Electronic Materials Letters, Vol. 8, No. 5 (2012), pp.

481-484
DOI: 10.1007/s13391-012-2048-4

TiO2 Nanotubes/Nanoparticles Composite Film with Higher Light Harvesting

and Electron Transfer for Dye-Sensitized Solar Cells

Chengcheng Liu,1 Zhifeng Liu,1,* Lei E,1 Yabin Li,1 Jianhua Han,1 Yun Wang,1
Zhichao Liu,1 Jing Ya,1 and Xuhuang Chen2

1
Department of Materials Science and Engineering, Tianjin Institute of Urban Construction,
300384, Tianjin, China
2
School of Chemical and Environmental Engineering, Hubei University of Technology, Wuhan 430068, China
(received date: 15 March 2012 / accepted date: 3 May 2012 / published date: October 2012)

TiO2 nanotubes with an inner diameter of 4-6 nm were synthesized by hydrothermal treatment method. TiO2
nanotubes/nanoparticles composite films were fabricated as a dye-sensitized solar cells work electrode using
TiO2 nanotubes and TiO2 nanoparticles as precursor. The structure of composite films has a remarkable influence
on the final performance of the cell due to high surface area, fast electron transfer, enhanced light-scattering
and light-harvesting, simultaneously. I-V characteristic measurement indicates an enhanced efficiency by 27%
as compared to TiO2 nanotubes film.
Keywords: TiO2, nanotubes/nanoparticles, composite film, dye-sensitized solar cells

1. INTRODUCTION conversion efficiency. Most recently, it was shown that an

Over the last few years, dye-sensitized solar cells (DSSCs)
have attracting lots of attentions since the initial report of
Gratzels group due to its potential for developing inexpen-
sive, large area photovoltaics.[1] DSSCs with TiO2 nanopo-
rous films have been demonstrated with a power conversion
efficiency of 11% in which a thick layer of nanoporous film
provides a large surface area anchoring the light harvesting
dye molecules.[1,2] However, slow electron transfer through the
interconnected nanoparticles and the charges recombination
between injected electrons and electron acceptors in the elec-
trolyte hinder the performance of TiO2 DSSCs seriously.[3,4]
Compared with nanoparticles, highly ordered one-dimen-
sional (1D) nanoarrays[5,6] were found to be superior in pho-
toelectrochemical performance due to their one-dimensional
channel for carrier transportation, in which the efficiency of
charge collection is improved originated from faster electron
transport and slower charge recombination. Recently, well-
aligned, self-organized TiO2 nanotubes (NTs) were applied
for solar energy conversion devices because of their good
charge-transport property.[7-14] However, the efficiencies of
these devices are still not as high as cells fabricated with
standard TiO2 nanoparticles (NPs), and several methods
have been used to improve the NTs geometry toward higher
*Corresponding author: tjulzf@163.com
KIM and Springer
increase in the efficiency from 1.6% to 1.9% by reducing the
disorder at the top of the NTs layers grown in non-aqueous
electrolytes. Besides, Wang group have prepared a series
bilayer photoelectrodes with TiO2 nanowires-covered nano-
tubes, which had an excellent cell efficiency.[15]
Here, in order to improve the efficiency of NTs solar cell,
we designed and fabricated TiO2 nanotubes/nanoparticles
(NTs/NPs) composite films by doctor blade method and the
DSSCs based on TiO2 NTs/NPs showed an increased effi-
ciency by 27% due to the high light harvesting efficiency
and light scattering features originated from more dye
anchoring and P25 decorated, respectively.
2. EXPERIMENTAL
2.1 Preparation of TiO2 NTs
The P25 TiO2 powders were used to prepare TiO2 NTs by
the following hydrothermal treatment process. Firstly, The
P25 TiO2 powders were treated with 10 mol/L NaOH aque-
ous solutions in a teflon vessel at 130C for 24 h. The
obtained precipitates were neutralized, and then dispersed in
a 0.1 mol/L HCl aqueous solution by ultrasonication. Sec-
ondly, the acid-treated precipitates were washed continually
with distilled water, then filtered and dried at 100C. Finally,
as-prepared samples were calcined in air at 500C for 1 h,
cooled to room temperature in air, and then TiO2 NTs were
obtained after milling.
482 C. Liu et al.: TiO2 Nanotubes/Nanoparticles Film for DSSCs

2.2 Preparation of TiO2 films

As-prepared TiO2 NTs were mixed with ethanol and
stirred overnight, forming a colloidal suspension with the
TiO2 content of 20 wt. %. The suspension was then coated
onto the clean indium tin oxide (ITO) glass substrate by doc-
tor blade method. This coating process was repeated several
cycles until the suitable thickness (about 5 m) was
obtained. After dried in air, the TiO2 NTs films were calcined
in air up to 550C at a heating rate of 2C/min. TiO2
NTs/NPs composite films were prepared with the same
method using different mixing ratio between TiO2 NTs and Fig. 1. TEM image of TiO2 NTs.
TiO2 NPs as precursor (mNTs:mNPs=1:0.5, mNTs:mNPs = 1:1 and
mNTs:mNPs = 1:2).

2.3 Assembly of dye-sensitized solar cells

The TiO2 NTs and TiO2 NTs/NPs films were used as pho-
toanodes in DSSCs with a 5-micrometer thickness, sensi-
tized in a 0.05 mM ethanol solution of N3 dyes for at least
12 h at 60C. The films were then rinsed with absolute etha-
nol to rinsed off excess unanchored dyes and dried in air,
after which platinum sheet were covered as counter elec- Fig. 2. SEM images of TiO2 NTs film (a) and TiO2 NTs/NPs compos-
trodes. The internal space of the cell was filled with liquid ite film (b).
electrolyte (0.5 M LiI, 0.05 M I2) dissolved in acetonitrile by
capillary forces.

2.4 Characterization
Morphology of the films was observed using a PHILIPS
XL-30 environment scanning electron microscopy (ESEM)
and transmission electron microscopy (TEM, JEOL 100CX-
II). X-ray diffraction (XRD) of films was performed with a
Rigaku D/max-2500 using Cu K radiation ( = 0.154059
nm). The optical transmittance of the films was detected by
DU-8B UV/VIS double-beam spectrophotometer. Photocur- Fig. 3. TEM image of TiO2 NTs/NPs.
rent of the TiO2 DSSCs was measured under irradiation of a
xenon lamp (100 mWcm2) with global AM1.5 condition,
and photocurrent-voltage curves of the TiO2 DSSCs were
obtained using a potentiostat. To collect accurate data, five
parallel cell samples for each photoanode film were assem-
bled and measured.

3. RESULTS AND DISCUSSION

Figure 1 shows the TEM image of TiO2 NTs prepared by

hydrothermal treatment. From the TEM image, the inner
diameter of TiO2 NTs film was measured to approximately
4-6 nm, while the outer diameter was about 11-14 nm.
Figure 2(a) and (b) give the SEM images of the TiO2 NTs
and TiO2 NTs/NPs composite films (mNTs:mNPs = 1:1). It is
evident that the NTs are deposited on ITO substrate ran- Fig. 4. XRD patterns of TiO2 NTs film and TiO2 NTs/NPs composite
domly. After decorated with P25 NPs, the surface of the film.
samples became rough and the interspaces between the NTs
turn smaller obviously, which contributes to a significantly TiO2 NTs/NPs, in which we can that TiO2 NPs are reversely
more dye adsorption. Figure 3 presents the TEM image of uniformly coated on the surface of NTs.

Electron. Mater. Lett. Vol. 8, No. 5 (2012)

 C. Liu et al.: TiO2 Nanotubes/Nanoparticles Film for DSSCs 483

Fig. 6. Optical transmittance spectra of TiO2 NTs film and TiO2 NTs/
Fig. 5. The I-V characteristics of TiO2 NTs film and TiO2 NTs/NPs
NPs composite film.
composite film.

Table 1. Parameters of dye-sensitized solar cells with different photo-

anode films
Rhoto anode Voc Jsc FF
film (mV) (mAcm-2) (%) (%)
NTs/NPs 624 6.55 61 3.12
NTs 601 5.25 62 2.45

In order to compare the different crystal structure of the

TiO2 NTs and TiO2 NTs/NPs composite film (mNTs:mNPs =
1:1), X-ray diffraction measurements were conducted in
Fig. 4. It can be seen that the TiO2 NTs film exhibits anatase
structure. However, small amount rutile phase was present in
the top XRD patterns, which indicated that the TiO2 NTs/
NPs composite film contained anatase and rutile crystallites.
Figure 5 presents the photocurrent-voltage curves of the
DSSCs based on TiO2 NTs and TiO2 NTs/NPs composite
films (mNTs:mNPs=1:1) using N3 as sensitizer, and the photo-
electrochemical properties of these DSSCs are listed in
Table 1. Cell efficiency () can be expressed by the follow-
ing equation during photocurrent measurement:
= (Voc JscFF) / Pin
FF = Vopt Jopt / Voc Jsc
The Pin is the power of incident white light, FF is fill fac-
tor, Vopt and Jopt are voltage and current for maximum powder
output, and Voc and Jsc are open-circuit photovoltage and
short-circuit photocurrent, respectively.
The cell performance of the NTs/NPs composite film
DSSCs higher than TiO2 NPs film DSSCs is expected to be
fine. The average values of Voc and Jsc for NTs/NPs film
DSSCs are 624 mV and 6.55 mAcm2, respectively. In con-
trast, these values are 601 mV and 5.25 mAcm2 for DSSCs
based on TiO2 NPs film. Moreover, the NTs/NPs film
DSSCs exhibit an improved efficiency by about 27% in
comparison with that based on TiO2 NPs film. The enhanced
Fig. 7. Schematics of the (a) TiO2 NTs film (b) TiO2 NTs/NPs com-
posite film and the light scattering occurring in corresponding film
(c), (d).
conversion efficiency is related to the increased dye loading
and more solar light scattering in the composite film.
(1)
Figure 6 shows the optical transmittance in the wavelength
(2)
() ranging from 300 nm to 800 nm for TiO2 NTs film and
TiO2 NTs/NPs film (mNTs:mNPs = 1:1). It can be seen that the
optical transmittance of TiO2 NTs/NPs film decreases in
comparison with that of NTs in the wavelength range of
350~800 nm, which indicates that NTs/NPs increase the
solar light scattering and decrease of transmission. However,
50% optical transmittances remain beyond the wavelength
of 430 nm.
Figure 7 is the schematic images of the composite film
photoanode and the main light scattering processes in the
composite films after solar light absorbing. The dye loading
of composite samples is much higher than that of bare NTs
owing to the enhanced surface area provided by the TiO2

Electron. Mater. Lett. Vol. 8, No. 5 (2012)

484 C. Liu et al.: TiO2 Nanotubes/Nanoparticles Film for DSSCs
NPs. It also reveals that the decorated TiO2 NPs play an
important role in the light harvesting by significantly scatter
and travel of light within the photoanode films. Furthermore,
a stronger internal light-scattering and fast electron transport
was existed in the TiO2 NTs due to their 1D structure. There-
fore, the TiO2 NTs/NPs composite film has remarkable influ-
ence on final performance of the DSSCs. We believe that
both the following efforts are helpful for the higher conver-
sion efficiency of TiO2 NTs/NPs composite film DSSCs.
First, the photo-excited electrons are easy to be transmitted
in TiO2 NTs/NPs photoanode due to the one-dimensional
oriented NTs structure. Second, the decorated TiO2 NPs can
improve the surface area of TiO2 NTs/NPs composite film,
which anchors more dye and improves the light-harvesting.
Better efficiency can be obtained by the TiO2 NTs/NPs com-
posite film due to the advantages of these two materials.
Moreover, the cell performance was also examined using
different TiO2 NTs/NPs composite films (mNTs:mNPs = 1:0.5
and mNTs:mNPs = 1:2) as photoanodes. The cell efficiency ()
was 3.01% and 2.87% for TiO2 NTs/NPs (mNTs:mNPs = 1:0.5)
and TiO2 NTs/NPs (mNTs:mNPs = 1:2), respectively. It is indi-
cated that the mixing ratio of NTs and NPs plays an impor-
tant role on the cell performance due to the actions of NTs
and NPs in composite photoanode film.
Although the opportunities of incident photons to be cap-
tured by the dye molecules and isolated NPs are increased,
which slow down the electron transport and limit the
devices efficiency by time-resolved photocurrent and photo-
voltage measurements[16,17] and modeling studies,[18,19] how-
ever, our research result provides an idea to design the
photoanode structure and improve the photovoltaic perfor-
mance of DSSCs even limitation existed. Therefore, seeking
for effective measures to resolve the above problem is the
key point of our following research.
4. CONCLUSIONS
In the present work, TiO2 NTs/NPs composite films were
prepared and assembled into dye-sensitized solar cells. The
TiO2 NTs/NPs composite films can be a effective structure to
work as photoanodes in DSSCs due to the high surface area,
fast electron transfer, as well as the enhanced light-scattering
and light-harvesting, which lead to an excellent photocon-
version efficiency of 3.12% under the AM 1.5 illumination
at 100 mWcm2.
Electron. Mater. Lett. Vol. 8, No. 5 (2012)
ACKNOWLEDGEMENTS
The authors gratefully acknowledge financial support
from National Natural Science Foundation of China
(51102174) and Natural Science Foundation of Tianjin
(11JCYBJC27000).
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