been the fast charge recombination in the large
surface area and grain boundaries between nanoparticles, where
photoinjected electrons move through trapping/detrapping
events [3]. Accordingly, to minimize the charge recombination
in the photoanode of DSSCs, one-dimensional (1-D) TiO
2
nanoparticles (e.g. nanorod, nanotube, nanowire etc.) have been
anticipated to give improved electron transport rate [4,5]. 1-D
TiO
2
nanoparticles have been enormously examined because of
their unique shape-dependent electronic and optical properties,
as well as their accepted applications in a wide variety of
electrochemical and photoelectrochemical devices [6,7]. In
particular, electrochemically anodized TiO
2
nanotubes (TONT)
has been widely employed as a photoanode for DSSCs on
account of easy, inexpensive, and reproducible technique. But,
the low surface area resulting from wide pore size of about
100 nm lowers the efciency [8]. Hence, varied approaches to
increase the actual surface area for dye loading have been
surveyed toward the post-treatment exploring of TiCl
4
and other
metal oxides [9,10]. Here, a novel 1-D nanostructure called
nanobranched TONT is suggested to facilitate the combinational
effect to increase the surface area as well as to enhance the
electron transport. Sometimes, the modication of nanotube
structure leads to the loss of electron transport, because of
providing the additional grain boundaries. However, the nano-
branch of this architecture may provide the enough surface area
without any loss of electron transport owing to a single crys-
talline property.
* Corresponding author. Tel.: 82 62 530 2497; fax: 82 062 530 2499.
E-mail address: skang@jnu.ac.kr (S.H. Kang).
Contents lists available at SciVerse ScienceDirect
Current Applied Physics
j ournal homepage: www. el sevi er. com/ l ocat e/ cap
1567-1739/$ e see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cap.2012.07.024
Current Applied Physics 13 (2013) 252e255
2. Experimental details
2.1. Synthesis of nanobranced TiO
2
nanotube
Two-step TONT was developed in an electrolyte of 0.25 wt%
NH
4
F using ethylene glycol containing an extremely small amount
of water, as reported elsewhere [11]. Herein, the electrochemical
anodization was performed for 30 min in a two-step process to
fabricate 7.1 (0.3) mm thick TONT, and subsequently thermally
treated in 450

C for 3 h. Afterward, the seed layer for the synthesis
of nanobranches was deposited on the TONT by dipping in the
aqueous solutions of 5 mM and 10 mM TiCl
4
for 30 min in a 70

C
oven, followed by annealing in air at 450

C for 30 min. The seeded
TONT were put in the aqueous solution composed of deionized (DI)
water (10 mL), HCl (0.03 mL), and TiCl
3
solution (0.01 mL) for 2 h in
a 80

C oven. Finally, the sample was thoroughly cleaned with DI
water and subsequently annealed at 450

C for 1 h under air.
2.2. Fabrication of dye-sensitized solar cells
DSSCs utilizing TONT photoanode were fabricated as already
described in a previous literature. Briey, the nanobranched TONT
lms and bare TONT as a control sample together were put in an
anhydrous ethanol solution containing Ru-complex dye (Ru 535-
bisTBA (N719), Solaronix) for over 12 h. The electrode was then
rinsed with anhydrous ethanol and dried under nitrogen gas. Pt
catalysts as the counter electrode were prepared by spreading
a drop of 3 mM H
2
PtCl
6
in 2-propanol on uorine-doped tin oxide
(FTO) glass and heating it to 350

C for 15 min in ambient air. The
dye-adsorbed TiO
2
photoanode was assembled using thermal
adhesive lms (thickness: 60 mm) in a Sandwich-type cell with
a counter electrode. Finally, a drop of electrolyte composed of 0.8 M
1-hexyl-2,3-dimethylimidazolium iodide and 50 mM iodine in
methoxypropionitrile was injected into the cell.
2.3. Characterization
A eld-emission scanning electron microscope (FE-SEM, JEOL
JSM-7000F), transmission electron microscope (TEM, JSM-5400,
JEOL) and X-ray diffraction (XRD, Scintag DMS-2000 diffractom-
eter using Cu Ka radiation) were used to conrm the surface
structure and crystallinity of the samples. The JeV curves were
obtained by measurements under the irradiation of one sun
condition (100 mW/cm
2
with AM 1.5 G).
3. Results and discussion
3.1. Characterization of nanobranced TiO
2
nanotube lm
The overall synthesis procedure is illustrated in Scheme 1,
involvinga fabricationof two-stepTiO
2
nanotubes byelectrochemical
anodization, a deposition of TiO
2
seed layer by solegel dip-coating
technique, and the synthesis of TiO
2
nanobranches by solution-
phase method on the TONT surface. Finally, the single crystalline
rutile nanobranches were applied to the entire area of TONT. In
general, the formation of seed layer is a starting point to grow
a certain material, being an essential step for the synthesis of
a material. Considering that the orientation of ZnOseed layer directly
determines the orientation of the nanorods, that is to say, the aligned
ZnO seed layer makes the aligned ZnO nanorod on the substrate,
while a powder formed ZnO seed layer rests at all angles on the
substrate [12], in the similar fashion, the TiO
2
seeds on the high
aspect-ratio TONT substrate exist preferentially at all angles because
the TiCl
4
treatment is facilitated as a seed solution that forms the
powder formed TiO
2
nanoparticles [13]. Upon this substrate, the TiO
2
nanorods concurrently grow at all angles, nally forming the nano-
branched TiO
2
structure. This scheme presents that the nano-
branched TONT can provide direct pathways for fast electron
transport.
Fig. 1 summarizes the surface- and cross-sectional viewof TONT
and nanobranched TONT. Two-step TONT (Fig. 1(a) and (d)) showed
unique morphological properties, where nanotubes with a uniform
surface structure are not separated independently but are joined to
each other by sharing a wall. A diameter of approx. 80 nm (10)
depending on the intrinsic surface morphology of Ti substrate was
achieved. Basically, the seed layer provides the starting point for the
synthesis of a certain material and should be formed with constant
size and uniform distribution as possible. Upon the 1-D nano-
structure as a base material, TiCl
4
treatment was chosen for
uniformcoating on the entire surface of TONT. The concentration of
TiCl
4
solution affects the density of the formed seed layer, therefore,
the effect on the seed layer of 5 mM and 10 mM TiCl
4
solutions was
investigated. The nanobranched TONT made from 5 mM TiCl
4
solution, shown in Fig. 1(b) and (e), exhibits scattered distribution
of nanotree-shaped branches having diverse sizes on the top of the
TONT surface. From the side-view of this image, the distribution of
various sized nanotrees in a hemispherical form was again
conrmed on the surface of TONT. This imperfect distribution of
nanotrees may have resulted from the insufcient supply of Ti
precursors in the lowconcentrated TiCl
4
seed solution. On the other
hand, the increase of TiCl
4
solution in the seed solution can provide
enough sources to form the TiO
2
seed particles throughout the
entire surface area of TONT, leading to the complete coating of
nanobranches throughout the TONT. Also, on the top of the surface,
large sized nanotrees were also formed that could bring about
a light scattering effect [14]. Furthermore, the specically directing
crystalline plane in the nanobranches was also observed to indicate
the single crystalline properties of the nanobranches. Also, to
conrm the conformal coating of nanobranches through the inner
pores of TONT, the TEM measurement was performed, shown in
Fig. 2. Though the inner pores of TONT, it was noticed that
unspecied shaped TiO
2
materials were coated instead of nanotrees
Scheme 1. Simple experimental procedure to make nanobranched TONT on the Ti substrate. Nanobranched TONT may enhance the electron transport property due to the 1-D
structural property of nanobranches without any loss of electrons.
S.H. Kang et al. / Current Applied Physics 13 (2013) 252e255 253
shaped particles, probably ascribed to different environment to the
top surface region of TONT, inuencing the formation and distri-
bution of seed layer. Noting that all TONT samples showed a length
of 7.1 mm (0.3 mm) for a 30 min anodization process with the
nanotubular structure.
The XRD patterns of the TONT and nanobranched TONT arrays
are shown in Fig. 3. In addition to the diffraction peaks corre-
sponding to the Ti substrate, the diffraction peaks of TONT
(Fig. 2(a)) can be indexed as those of anatase (101), (200), (004),
(105), (211) planes according to the JCPDS-84-1286 [13]. The
nanobranched TONT contained extra diffraction peaks manifesting
the presence of rutile (110) and (200) planes, which is in good
agreement with reported data of JCPDS-88-1175 [15]. Then, it was
observed that with increasing concentration of seed solution, the
intensity of the (110) rutile plane in the nanobranches increased.
This represents that the seed solution effectively inuences the
formation of nanobranches on the TONT.
3.2. Current-voltage characteristics of nanobranced TONT based
DSSCs
Fig. 4 shows the currentevoltage (JeV) characteristics of
TONT and nanobranched TONT based DSSCs under one sun (AM
1.5 G) illumination. In the case of bare TONT lm, 0.77 V of V
oc
,
3.16 mA/cm
2
of J
sc
, 51.3% of ll factor, and 1.25% (0.1%) of ef-
ciency were attained, while nanobranched TONT lm treated
with 5 mM TiCl
4
showed 0.78 V of V
oc
, 3.15 mA/cm
2
of J
sc
, 63.1%
of ll factor, and 1.55% (0.15%) of efciency, disclosing the
considerable increase of J
sc
and ll factor. Furthermore, in the
case of 10 mM TiCl
4
-treated nanobranched TONT, 0.78 V of V
oc
,
3.4 mA/cm
2
of J
sc
, 63.0% of ll factor, and 1.67% (0.09%) of
efciency were obtained, entailing little improvement of J
sc
. The
enhancement of J
sc
may be ascribed from the increase of surface
area by nanobranches, leading to high dye uptake (cm
2
,
3.1 10
14
vs. 2.3 10
14
of bare TONT) achieved by the dissolu-
tion in 0.1 M NaOH. Additionally, the light scattering effect from
Fig. 1. FE-SEM images of bare TONT (a) surface- and (d) side-view, nanobranched TONT synthesized in 5 mM TiCl
4
seed solution (b) surface- and (e) side-view, and nanobranched
TONT synthesized in 10 mM TiCl
4
seed solution (c) surface- and (f) side-view on the Ti substrate.
Fig. 2. TEM image of nanobranced TONT synthesized in 10 mM TiCl
4
seed solution.
Fig. 3. XRD spectra of (a) bare TONT, (b) nanobranched TONT synthesized in 5 mM
TiCl
4
seed solution, and (c) nanobranched TONT synthesized in 10 mM TiCl
4
seed
solution. Large capital, R represents the rutile phase of TiO
2
. (Full squares indicate the
peaks from Ti substrate.).
S.H. Kang et al. / Current Applied Physics 13 (2013) 252e255 254
the rutile nanobranches with high refractive index may also
contribute to increase the J
sc
. However, the conduction band
edge of rutile TiO
2
is positioned at about 0.2 V lower potential
compared with that of anatase TiO
2
phase [16], which may have
retarded the electron transport. Note that small offset may have
happened in the J
sc
of DSSC. Also, the ll factor may have been
enhanced on account of the fast electron transport ascribed from
the single crystalline nanobranched structure. As a result, ef-
ciency above 33% for the 10 mM TiCl
4
-treated nanobranched
structure is enhanced, and in particular, the J
sc
and ll factor
dominantly contribute to the increase of efciency.
4. Conclusions
Nanobranched TiO
2
nanotubes were synthesized by solegel
dipping for the formation of a seed layer and solution-phase
method for the growth of nanobranches. Depending on the
concentration of seed solution, the surface coverage of nano-
branches was determined, and the 10 mM TiCl
4
-treated nano-
branched TONT showed complete coverage of nanobranches
throughout the TONT surface, and sometimes, nanotree-shaped
structure appeared on the top of TONT. This affects the DSSC
performance to result in the enhancement of efciency above
33%, and in particular, J
sc
and ll factor were increased on
account of the increased surface area and light scattering effect
from rutile nanobranches. The ll factor was also increased by
the electron transport property, leading to degraded charge
recombination.
Acknowledgments
This work was supported by the National Research Foundation
of Korea Grant funded by the Korean Government (Ministry of
Education, Science and Technology). (NRF-2011-0840) (SHK). Also,
this study was nancially supported by Chonnam National
University, 2011
References
[1] B. ORegan, M. Grtzel, A low-cost, high-efciency solar cell based on dye-
sensitized colloidal TiO
2
lms, Nature (London) 353 (1991) 737e740.
[2] A. Yella, H.W. Lee, H.N. Tsao, C. Yi, S.M. Zakeeruddin, M. Grtzel, Porphyrin-
sensitized solar cells with cobalt (II/III)-based redox electrolyte exceed 12
percent efciency, Science 334 (2011) 629e634.
[3] N. Kopidakis, K.D. Benkstein, J. van de Lagemaat, A.J. Frank, Transport-limited
recombination of photo carriers in dye-sensitized nanocrystalline TiO
2
solar
cells, J. Phys. Chem. B 107 (2003) 11307e11315.
[4] S.H. Kang, S.H. Choi, T. Hyeon, Y.E. Sung, Nanorod-based dye-sensitized solar
cells with improved charge collection efciency, Adv. Mater. 20 (2008) 54e58.
[5] K. Zhu, N.R. Neale, A. Miedaner, A.J. Frank, Enhanced charge-collection ef-
ciencies and light scattering in dye-sensitized solar cells using oriented TiO
2
nanotubes arrays, Nano Lett. 7 (2007) 69e71.
[6] A. Kumar, A.R. Madaria, C. Zhou, Growth of aligned single-crystalline rutile
TiO
2
nanowires on arbitrary substrates and their application in dye-sensitized
solar cells, J. Phys. Chem. C 114 (2010) 7787e7792.
[7] J. Liu, Y. Li, X. Huang, R. Ding, Y. Hu, J. Jiang, L. Liao, Direct growth of SnO
2
nanorod array electrodes for lithium-ion batteries, J. Mater. Chem. 19 (2009)
1859e1864.
[8] S.H. Kang, J.Y. Kim, Y.E. Sung, Surface modication of stretched TiO
2
nanotubes
for solid-state dye-sensitized solar cells, J. Phys. Chem. C 111 (2007)
9614e9623.
[9] J.H. Park, J.Y. Kim, J.H. Kim, Y.E. Sung, K.S. Ahn, Enhanced efciency of dye-
sensitized solar cells through TiCl
4
-treated, nanoporous-layer-covered TiO
2
nanotube arrays, J. Power Sources 196 (2011) 8904e8908.
[10] H. Yu, J. Yu, B. Cheng, M. Zhou, Effects of hydrothermal post-treatment on
microstructures and morphology of titanate nanoribbons, J. Solid State Chem.
179 (2006) 349e354.
[11] M. Paulose, K. Shankar, S. Yoriya, H.E. Prakasam, O.K. Varghese, G.K. Mor,
T.A. Latempa, A. Fitzgerald, C.A. Grimes, Anodic growth of highly ordered TiO
2
nanotube arrays to 134 mm in length, J. Phys. Chem. B 110 (2006)
16179e16184.
[12] L.E. Greene, M. Law, G. Somorjai, P. Yang, General route to vertical ZnO
nanowire arrays using textured ZnO seeds, Nano Lett. 5 (2005) 1231e1236.
[13] S. Ahmed, A.D. Pasquier, T. Asefa, D.P. Birnie, Improving microstructured TiO
2
photoanodes for dye sensitized solar cells by simple surface treatment, Adv.
Energy Mater. 1 (2011) 879e887.
[14] T.A. Kandiel, R. Dillert, A. Feldhoff, D.W. Bahnemann, Direct synthesis of
photocatalytically active rutile TiO
2
nanorods partly decorated with anatase
nanoparticles, J. Phy. Chem. C 114 (2010) 4909e4915.
[15] K. Thamaphat, P. Limsuwan, B. Ngotawornchai, Phase characterization of TiO
2
powder by XRD and TEM, Kasetsart J. Nat. Sci. 42 (2008) 357e361.
[16] L. Kavan, M. Grtzel, S.E. Gilbert, C. Klemenz, H.J. Scheel, Electrochemical and
photoelectrochemical investigation of single-crystal anatase, J. Am. Chem. Soc.
118 (1996) 6716e6723.
Fig. 4. JeV characteristic of DSSC consisting of bare TONT and nanobranched TONTs
prepared in 5 mM and 10 mM TiCl
4
seed solution photoanodes measured under one
sun condition (100 mW/cm
2
, AM 1.5G).
S.H. Kang et al. / Current Applied Physics 13 (2013) 252e255 255