Electrochimica Acta 78 (2012) 384391

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

Controlling electron transport rate and recombination process of TiO2

dye-sensitized solar cells by design of double-layer lms with different
arrangement modes
A.M. Bakhshayesh a , M.R. Mohammadi a, , D.J. Fray b
a
Department of Materials Science and Engineering, Sharif University of Technology, Azadi Street, Tehran, Iran
b
Department of Materials Science & Metallurgy, University of Cambridge, Pembroke Street, Cambridge CB2 3QZ, UK

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

Article history: TiO2 dye-sensitized solar cells (DSSCs) in the form of double-layer lms, containing an under-layer and an
Received 22 May 2012 over-layer, with various crystal structures (i.e., anatase and rutile phases) and morphologies (i.e., nanopar-
Accepted 6 June 2012 ticle and nanowire) were reported. It was found that the photovoltaic performance of TiO2 DSSCs depends
Available online 1 July 2012
on the morphology, crystal structure, light scattering effect, optical band gap energy and arrangement
of the under- and over-layer lms. The double-layer solar cell made of anatase-TiO2 nanoparticles as
Keywords:
the under-layer and anatase-TiO2 nanowires as the over-layer (i.e., AW solar cell) showed the highest
Dye-sensitized solar cell
power conversion efciency and ll factor of 6.34% and 62.6%, respectively. High electron lifetime, rapid
Double-layer
EIS
transportation and less recombination of photogenerated electrons are the factors affect the efciency
TiO2 nanowires improvement of AW lm and was demonstrated by electrochemical impedance spectroscopy (EIS). X-
TiO2 nanoparticles ray diffraction (XRD) and eld emission scanning electron microscope (FE-SEM) analyses revealed that
TiO2 nanoparticles had uniform and nanometer grains with particle size around 20 nm, whereas TiO2
nanowires with length of several m had diameter in the range 2050 nm. The optical properties and
band gap energies of TiO2 nanoparticles and nanowires were studied through UVvis absorption. The
indirect optical band gap energy of TiO2 nanowires, anatase-TiO2 and rutile-TiO2 nanoparticles was cal-
culated 3.61, 3.47 and 3.41 eV, respectively. The design of double-layer solar cells by manipulation of
morphology and crystal structure of TiO2 nanostructures will open a new concept for improvement of
power conversion efciency of dye sensitized solar cells.
2012 Elsevier Ltd. All rights reserved.

1. Introduction is important to collect these photo-generated charge carriers as

Nowadays, a wide range of research works are being carried
out on dye-sensitized solar cells (DSSCs) due to the good power
conversion efciency, low cost, optional high vacuum and mate-
rials purication steps compared with pn junction photovoltaic
devices [1]. The materials used to make DSSCs are abundantly avail-
able so that the technology can be scaled up to the terawatt scale
without running into feedstock supply problems [25]. The power
efciencies of DSSCs based on TiO2 nanoparticles and nanowires
can reach 11% [611] and 1.5% [12,13], respectively.
When a DSSC is irradiated by sunlight, the dye molecules inject
electrons in the TiO2 band gap and holes in the electrolyte. In
order to reach high conversion efciencies with the solar cell, it
Corresponding author at: Department of Materials Science and Engineering,
Sharif University of Technology, Azadi Street, Tehran, Iran. Tel.: +98 21 6616 5211;
fax: +98 21 6600 5717.
E-mail addresses: mrm41@cam.ac.uk, mohammadi@sharif.edu
(M.R. Mohammadi).
electric current before they recombine. In order to achieve this
goal, the charge carrier collection has to be signicantly faster than
their recombination. One promising solution to this impasse is
to increase the electron diffusion length in the anode by replac-
ing the nanoparticle lm with one-dimensional TiO2 . Generally,
high electron mobility, excellent electronhole separation power
and long-distance transport ability are unique advantages of one-
dimensional TiO2 compared to that of bulk TiO2 [14,15]. It is known
that, the surface is the main reacting portion of solar-ray capture
and photoelectric conversion. Furthermore, the surface morphol-
ogy, stability and equilibrium shape of chemically prepared TiO2
are strongly affected by their surface conditions [16]. The prepared
TiO2 nanowires always have square-like cross sections due to the
perfect tetragonal lattice. The parallel surfaces may introduce the
notable surfaces interaction in the nanowires with small diameters,
because of the close distance between surfaces [17]. Previously,
nanowires with different compositions have been prepared, using
various methods including vapor phase transport process [18],
chemical vapor deposition [19,20], arc-discharge [21], laser abla-
tion [20,22], solution process [23] and template-based method

0013-4686/$ see front matter 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.electacta.2012.06.087
 A.M. Bakhshayesh et al. / Electrochimica Acta 78 (2012) 384391
[24,25]. The rst claim on the successful synthesis of crystalline
TiO2 nanotubes with the anatase phase was made by Kasuga et al.
[26,27]. The raw anatase or rutile phase TiO2 materials were treated
with NaOH solution and nally the product was washed with HCl
aqueous solution.
In the previous studies, TiO2 solar cells in the form of a
monolayer lm composed of a mixture of TiO2 nanoparticles and
nanowires with various weight ratios were reported. For exam-
ple, Tan et al. [28] fabricated dye-sensitized solar cells based
on nanoparticle/nanowire composite lms and investigated the
effect of nanowire to nanoparticle weight ratio on their per-
formance. They found that a mixture of 20 wt% nanowire and
80 wt% nanoparticle had the maximum power conversion ef-
ciency of 8.6%. Asagoe et al. [13] reported that the DSSC made of
10 wt% anatase nanowire and 90 wt% P-25 nanoparticle showed
higher photovoltaic performance (e.g., power conversion ef-
ciency of 6.53%) than the DSSC made of pure P-25 nanoparticle
(power conversion efciency of 5.59%). In addition, dye-sensitized
solar cells made of double-layer lms containing TiO2 nanopar-
ticles as the under-layer and TiO2 nanospindles [29], nanotubes
[30], nanobres [31] and hollow sphere [32] as the over-layer
were reported. For example, Qiu et al. [29] prepared a double-
layered photoanode in which the over-layer was made of large
TiO2 nanospindles, enhancing light scattering, and the under-
layer was consisted of small TiO2 nanospindles, increasing the
dye adsorption. Firstly, hydrogen titanate was synthesized by
hydrothermal method using TiO2 powder (Degussa P25, about 20%
rutile and 80% anatase with a particle size of about 2030 nm).
TiO2 nanospindles were grown by solvothermal method using
hydrogen titanate as titanium source and a mixture of dimethy-
lamine, water and ethanol or dimethylamine, water and ethylene
glycol as solvents at 180 C for 10 h. TiO2 nanospindles had diam-
eter in the range 645 nm and length in the range 20300 nm.
It was concluded that the double-layer TiO2 lm could signi-
cantly improve the power conversion efciency of dye-sensitized
solar cells up to 8.3%, owing to its synergic effects. Xu et al.
[30] reported bilayer-structured DSSC containing TiO2 nanocrys-
tals as under-layer and TiO2 nanotubes as over-layer with a
power conversion efciency of 6.15%. Yang et al. [31] prepared
a DSSC with power conversion efciency about 8% made of one-
dimensional bilayer nanobre photoanode. Three-dimensional
(3D) dye-sensitized solar cells fabricated with TiO2 bilayer lm con-
taining radial free-standing TiO2 nanowires were rooted into TiO2
nanoparticles lm were reported by Wang et al. [33]. The results
revealed that the max output power of 3D dye-sensitized solar
cells increased by 32.7% as compared to the TiO2 nanoparticles
lm. Wang et al. [34] reported DNA-like dye-sensitized solar cell
based on TiO2 nanowire-covered nanotube bilayer lm electrode
with maximum power of 0.51 mW. TiO2 nanotubes were grown by
electrochemical anodization of Ti sheet and TiO2 nanowires were
prepared by hydrothermal method. They observed that bilayer
lm had higher power than the cell made of TiO2 nanotube
(Pmax = 0.14 mW).
So far no signicant work has been reported on design of
double-layer solar cells made of the proper under- and over-layer
lms by tailoring the crystal structure and morphology of TiO2
nanostructures. The morphology, crystal structure and optical band
gap energy of TiO2 lm are the effective parameters in electron
transport rate and recombination process of double-layer DSSCs.
Therefore, in the present work the effect of arrangement modes
of TiO2 nanowire and TiO2 nanoparticle layers in the form of
double-layer lms is investigated. Furthermore, the improvement
mechanism of DSSCs was studied by measurement of their inter-
nal resistance, electron lifetime and electron transit time using
electrochemical impedance spectroscopy (EIS). Photovoltaic char-
acteristics of TiO2 double-layer solar cells were also systematically
385
studied compared with TiO2 monolayer lms made of pure TiO2
nanoparticles and nanowires.
2. Experimental
2.1. Preparation of anatase-TiO2 nanowires
TiO2 nanowires were grown by a two-step hydrothermal
method. Hydrogen titanate nanowires were rstly prepared
according to an analogous procedure reported in the literature,
based on hydrothermal process [27]. Hydrogen titanate nanowires
were converted into TiO2 nanowires by rehydrothermal process.
In the rst step, one gram of TiO2 powder (anatase, Alfa Aesar,
99%) was placed into 50 ml Teon-lined stainless steel autoclave,
which was then lled with 10 M NaOH aqueous solution up to 80%
of the total volume. The autoclave was heated at 180 C for 72 h and
subsequently cooled naturally to room temperature. The collected
precipitates (i.e., hydrogen titanate nanowires) were washed with
dilute HCl and water several times and dried at 25 C. In the sec-
ond step TiO2 nanowires were grown by rehydrothermal process.
Hydrogen titanate nanowires were placed into the Teon-lined
autoclave, which was then lled with deionized water (pH = 7) up
to 80% of the total volume. The autoclave was heated at 180 C
for 12 h and subsequently cooled to room temperature naturally.
Finally, the resulting precipitates were collected and dried at room
temperature.
2.2. Preparation of TiO2 nanoparticles
TiO2 nanoparticles were prepared according to the method
reported in our previous work [35]. Titanium tetraisopropoxide
(TTIP) with a purity of 97% (Aldrich, UK) was used as a titanium
precursor; analytical grade hydrochloric acid (HCl) 37% (Fisher, UK)
was used as a catalyst for the peptization and deionized water was
used as a dispersing media. The wateracid mixture (in the range
of pH = 12) was stabilized at a constant temperature. TTIP was
added, forming a white thick precipitate, which gradually peptized
after 2 h to form a clear sol. The molar ratio of TTIP:HCl:H2 O was
0.1:0.06:50, which makes a 0.1 M TiO2 sol. The sol was heated at
70 C for 24 h and TiO2 powder collected. It was then sintered at
900 C for 2 h to obtain TiO2 -rutile nanoparticles or was treated by
hydrothermal process using deionized water (pH = 7) at 230 C for
8 h to obtain TiO2 -anatase nanoparticles.
2.3. Preparation of DSSCs
Three TiO2 pastes with various morphologies and crystal struc-
tures were prepared using pure TiO2 -anatase nanowires (W), pure
TiO2 -anatase nanoparticles (A) and pure TiO2 -rutile nanoparticles
(R). For preparation of TiO2 paste, 6 ml of deionized water was
injected into 1.2 g of TiO2 powder and grounded with a pestle to
obtain a more porous structure. 0.68 ml acetylacetone was added
next in order to sustain TiO2 particles in a colloidal state. Further-
more, 100 l of Triton X-100 was added to the precursor in order
to fully disperse the TiO2 nanoparticles and nanowires. After 1 h of
stirring, the dispersion was treated with a 40 W ultrasonic titanium
probe at a frequency of 15 pulses/s.
Three monolayer TiO2 lms, from the prepared pastes, were
coated on FTO (15 /sq) substrate by spin coating technique using
Pasargard nanotechnology spin-coater, as listed in Table 1. In
addition, four double-layer TiO2 lms containing the under- and
over-layers, with almost the same thickness, were also deposited
on FTO substrate by spin coating technique, as presented in Table 2.
The deposited TiO2 lms, as photoanode electrodes, were sintered
at 450 C for 2 h in air atmosphere. The post-treatment with TiCl4
solution was applied to freshly sintered TiO2 electrodes as reported
386 A.M. Bakhshayesh et al. / Electrochimica Acta 78 (2012) 384391

Table 1 monolayer lms had porous structure as a result of removal of

Characteristics of TiO2 monolayer lms.
the dispersing agent and solvents. Consequently, TiO2 monolayer
Sample Crystal structure Morphology Thickness (m) electrodes containing nanoparticles had high surface area which is
W Anatase Nanowire 11.6 essential for a high-efciency DSSC, because it allows adsorption
A Anatase Nanoparticle 11.3 of sufciently large number of dye molecules needed for ef-
R Rutile Nanoparticle 11.4 cient light harvesting, as conrmed by a spectroscopic method (see
Section 3.4). It can be observed that TiO2 monolayer electrode con-
taining nanowires (i.e., W lm) was uniformly covered with TiO2
in the literature [36]. An aqueous stock solution of 2 M TiCl4 was
nanowires with length of several m and diameter in the range
diluted to 0.04 M. TiO2 electrodes were immersed into this solution
2050 nm.
and stored in an oven at 70 C for 30 min in a closed vessel. After
Cross-sectional view of the double-layer lms containing TiO2
ushing with distilled water, the electrodes were sintered again at
nanoparticle and nanowire layers was shown in Fig. 2. It can be
450 C for 30 min.
observed that the under- and over-layers had almost the same
The resulting TiO2 electrodes were soaked in 0.5 mM ruthe-
thickness around 5 m. The layer made of TiO2 nanowires showed
nium (II) dye (Ruthenium 535bisTBA dye, or N719, Solaronix)
higher porosity than the layer made of TiO2 nanoparticles. Defects
solution (using ethanol as a solvent) for 18 h. The electrodes were
in the porous TiO2 layer may act as electron traps at the grain
washed with ethanol, dried, and then immediately used for pho-
boundaries of the contacts between the nanowires. The depth of
tovoltaic measurements. The redox electrolyte was composed of
the traps that participate in the electron motion affects the value
0.6 M dimethylpropylimidazolium iodide, 0.1 M LiI, 0.05 M I2 , and
of the diffusion coefcient [10].
0.5 M 4-tertbutylpyridine in acetonitrile [37]. Platinum coated FTO
substrate was prepared as a counter electrode. The platinum elec-
3.2. Crystal structure
trode was placed over the dye-adsorbed TiO2 electrode, and the
edges of the cell were sealed with sealing sheet (SX 1170-60,
Fig. 3 shows XRD patterns of TiO2 nanostructures including
Solaronix). Sealing was accomplished by hot-pressing the two elec-
rehydrothermally grown nanowires (W), nanoparticles treated by
trodes together at 120 C. The redox electrolyte was injected into
hydrothermal process (A) and nanoparticles sintered at 900 C (R).
the cell through the small holes and sealed with a small square of
The rehydrothermally grown nanowires and hydrothermally pre-
sealing sheet.
pared nanoparticles had anatase-TiO2 structure with the strongest
peak at 2 = 25.3 (1 0 1), whereas nanoparticle sintered at 900 C
2.4. Characterization and measurements
showed rutile-TiO2 phase with the strongest peak at 2 = 27.4
(1 1 0). The broad peaks indicated the ultra-ne primary parti-
TiO2 lms were characterized by X-ray diffraction diffractome-
cles. The average crystallite size of anatase-TiO2 (hydrothermally
ter (XRD) using a Philips Xpert PW3020, Cu K and eld emission
prepared) and rutile-TiO2 (900 C sintered) nanoparticles was cal-
scanning electron microscope (FE-SEM) using a JEOL 6340. The
culated around 18 nm and 24 nm, respectively by the Scherrer
thickness of TiO2 lms was measured with a Tensor Alpha-step
formula. It is worth noting that basically, the as-grown nanowires
Proler. It should be noted that all tested cells in this study con-
prepared by hydrothermal process consisted of hydrogen titanate
tained no apparent cracks and delimitation, which was conrmed
phase [13] rather than anatase-TiO2 phase. We also obtained the
by the optical microscope and SEM. The absorption spectrum
same phase in the rst step of hydrothermal process which was
was analyzed by Ultravioletvisible (UVvis) spectroscopy using
converted into anatase-TiO2 by rehydrothermal process in the sec-
a 6705 JENWAY spectrometer. The density of TiO2 nanostructures
ond step.
measured by a Micromeritics AccuPyc 1330 pycnometer analyzer.
Photovoltaic measurements were performed under 1 Sun AM 1.5G
3.3. UVvis analysis
simulated sunlight. The setup and method used for such measure-
ments have been previously described [38]. The electrochemical
Optical absorbance spectra of TiO2 nanowires and nanoparticles
impedance spectroscopy (EIS) measurements of the DSSCs were
are shown in Fig. 4. To quantify the optical band gap of the lms,
recorded with a potentiostat/galvanostat (PGSTAT 302N, Autolab,
Tauc Model [39] was employed in the high absorbance region of
Eco-Chemie, The Netherlands) under 100 mW/cm2 . The frequency
the transmittance spectra according to the following equation:
range was explored from 0.01 Hz to 106 Hz. EIS spectra were simu-
r
lated using Zview software. h = A(h Eg ) (1)
where h is the photon energy, Eg is the optical band gap, A is a con-
3. Results and discussion
stant which does not depend on photon energy, r has four numeric
values (1/2 for allowed direct, 2 for allowed indirect, 3 for forbid-
3.1. Microstructure
den direct and 3/2 for forbidden indirect optical transitions) and
is the absorption coefcient, which is calculated from the following
Fig. 1 shows surface morphology of TiO2 monolayer elec-
equation:
trodes. TiO2 monolayer electrodes containing nanoparticles (i.e.,
A and R lms) showed uniform, homogeneous and nanometer TiO2 2.303K.
= (2)
lms with average grain size around 20 nm. In addition, A and R L.C

Table 2
Characteristics of TiO2 double-layer lms.

Sample Under-layer Over-layer Total thickness (m)

Crystal structure Morphology Thickness (m) Crystal structure Morphology Thickness (m)

AW Anatase Nanoparticle 5.4 Anatase Nanowire 5.7 11.1

WA Anatase Nanowire 5.6 Anatase Nanoparticle 5.4 11.0
RW Rutile Nanoparticle 5.5 Anatase Nanowire 5.3 10.8
WR Anatase Nanowire 5.4 Rutile Nanoparticle 5.7 11.1
 A.M. Bakhshayesh et al. / Electrochimica Acta 78 (2012) 384391 387

Fig. 1. FE-SEM images of surface morphology of TiO2 monolayer lms: (a) A, (b) R and (c) W.

Fig. 2. FE-SEM images of cross sectional view of TiO2 double-layer lms: (a) AW and (b) WA.

where K is the absorbance of the sample;  is the density of TiO2 ; adsorption on TiO2 surface. The amount of dye adsorbed was deter-
C is the concentration of the particles and L is the optical path mined by a spectroscopic method by measuring the concentration
length. The density of TiO2 nanowires, anatase-TiO2 and rutile-TiO2 of dye desorbed on the titania surface into solution of 0.1 molar
nanoparticles, was measured 3.35, 3.85 and 4.25 g cm3 , respec- NaOH. According to BeerLambert law, the amount of adsorbed
tively. Indirect band gap was determined by plotting (h)2 versus dye was calculated with regards to the macroscopic geometric area
h, with the extrapolation of the linear region to the low energies. of the TiO2 electrode [41]. It is clear that solar cells made of pure
From Fig. 4, it is estimated that the indirect optical band gap of TiO2 nanoparticles can absorb more ruthenium dye than pure nanowire
nanowires, anatase-TiO2 and rutile-TiO2 nanoparticles is 3.61, 3.47 and double-layer electrodes due to possessing higher surface area.
and 3.41 eV, respectively. Therefore, all samples displayed a blue It can be seen that double-layer solar cells showed higher ll fac-
shift relative to that of bulk TiO2 due to the quantum connement tor than their corresponding monolayer solar cells with the same
effect. Rutile-nanoparticles have higher capability to absorb and crystal structure. Moreover, both monolayer and double-layer solar
scatter the light than anatase-nanoparticles and nanowires due to cells made of anatase-TiO2 crystal structure had higher ll fac-
their lower band gap energy. tor than those contained rutile-TiO2 phase. The double-layer solar
cell made of anatase-TiO2 nanoparticles as the under-layer and
anatase-TiO2 nanowires as the over-layer (i.e., AW sample) showed
3.4. Photovoltaic performance of DSSCs the highest ll factor of 62.6% among all fabricated solar cells. This
can be explained by the internal resistance of the cells as the most
The photocurrent densityvoltage (JV) characteristics of mono- effective parameter of the ll factor. It seems the internal resistance
layer and double-layer TiO2 DSSCs with different crystal structures of anatase crystal structure is lower than that of rutile phase due to
were illustrated in Fig. 5. In addition, the corresponding photo-
voltaic parameters such as short circuit current (Jsc ), open circuit
voltage (VOC ), ll factor (FF) and power conversion efciency ()
were summarized in Table 3. It can be observed that the solar
cells contain anatase-TiO2 crystal structure had higher power con-
version efciency and ll factor than those made of rutile-TiO2
crystal structure. The difference in photocurrent is found to be
related to the lower surface area of the rutile lm compared with
that of the anatase lm per cell volume. Therefore, the anatase-
TiO2 phase is more favor than the rutile-TiO2 phase in solar cell
application. Intensity-modulated photocurrent spectroscopy and
scanning electron microscopy studies indicate that electron trans-
port is slower in the rutile layer than in the anatase layer due
to differences in the extent of inter-particle connectivity associ-
ated with the particle packing density [40]. The maximum value of
JSC was obtained for A monolayer solar cell, whereas WA double-
layer solar cell had the greatest value of VOC . The most likely
reason for the enhanced JSC is attributed to the increase of dye Fig. 3. XRD patterns of TiO2 nanostructures: (a) W, (b) A and (c) R.
388 A.M. Bakhshayesh et al. / Electrochimica Acta 78 (2012) 384391

Fig. 4. Optical absorbance spectra and the plots of (h)0.5 versus photon energy of: (a) W, (b) A and (c) R.

Fig. 5. Photocurrent densityvoltage curve of monolayer and double-layer TiO2 solar cells with different crystal structures: (a) based on anatase-TiO2 and (b) based on
rutile-TiO2 .
 A.M. Bakhshayesh et al. / Electrochimica Acta 78 (2012) 384391 389

Table 3
The photoelectrical parameters of monolayer and double-layer TiO2 solar cells.

Sample JSC (mA/cm2 ) VOC (mV) FF (%) Efciency (%) Thickness (m) Adsorbed dye (108 mol/cm2 )

W 2.74 790 62.1 1.36 11.6 06.32

A 17.81 720 46.9 5.98 11.3 10.15
AW 14.33 810 62.6 6.34 11.1 08.97
WA 8.41 860 61.4 4.35 11.0 08.52
R 15.49 740 39.2 4.44 11.4 09.73
RW 14.08 790 41.1 4.58 10.8 08.43
WR 11.82 720 44.3 3.81 11.1 08.65

Fig. 6. Electrochemical impedance spectroscopy Nyquist plots of: (a) W, R, A, (b) AW, WA, (c) RW, WR and (d) equivalent circuits of DSSCs.

arrangement of parallel octahedral connected by their vertices in
the case of anatase compared to 90 rotated octahedral connected
by their edges in the case of rutile. It is evident that, AW double-
layer solar cell had the highest power conversion efciency of 6.34%
among all fabricated monolayer and double-layer solar cells. The
improvement in the photovoltaic performance of AW double-layer
solar cell can be explained due to its synergic effect. On one side, the
under-layer has the highest surface area, resulting in high adsorp-
tion of dye molecules. The over layer, on the other hand, causes
improvement in light scattering and electron transport rate by
multiple scattering of photons increasing the optical path length.
Consequently, a systematic design of a double-layer solar cell made
of the proper under- and over-layers, by tailoring their crystal struc-
ture and morphology, can improve the photovoltaic performance
of TiO2 dye sensitized solar cells.
3.5. Electrochemical impedance spectroscopy analysis
The internal resistances and the electron transport rate of
TiO2 DSSCs were studied using the electrochemical impedance
spectroscopy (EIS). Fig. 6 shows the Nyquist plots of EIS of the
DSSCs under 100 mW/cm2 in the dark. The impedance spec-
tra were t to a geometrically appropriate equivalent circuit,
as presented in Fig. 6d. The diameter of the arc radius on the
EIS Nyquist plot of AW cell is obviously smaller than that of
other cells. The smaller the arc radius is, the higher the ef-
ciency of charge separation will become [42]. All spectra can be
described by three typical semicircles observed in the measured
frequency at both of the nanocrystalline TiO2 mono- and double-
layer photoelectrodes, which are assigned to the electrochemical
reaction at the Pt counter electrode (Rpt ), charge transfer at the

Table 4
Recombination and electronic transfer properties of TiO2 lms determined by tting EIS spectra.

Sample Rs ( cm2 ) Rpt ( cm2 ) Rtr ( cm2 ) Rct ( cm2 )  e (ms) t (ms)

W 4.34 1.12 1.01 71.86 1.117 0.016

A 4.31 1.22 2.43 3.02 4.903 3.945
AW 4.32 1.12 1.29 3.52 5.769 2.114
WA 4.31 1.13 1.36 16.27 3.516 0.293
R 4.33 1.39 5.99 19.13 4.097 1.282
RW 4.32 1.13 5.18 18.71 4.353 1.205
WR 4.32 1.74 5.90 28.35 2.763 0.575
390 A.M. Bakhshayesh et al. / Electrochimica Acta 78 (2012) 384391
TiO2 /dye/electrolyte interface (Rct ) and Warburg diffusion process
of I /I3 (Rs ) [43].
The electron lifetime ( e ) can be related to the characteristic
frequency in TiO2 lm and can be calculated as follows [44]:
e = Rct .C (3)
where Rct and C are the charge recombination resistance and
the chemical capacitance at TiO2 /dye/electrolyte interface, respec-
tively. The chemical capacitance is an equilibrium property that
relates the variation of the carrier density to the displacement of the
Fermi level. In simulation process, C was replaced with constant
phase element (CPE) in the tting procedure due to the non-ideal
capacitive response of TiO2 lm/solution interface. C can be cal-
culated by the following equation:
(Rct .CPET )1/CPEP
C = (4)
Rct
where CPET is the admittance magnitude of CPE, and CPEP is the
exponential term. The electron transit time (t) through the TiO2
lms can be obtained by the following equation [45]:
t Rtr
= (5)
e Rct
where Rtr is the transport resistances.
Table 4 shows recombination and electronic transfer properties
of TiO2 lms after tting the obtained data by a proper equiva-
lent circuit [46]. It can be observed that the charge recombination
resistance (Rct ) is much larger than the transport resistances (Rtr )
which is a feature generally necessary for good performance of
the DSSCs [47]. The lms containing anatase nanoparticles reached
lower charge transport resistance (Rtr ) than the rutile based lms,
measured in the dark. A and AW cells had the lowest Rct ; showing
that the electrons were well transmitted from electrolyte to dye
molecules and from dye molecules to TiO2 lm. It is interesting
to note that A and AW cells showed higher electron lifetime ( e )
and electron transit time (t) among all prepared cells due to slower
recapture of conduction band electrons by I3 ions. Therefore, A
and AW solar cells showed the least recombination process.
4. Conclusions
A systematic study of TiO2 DSSCs by fabrication of monolayer
and double-layer lms with various morphologies (i.e., nanoparti-
cle and nanowire) and crystal structures (i.e., anatase and rutile)
was presented. The monolayer solar cells made of a single TiO2
lm, while the double-layer solar cells contained an under-layer
and an over-layer TiO2 lms. The double-layer lms were fabri-
cated to improve the surface area, electron transport rate and the
light scattering effect of the solar cells. The average crystallite size
of anatase- and rutile-TiO2 nanoparticles was calculated around
18 nm and 24 nm, respectively. TiO2 nanowires showed length of
several m and diameter in the range 2050 nm. Furthermore, the
density of TiO2 nanowires, anatase-TiO2 and rutile-TiO2 nanoparti-
cles was measured 3.35, 3.85 and 4.25 g cm3 , respectively. UVvis
spectra of TiO2 nanostructures showed a blue shift relative to that
of bulk TiO2 due to the quantum connement effect. The photo-
voltaic parameters of solar cells were studied under 1 Sun AM 1.5G
simulated sunlight. It was found that the double-layer solar cells
showed higher ll factor than their corresponding monolayer solar
cells with the same crystal structure. Moreover, both monolayer
and double-layer solar cells made of anatase-TiO2 crystal structure
had higher ll factor and power conversion efciency than those
contained rutile-TiO2 phase. The double-layer solar cell made of
anatase-TiO2 nanoparticles as the under-layer and anatase-TiO2
nanowires as the over-layer showed the highest power conversion
efciency of 6.34% among all fabricated monolayer and double-
layer solar cells. The improved photoelectrical performance of AW
solar cell was attributed to high electron lifetime, rapid transporta-
tion, less recombination of photogenerated electrons, efcient light
scattering and good dye adsorption. The concept of double-layer
solar cells will open up new insight into fabrication and struc-
tural design of low-cost TiO2 DSSCs with high power conversion
efciency.
Acknowledgements
A.M. Bakhshayesh and M.R. Mohammadi would like to thank the
nancial support from Iran Nanotechnology Initiative Council.
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