Electrochimica Acta 129 (2014) 379388

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

CdS/CdSe Quantum dots Co-sensitized TiO2 Nanowire/Nanotube Solar

Cells with Enhanced Efciency
Zhen Li, Libo Yu, Yingbo Liu, Shuqing Sun
Department of Chemistry, Tianjin University, Tianjin 300072, P. R. China

a r t i c l e

i n f o

Article history:
Received 19 November 2013
Received in revised form 12 January 2014
Accepted 24 February 2014
Available online 11 March 2014
Keywords:
TiO2 nanowires/nanotubes
Electrochemical oxidization
CdS
CdSe
Quantum dots sensitized solar cells

a b s t r a c t
Translucent TiO2 nanowires/nanotubes (TiO2 NW/NT) lm would be a promising candidate in constructing photoelectrochemical solar cells for its advantages in sensitizer loading, charge separation, electronic
transport and light harvesting. In this report, translucent TiO2 NW/NT lm was prepared by a two-step
anodization method. The formation mechanisms of nanowires originated from nanotubes were explored.
The hydrogen ions generated by electrolysis of water were driven by electric eld to form ions ow,
which altered the interfacial stress of nanotubes, resulting in vertically or spirally splitting the mouth of
nanotubes to form nanowires. The CdS, CdSe and CdS/CdSe quantum dots (QDs) sensitized TiO2 NW/NT
solar cells were constructed. Among them, The TiO2 NW/NT solar cells co-sensitized with CdS/CdSe QDs
showed higher efciencies than ones sensitized with CdS or CdSe QDs. By varying successive ionic layer
adsorption and reaction (SILAR) cycles of CdS/CdSe, it was found that CdS(9)/CdSe(6)/TiO2 NW/NT device
reached to a maximum power conversion efciency of 2.41%, which was 78.5% higher than that of the
CdS(9)/CdSe(6)/TiO2 NT solar cell. The excellent photoelectrochemical properties of our solar cell suggest
that the translucent TiO2 NW/NT lms co-sensitized with CdS and CdSe QDs have potential application
in photovoltaic cells.
2014 Elsevier Ltd. All rights reserved.

1. Introduction
Inexhaustible solar energy is becoming an economically viable
source of energy to provide a clean solution to the current energy
crisis. Recently, semiconductor nanocrystals (NCs), often referred
to as quantum dots (QDs), have been the focus of considerable
research attention for the development of photovoltaic cells due
to their fascinating photoelectric properties [17]. The band gap
of QDs can be tuned by controlling their size to match the solar
spectrum [8,9]. Their large intrinsic dipole moments and high
extinction coefcient can lead to rapid charge separation [10].
Moreover, the QDs provide new opportunities to generate hot electrons and multiple electron-hole pairs with a single photon through
impact ionization [11,12]. For these reasons, narrow band gap semiconductors QDs are ideal candidates for the optimization of solar
cell to achieve improved performance.
A typical strategy to construct quantum dots sensitized solar
cells (QDSSCs) is to use semiconductor QDs as light absorber to
sensitize wide band gap metal oxide nanostructure lms such
as TiO2 [1316], ZnO[17,18], and SnO2 [19]. TiO2 lms have been

Corresponding author. Tel.: +8613920690912.

E-mail address: sunshuqing@tju.edu.cn (S. Sun).
http://dx.doi.org/10.1016/j.electacta.2014.02.145
0013-4686/ 2014 Elsevier Ltd. All rights reserved.

demonstrated to be a promising candidate as photoanodes due to

their appropriate energy band position and both thermal and chemical stability in solution [20]. To date, TiO2 NTs [2126] have been
a focus of investigation to enhance the electron transport owning
to several advantages. First, TiO2 NTs have less grain boundaries
that electrons have to pass [22], which leads to fast transport of
excited electrons. Second, highly ordered TiO2 NTs offer a vertical
path way for electron transport along the tube, which minimizes
electron loss during diffusion process [27]. What is more, the vertical tubular structure facilitates the lling of QDs sensitizer or
redox couple electrolyte [28]. In spite of these advantages, sufcient QDs loading into TiO2 NTs is still a challenge in practice,
resulting in low light harvesting efciency. Therefore, the power
conversion efciency of QDSSCs based on TiO2 NT solar cells is
usually in lower than 1.5% [29]. Design of hierarchical structure
TiO2 lm [26,28] is a good approach to overcome the disadvantages of poor sensitizers loading, therefore translucent hierarchical
TiO2 NW/NT lm was designed by us. Two important issues can be
resolved with application of this translucent TiO2 NW/NT lm in
QDSSCs. First, the TiO2 nanowires entangled with each other on top
of nanotubes allows the diffusion of QDs sensitizers through multiple pathways to enhance QDs loading and light harvesting. Second,
the TiO2 NW/NT possesses a larger surface exposure area to the liquid redox couple electrolyte, which increases area of solid-liquid

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junction. This can promote the charge separation of the photogenerated electrons and holes so as to enhance photocurrent. To
our best knowledge, this translucent TiO2 NW/NT lm applied to
QDSSCs is rarely reported.
In this report, translucent TiO2 NW/NT lms were successfully
fabricated by a two-step anodization approach, and the formation
mechanism of the TiO2 NW/NT was explored as well. The TiO2
NW/NT lm co-sensitized with CdS/CdSe QDs was used as front
side illuminated photoanode in solar cells. By optimizing the SILAR
cycles of CdS/CdSe QDs, the CdS(9)/CdSe(6)/TiO2 NW/NT lm solar
cell reached to a maximum power conversion efciency of 2.41%,
which is signicantly higher than that of the CdS(9)/CdSe(6)/TiO2
NT lm solar cell (1.35%). Our CdS/CdSe QDs co-sensitized translucent TiO2 NW/NT lm solar cells open up a new way for designing
high efciency QDSSCs.
2. Experimental
2.1. Materials
The following chemical agents were used: titanium foils (99.6%
purity, Tianjin, China), ammonium uoride (NH4 F, AR), ethylene
glycol (HOCH2 CH2 OH, AR), hydrogen peroxide (30 wt % H2 O2 ),
deionized water (H2 O, 18.2 Mcm resistivity), cadmium nitrate
(Cd(NO3 )2 4H2 O, AR), sodium sulde (Na2 S9H2 O, AR), sodium
sulte (Na2 SO3 , AR), selenium powder (Se, AR), sulfur powder (S,
AR). All these materials were used directly in experiments without
further purication.
2.2. Fabrication of translucent TiO2 NW/NT lm
The TiO2 NW/NT lm was prepared by a two-step electrochemical anodization method. Ti foil with the dimension of 20 mm
10 mm 0.1 mm was degreased by sonicating in acetone, deionized
water and ethanol for 10 min respectively, and nally dried in air.
In the rst electrochemical anodization process, the cleaned Ti foil
was anodized in Teon electrolysis cell with a two-electrode conguration, which Ti foil worked as working electrode and graphite
sheet (15 mm 25 mm) worked as counter electrode. The distance
between the two electrodes was 50 mm. The electrolyte consisted
of ethylene glycol, NH4 F (0.5 wt %) and deionized water (3vol %).
After anodization, the anodized Ti foil was ultrasonically washed
in ethanol for 5 min to remove the debris on the surface of sample, and then dried in air. In order to form anatase TiO2 phase, the
anodized Ti foil was calcined in mufe furnace at 450 C for 1 h with
heating rate of 5 C/min, and then was cooled to room temperature
with cooling rate of 2 C/min.
After sintering treatment, the rst anodized product was
anodized again in the same stock electrolyte at constant potential of 10 V for 3 h. Then the second anodized Ti foil was rinsed in
ethanol and dried in air. Subsequently, the product was immersed
into 10 wt % H2 O2 aqueous solution for 12 h. Following this, the
free-standing translucent TiO2 membrane would be separated
automatically or detached by tweezers from the Ti substrate.
2.3. Construction of CdS/CdSe QDs co-sensitized TiO2 NW/NT lm
on FTO Electrodes

NW/NT lm on FTO glass was annealed at 450 C for 30 min. The

size of the TiO2 NW/NT lm was 0.25 cm2 (5 mm 5 mm).
The TiO2 NW/NT lms electrodes were sensitized in situ with
CdS and CdSe by SILAR. The electrodes were immersed in 0.1 M
Cd(NO3 )2 aqueous solution for 3 min and rinsed with deionized
water and ethanol for 30s respectively; then dipped for an additional 3 min in 0.1 M Na2 S aqueous solution and rinsed with water
and ethanol respectively for 30s. All of these processes constituted
one SILAR cycle. The deposition of CdSe was also conducted by
SILAR with alternately immersing electrodes in 0.1 M Cd(NO3 )2 and
0.1 M NaSeSO3 aqueous solution for 5 min, respectively. NaSeSO3
solution was prepared by reuxing Se powder and NaSO3 at 96 C
[30]. Different SILAR cycles of CdS and CdSe were conducted to
investigate the optimal combination cycles of the two kinds of QDs
for the best performance of solar cells. In addition, TiO2 NT lm of
the same thickness to TiO2 NW/NT was also prepared to explore
if the TiO2 NW/NT electrode has signicant effect on the power
conversion efciency of QDSSCs.
2.4. Fabrication of counter electrodes and cell assembly
Cu1.8 S/CuS counter electrodes were prepared via hydrothermal
method reported by Kalanur et al. [31]. In brief, FTO glasses
predrilled with two holes for injection of electrolyte were cleaned
by sonication in acetone, deionized water and ethanol for 10 min
respectively. Then 25 mL of 0.1 M copper sulfate and 0.05 M
thiourea aqueous solution were mixed together. The mixed solution was quickly transferred to the autoclave, lling 80% volume.
The FTO substrate was placed at an angle against the wall of Teonliner with the conducting side facing down. The hydrothermal
reaction was conducted at 150 C for 2 h.
The QDs sensitized TiO2 NW/NT electrodes and Cu1.8 S/CuS
counter electrodes were assembled in a sandwich fashion cell. The
Surlyn lm with thickness of 60 m was used as spacer. The solution of 0.5 M sodium sulde and 0.1 M sulfur dissolved in deionized
water as liquid electrolyte was injected into the space of solar cell
through one hole on the counter electrode.
2.5. Characterization
Scanning electron microscopy (SEM) images were recorded
using a Hitachi S-4200 eld emission SEM equipped with an
energy dispersive X-Ray (EDX) spectrometer. Transmission electron microscope (TEM) images of samples were obtained by a
Tecnai G2 F20 at 200 kV. The crystalline nature and structure of
TiO2 NW/NT lm were analyzed by X-Ray diffraction (XRD, D/MAX2400, Rigaku) using a Cu K source operated at 40 kV and 30 mA
with scanning rate of 2 /min. The optical absorbance of the samples
was recorded using a UV2501PC (SHIMADZU) spectrometer with
an ISR-2200 integrating sphere attachment for diffuse reection
measurement. The current-voltage characteristics were performed
with Oriel I-V test station by Newport. A solar simulator (PecellL15, Japan) which calibrated by standard silicon solar cell (BS-520,
Japan) was used to simulate sunlight with irradiation intensity of
100 mW/cm2 . The incident photo-to-current conversion efciency
(IPCE) was measured as a function of wavelength from 300 nm to
800 nm by using a model 7-SCSspec II system.
3. Results and discussion

The following procedures were undertaken in order to construct

photoanode electrodes. First, 2 mmol of butyl titanate was added
into the 10 mL of anhydrous ethanol under slowly stirring to form
a viscous solution. After a few minutes stirring, two drops of the
solution were dropped on the FTO glass (20 mm 20 mm) as adhesive. Then translucent TiO2 NW/NT lm was covered on the top of
the adhesive and dried in air for a few minutes. After that, the TiO2

3.1. The Formation of Translucent TiO2 NW/NT Film

The top morphology of TiO2 NT, TiO2 NW/NT and their corresponding cross-section images were obtained from FE-SEM. As
shown in Fig. 1a, highly ordered TiO2 NT arrays were formed on
Ti substrate after the rst electrochemical anodization at 50 V for

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381

Fig. 1. Top morphology of (a) TiO2 NT and (b) TiO2 NW/NT. Inset of (b) is optical image of NW/NT lm. (c) SEM image of NWs on top of NTs. (d) Cross-section images of
TiO2 NT and (e) TiO2 NW/NT. (f) Back side morphology of TiO2 NW/NT. (g) TEM of TiO2 NT. (h) SAED of TiO2 NT without annealing treatment and (i) TiO2 NT with annealing
treatment.

6 h. The diameter of the NT is around 110 nm and the wall thickness is about 15 nm. Fig. 1b gives the top view of translucent TiO2
NW/NT lm. It shows NWs appeared on the surface of the TiO2
NT arrays after the second anodization at 10 V for 3 h and the
tubular structure beneath the wires still remain ordered, which
indicates this two-step electrochemical anodization approach is
feasible for the synthesis of hierarchical TiO2 NW/NT nanostructure. The whole TiO2 NW/NT membrane with faint yellow color and
translucence remained integrity after being peeled off from the Ti
substrate (inset of Fig. 1b), providing its application value as front
illuminated photoanode in QDSSCs. The NWs are about 11.5 m
in length and 2030 nm in diameter as shown in large magnication SEM of Fig. 1c. Although the nanowires originated from the
second anodization, the thickness of NW/NT lm is almost unvaried comparing with the TiO2 NT lm prepared by rst anodization.
Both Fig. 1d and 1e present that the thicknesses of the TiO2 NT lm
and TiO2 NW/NT lm are about 6 m, indicating that the second
anodization process only contributed to the formation of nanowires
on top of TiO2 NT arrays and has no obvious effect on the longitudinal growth of nanotube. The backside view of the translucent TiO2
NW/NT lm in Fig. 1f shows that the nanotubes possessed sealed
ends, and the integrity of the TiO2 NT arrays was preserved well
after the separation from titanium substrate. Fig. 1 g is The TEM of
the TiO2 NT, showing that the rst anodized sample has an ordered
tubular structure. The selected area electron diffraction (SAED) patterns from the TEM of TiO2 NT before and after annealing treatment
at 450 C were given in Fig. 1h and Fig. 1i, respectively. Before
the heat treatment, no electronic diffraction rings can be seen in
Fig. 1h, which indicates that the TiO2 NT produced by anodization was amorphous. The TiO2 NT transformed from amorphous
to crystalline after the annealing treatment, which was proved by
the appearance of electronic diffraction rings in SAED of Fig. 1i.

X-ray diffraction (XRD) patterns were used to further characterize the phase structure transformation of TiO2 from amorphous
to crystalline. As shown in Fig. 2a, only diffraction peaks of titanium can be indexed (JCPDS le 44-1294) in the rst anodized
Ti foil, which means the as-prepared TiO2 NT on Ti substrate
was probably amorphous. This result was in accordance with
the SAED from TEM of un-annealed TiO2 NT. After annealing at
450 C for 1 h, the TiO2 transformed from amorphous to anatase
phase. In XRD pattern of anatase TiO2 NT, both diffraction peaks
of Ti and anatase TiO2 (JCPDS le 21-1272) can be indexed. The
typical sharp peak at 25.3 corresponding to the (101) plane
of anatase TiO2 conrms the crystalline phase transformation
from amorphous to anatase at 450 C. For the translucent TiO2
NW/NT lm, the peaks belonging to Ti have been disappeared,
and all of diffraction peaks can be attributed to the anatase TiO2
phase.
The elementary composition analysis of the free-standing TiO2
NT and TiO2 NW/NT lms were carried out by energy dispersive
X-Ray (EDX) spectrometer. The peaks corresponding to carbon,
oxygen and titanium appeared in the spectra of Fig. 2b and 2c. Ethylene glycol was absorbed into TiO2 NTs during the process of rst
anodization and was burned to CO2 and H2 O in furnace atmosphere.
However, it is possible that not all the ethylene glycol was consumed to produce CO2 , some maybe transform into carbon residing
in TiO2 NTs due to the insufcient of oxygen in the furnace, which
resulted in the presence of carbon in EDX spectra. The dominant
elements in the two EDX spectra are titanium and oxygen, implying that the lms were mainly composed of Ti and O. However, both
of the two EDX spectra showed that the ratio between Ti and O is
much more than 1:2. It seems that there was more Ti than O. The
possible reason may be that amorphous Ti was introduced into the
TiO2 NT and TiO2 NW/NT during the rst and second anodization

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to previous report [32]. At rst, the amorphous TiO2 barrier layer

was formed by EO; meanwhile the F- in electrolyte began to etch
the surface of barrier layer to produce pits, which is called pitting
attack process. Then the pits were developed into tubular structure by prolonging anodization time. A thin amorphous TiO2 barrier
layer would exist between nanotubes layer and Ti substrate due
to the rate of EO superiors to the rate of CE; and after annealing
at 450 C for 1 h, the amorphous TiO2 was transformed to anatase
TiO2 as shown in rst anodization part of Fig. 3.
The formation process of the translucent TiO2 NW/NT lm is
summarized in second anodization part of Fig. 3. During the second anodization, a lower potential of 10 V was applied to the rst
anodized sample in the same stock electrolyte. The TiO2 NWs were
generated from the top of the TiO2 nanotubular arrays in this
step; meanwhile, a new amorphous TiO2 barrier layer was formed
again beneath the anatase TiO2 NT arrays. After rinsed in ethanol
and dried in air, the second anodized sample was immersed in
10wt% H2 O2 aqueous solution for 3 h to dissolve the new formed
amorphous TiO2 layer, and then the TiO2 NW/NT membrane was
separated from the Ti substrate.
The possible models for the origination of nanowires from
TiO2 NT arrays are proposed in Fig. 4. We hypothesized that the
nanowires originated from the split of the TiO2 nanotubes. Water
played an important role in secondary anodization with the applied
potential of 10 V. In this stage, water was electrolyzed at the bottom
of the TiO2 tubular anode. Two main reactions probably happened
as follows:
-

H2 O H+ + OH
-

2OH H2 O + O

Fig. 2. (a) XRD patterns for amorphous TiO2 NT on Ti, anatase TiO2 NT on Ti, and
translucent TiO2 NW/NT lm, respectively. (b) EDX spectrum of TiO2 NT lm. (c)
EDX spectrum of TiO2 NW/NT lm.

since the XRD did not show any crystalline Ti in the TiO2 NW/NT
lm.
The growth of TiO2 NT on Ti substrate was determined by two
main reactions as follows:
Ti + 2H2 O TiO2 + 4H+ + 4e-

(1)

TiO2 + 4H + 6F- [TiF6 ]2- + 2H2 O

(2)

The reaction (1) is the process of electrochemical oxidation (EO),

leading to the formation of amorphous TiO2 barrier layer on the
surface of Ti substrate, and the reaction (2) is called the chemical
etching (CE) process which results in the formation of pits on amorphous TiO2 surface. Only when the reaction rate of EO is faster than
the reaction rate of CE, the TiO2 NTs can be produced according

(3)
2

(4)

The O2 generated from electrolysis as source of oxygen contributed to the new amorphous TiO2 layer which would be
dissolved by H2 O2 to produce free-standing TiO2 NWNT lm in
post-treatment, while H+ would help to generate the wires at the
mouth of nanotubes. According to the reported literature [33],
H+ was limited at the bottom of nanotubes under high potential
(>20 V), forming a localized acidication atmosphere which was
favorable to chemical etching for prolonging nanotubes. However,
the voltage of 10 V in our second anodization process was not high
enough to conne the H+ at the bottom of the tubes in the viscous
ethylene glycol solution, therefore, the H+ generated at the bottom
of nanotube would be driven to the cathode by electric eld, this
may lead to H+ ow through the bottom to the mouth of nanotubes. However, the moving way of H+ ow in nanotube may have
two different forms: vertical motion or spiral motion in the nanotubes. At the tube mouth, the H+ ow creates an interfacial stress of
nanotubes in the viscous electrolyte. With the assistance of chemical dissolution along this stress on TiO2 nanotubes electrode, the
mouth of nanotubes split vertically or spirally to form nanowires
as depicted in Fig. 4. In addition, water electrolysis in ethylene glycol medium was an inefcient reaction [34], the chemical etching
process was suppressed and the splitting reaction was also limited
to the mouth of the nanotubes, which led to the nanowires originated only on the surface of TiO2 nanotubular arrays. The path 1
is similar to the mechanism bamboo-splitting model previously
reported by J. H. Lim [33], and we infer that if the vertical split of
nanotube is the dominant reason for the formation of TiO2 NWs,
the length of the nanotube would be shorted. However, in contrast
with cross-section image of Fig. 1d and 1e, it can be distinguished
that the lengths of tubes for TiO2 NW/NT and TiO2 NT are almost the
same. Therefore, we proposed the spiral split mechanism (path 2)
to interpret this phenomenon. The diameter of the TiO2 NT is about
110 nm when prepared at 50 V for 6 h; hence the circumference of
the tube is about 345 nm, which means that only three to four circles of spiral split are enough for the nanowires length of around

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383

Fig. 3. The formation process of free-standing translucent TiO2 NW/NT membrane by a two-step anodization approach.

11.5 m. No obvious variation of the tubes length between TiO2

NW/NT and NT lm conrmed the rationality of the spiral splitting
mechanism. We believe that both the vertical and spiral splitting
paths contributed to the origination of nanowires from TiO2 NT
arrays in secondary anodization process, and the spiral splitting
may have more contribution.
3.2. Photoanodes Analysis
QDs sensitized photoanodes were fabricated by variation of
SILAR cycles in Cd, S and Se precursor solution respectively. The
whole surface of TiO2 NW/NT lm and CdS(9)/CdSe(6) QDs sensitized TiO2 NW/NT lm are presented in Fig. 5a and5b respectively.
The surface of CdS(9)/CdSe(6) NW/NT lm (Fig. 5b) was obviously
rougher than that of TiO2 NW/NT lm, indicating the successful
deposition of CdS/CdSe QDs on TiO2 NW/NT lm. Especially in the
area with NWs in Fig. 5b, the surface of the lm was almost covered by quantum dots, which suggested that the NWs on top of

NTs boost the adsorption of CdS/CdSe QDs. In addition, TiO2 NTs

beneath wires also adsorbed QDs, which were conrmed by the
decrease of inner tube diameter as shown in the inset of Fig. 5b. The
image of TiO2 NWs that adsorbed QDs was given by SEM in Fig. 5c,
it can be seen that the large amount of QDs were lled in the interspaces among the nanowires after the SILAR, and TEM image (inset
of Fig. 5c) clearly showed that the distribution of QDs on TiO2 NWs.
Fig. 5d is the TEM of the tubular part of the sensitized TiO2 NW/NT
lm, showing that QDs can also be found inside the nanotubes.
The distribution of QDs in nanowires and nanotubes manifested
that this TiO2 NW/NT hierarchical structure can enlarge the QDs
loading.
The photographs of CdS(15)/TiO2 NW/NT, CdSe(15)/TiO2
NW/NT and CdS(9)/CdSe(6)/TiO2 NW/NT electrodes are shown in
Fig. 6a, 6c and 6e respectively. Visibly, these samples showed single and unique colors with good uniformity across the surface and
the color changed from yellow to red as the introduction of CdSe
QDs to the NW/NT lm. In order to further conrm the successful

Fig. 4. Origination mechanism of nanowires from TiO2 nanotube by secondary anodization.

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Z. Li et al. / Electrochimica Acta 129 (2014) 379388

Fig. 5. SEM images of (a) TiO2 NW/NT lm and (b) CdS(9)/CdSe(6)/TiO2 NW/NT lm, inset is large magnication SEM from tubes area. (c) Large magnication SEM from
wires area, inset is the TEM of NWs sensitized with QDs. (d) TEM of the TiO2 NTs sensitized with QDs.

deposition of CdS/CdSe QDs on TiO2 NW/NT lm, three types of photoanodes were analyzed by EDX spectra. Fig. 6b, 6d and 6f show the
EDX spectra of the CdS(15)/TiO2 NW/NT, CdSe(15)/TiO2 NW/NT and
CdS(9)/CdSe(6)/TiO2 NW/NT electrodes. The characteristic peaks of
Cd and S elements are presented in Fig. 6b, indicating that the CdS
QDs have been successfully assembled on the TiO2 NW/NT lm.
Apparently, atom content of Cd and Se in EDX spectrum of Fig. 6d
is extremely low, which means that only a few CdSe QDs can be
deposited on TiO2 NW/NT lm with 15 SILAR cycles. However, rst
deposition of CdS on TiO2 is favorable for further sensitization of
CdSe QDs, which is veried by EDX spectrum of Fig. 6f. As we can
see, the atom content of Se is greatly enhanced, and the atomic
ratio of S and Se to Cd nearly equal to 1:1 (3.09 At% of Se, 4.24
At% of S and 6.21 At% of Cd). This chemical analysis provides the
evidence of the formation of CdS/CdSe QDs on TiO2 NW/NT lm
photoanode. The effective deposition of the quantum dots can also
be identied by naked eyes, as there is no observable coloration
inhomogeneous across the surface of CdS(9)/CdSe(6)/TiO2 NW/NT
electrode in Fig. 6e.

3.3. UV-Visible Diffuse-Reectance

The UV-vis diffuse reectance absorbance spectra of our samples are illustrated in Fig. 7. The TiO2 NW/NT lm (Fig. 7a) showed a
main absorption edge at 380 nm, corresponding to 3.26 eV, which
was in accordance with the bandgap of anatase TiO2 . However, the
UV-vis spectrum of CdS(9)/TiO2 NW/NT lm (Fig. 7b) exhibited red
shift of broad absorption edge to 530 nm. This result indicated that
the deposition of CdS QDs on TiO2 NW/NT lm enlarged the light
absorption range to visible region. While in the UV-vis spectrum of
CdS(9)/CdSe(6)/TiO2 lm (Fig. 7c), a further red shift of adsorption
edge to 700 nm implied that successful deposition of CdSe QDs on
CdS/TiO2 NW/NT. This variation demonstrated that the deposition

of CdS/CdSe QDs has signicantly extended the photoresponse of

TiO2 NW/NT electrode from ultraviolet light to nearly entire visible
light region. The outcome can be interpreted as follows: the CdS
QDs on TiO2 NW/NT may act as a seed layer to facilitate the nucleation of CdSe QDs due to the small lattice mismatch between CdS
and CdSe [14]. Therefore, it is anticipated that the CdS/CdSe/TiO2
NW/NT lm structure is a promising candidate in photovoltaic
devices.

3.4. J-V Performances of the QDSSCs

Various CdS/CdSe co-sensitized TiO2 /NW/NT solar cells were
assembled and their photovoltaic performances were investigated
by Oriel I-V test station under 1 sun (= 100 mW/cm2 AM1.5G
solar illumination). Fig. 8a compares the current density-voltage
characteristics of three solar cells assembled with CdS(15)/TiO2
NW/NT, CdSe(15)/TiO2 NW/NT and CdS(9)/CdSe(6)/TiO2 NW/NT
electrodes. The CdS(15)/TiO2 NW/NT exhibited short circuit current (Jsc ), open voltage (Voc ) and power conversion efciency
values () of 4.78 mA/cm2 , 0.34 V and 0.59%, respectively. While
the CdSe(15)/TiO2 NW/NT showed much lower Jsc (1.94 mA/cm2 )
due to low coverage of CdSe on TiO2 NW/NT. It is worth noting
that the photovoltaic performance of CdS(9)/CdSe(6)/TiO2 NW/NT
photovoltaic device was signicantly improved, possessing Jsc , Voc
and of 14.73 mA/cm2 , 0.47 V and 2.41%, respectively. Two main
reasons are probably responsible for the improvement. First, CdS
QDs layers were favorable for more adsorption of CdSe QDs, resulting in a complementary effect [16] in light harvesting due to the
expansion of the scope of light absorption (as shown in Fig. 7b and
7c), which benets for the increase of Jsc . In addition, TiO2 NW/NT
lm co-sensitized with CdS and CdSe increased the Voc by forming
cascading band structure, which can effectively separate excitons
at the junctions [18].

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385

Fig. 6. Optical images and EDX spectra of CdS (a, b), CdSe (c, d), and CdS/CdSe (e, f) sensitized TiO2 NW/NT photoanode.

Fig. 7. Diffuse-reectance UV-visible spectra of (a) TiO2 NW/NT lm, (b) CdS(9)/TiO2
NW/NT photoanode, (c) CdS(9)/CdSe(6)/TiO2 NW/NT photoanode.

To further investigate the optimal combination of CdS and

CdSe, CdS/CdSe/TiO2 NW/NT solar cells with different SILAR cycles
were fabricated. Fig. 8b depicts the J-V performance variation of
these solar cells, and Fig. 8c gives the power conversion efciency as the function of different SILAR cycles of CdS/CdSe. The
CdS(9)/CdSe(6)/TiO2 NW/NT solar cell yielded the highest of
2.41% with the Jsc , Voc and ll factor (FF) values of 14.73 mA/cm2 ,
0.47 V and 0.35 respectively. The performance parameters of various solar cells are summarized in Table 1. As it shows, the values of
Jsc , Voc and of single CdS or CdSe QDs sensitized TiO2 NW/NT solar
cells are lower than any of CdS/CdSe/TiO2 NW/NT solar cells. The
values of co-sensitized solar cells were inuenced by the different
SILAR cycles of CdS and CdSe QDs. Appropriate cycles of CdS were
not only benecial for the absorption of light but also in favor of
the deposition of CdSe, which is helpful for the improvement of .
As illustrated in Fig. 8c, The CdS(3)/CdSe(12)/TiO2 NW/NT solar cell
has a lower value (0.77%). The reached to the maximum value of
2.41% when the SILAR cycles of CdS and CdSe were 9 and 6, respectively. However, further increase SILAR cycles of CdS resulted in the
reduction of , which was presented by the CdS(11)/CdSe(4)/TiO2
NW/NT solar cell with of 1.08%. An excessive amount of CdS QDs
on TiO2 NW/NT probably provided more recombination sites or

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Z. Li et al. / Electrochimica Acta 129 (2014) 379388

Fig. 8. Illuminated J-V characteristics of (a) TiO2 NW/NT sensitized by CdS(15), CdSe(15) and CdS(9)/CdSe(6). (b) TiO2 NW/NT lm solar cells with different SILAR cycles of
CdS and CdSe. (c) The power conversion efciency as the function of different CdS/CdSe SILAR cycles. (d) J-V curves of CdS(9)/CdSe(6) devices employing TiO2 NW/NT and
TiO2 NT.

led to local block in nanotubes, which hindered the efcient transport of photogenerated electrons from QDs to the TiO2 photoanode,
causing the decrease of the power conversion efciency.
In order to interpret that the performance of TiO2 NW/NT solar
cell is better than TiO2 NT solar cell, the translucent TiO2 NT lm
was prepared according to the method proposed by Chen et al.
[35] as comparison group. The TiO2 NT lm possessed the identical
diameter and thickness to TiO2 NW/NT was obtained by controlling reaction conditions to insure only the structure is the factor
that inuence the performance of solar cells. Fig. 8d illustrates the
J-V characteristics of TiO2 NW/NT and TiO2 NT lm solar cells sensitized with CdS(9)/CdSe(6) QDs. Both of the solar cells presented

almost same Voc and FF. However, the Jsc of TiO2 NW/NT solar cell
is markedly enhanced in contrast with that of TiO2 NT solar cell.
The increment of Jsc resulted in the enhancement of from 1.35%
to 2.41%.
The incident photo-to-current conversion efciency (IPCE) of
TiO2 NW/NT and TiO2 NT solar cells sensitized with CdS(9)/CdSe(6)
QDs are shown in Fig. 9. In general, the IPCE spectra of the two solar
cells were consistent with the corresponding UV-vis spectrum of
CdS(9)/CdSe(6)/TiO2 NW/NT photoanode (Fig. 7c), which indicated
that most of the visible region light was absorbed by CdS/CdSe
quantum dots and involved in the photocurrent generation. IPCE
values as high as 48.6% can be achieved by the TiO2 NW/NT solar

Table 1
I-V curve parameters measured at 1 sun illumination.
Sample

Jsc (mA/cm2 )

Voc (V)

FF

Efciency (%)

CdS(15)/TiO2 NW/NT
CdSe(15)/TiO2 NW/NT
CdS(3)/CdSe(12)/TiO2 NW/NT
CdS(5)/CdSe(10)/TiO2 NW/NT
CdS(7)/CdSe(8)/TiO2 NW/NT
CdS(9)/CdSe(6)/TiO2 NW/NT
CdS(11)/CdSe(4)/TiO2 NW/NT
CdS(9)/CdSe(6)/TiO2 NT

4.78
1.94
6.65
8.54
12.17
14.73
7.96
9.02

0.34
0.34
0.38
0.44
0.38
0.47
0.42
0.47

0.36
0.38
0.30
0.33
0.39
0.35
0.32
0.32

0.59
0.25
0.77
1.22
1.80
2.41
1.08
1.35

Z. Li et al. / Electrochimica Acta 129 (2014) 379388

Fig. 9. IPCE spectra of the CdS(9)/CdSe(6) based on TiO2 NW/NT and TiO2 NT solar
cells.

cell, but the values obtained by the TiO2 NT device are only about
38.7%. This result indicates that the TiO2 NW/NT structure not only
maintains the advantage of the nanotube such as efcient charge
separation and swift electron transport properties, and even performs better than TiO2 NT. The relatively excellent IPCE value of
the CdS/CdSe/TiO2 NW/NT solar cell manifested its great promise
for the construction of high performance quantum dots sensitized
solar cells.
The congurations of our co-sensitized solar cells are depicted
in Fig. 10a and 10b. Based on these schemes, We here proposed several possible reasons to interpret the enhancement of performance
for TiO2 NW/NT solar cell: rst, the TiO2 NW/NT structure retains
the advantage of the nanotube such as efcient charge separation
and swift electron transport properties, which was conrmed by
IPCE spectra; second, the appearance of nanowires on top of tubes
have signicantly enlarged the adsorption of quantum dots, which
was evidenced by SEM and TEM images from Fig. 5; third, the ne
heterojunction formed between CdS and TiO2 NW/NT is benecial
for CdS QDs to collect excited electrons from CdSe QDs to the conduction band of TiO2 in the stepwise band edge alignment as shown
in Fig. 10d; nally, TiO2 NW/NT structure increases the deposition areas of CdSe, which probably leads to the local existence of

387

Fig. 11. Photocurrent stability of CdS(9)/CdSe(6)/TiO2 NW/NT cell under continuous

illumination of 100mW/cm2 .

CdSe/TiO2 interface that will aggrandize the effect cover area and
consequently improve the photocurrent [36].
The photostability of QDSSC is another very important issue.
Thus the stability of CdS(9)/CdSe(6)/TiO2 NW/NT solar cell was
investigated by recording Jsc variation under the continuous illumination (Fig. 11). During the rst 60 min of irradiation, a stable short
circuit current density of 14.714.5 mA/cm2 was observed, which
demonstrated an excellent stability of the solar cell during the measurement. The photostability could be attributed to efcient holes
scavenging capability of polysulde electrolyte, which successfully
suppresses hole-induced anodic corrosion of the CdS/CdSe QDs.
Despite the CdS(9)/CdSe(6)/TiO2 NW/NT solar cell has achieved
an acceptable conversion efciency of 2.41%, it can be anticipated
that there is still much space for further improvement of the power
conversion efciency, in particular by augmentation of Voc and FF.
For instance, a ZnS capping layer[9] and annealing treatment may
reduce the undesired surface trapping, or new counter electrode
materials[37,38] being applied to facilitate the catalytic reduction
of the redox electrolyte. This will be the focus of our continuing
research work. In this research, our CdS/CdSe/TiO2 NW/NT solar
cell opens up new avenue for further development of high power
conversion efciency QDSSCs.

Fig. 10. Conguration of CdS/CdSe co-sensitized solar cells based on (a) TiO2 NW/NT and (b) TiO2 NT, respectively. (c) Band-edge positions of TiO2 , CdS, and CdSe in bulk. (d)
Proposed realignment band-edges for CdS/CdSe/TiO2 electrode in equilibrium with the redox couples electrolyte.

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Z. Li et al. / Electrochimica Acta 129 (2014) 379388

4. Conclusion
In conclusion, a novel translucent TiO2 NW/NT lm was successfully fabricated by a two-step anodic oxidization method.
According to the results of SEM characterization, two possible
mechanisms for the generation of nanowires from nanotubes were
proposed. By SILAR approach, CdS and CdSe QDs co-sensitized
TiO2 NW/NT lms were used as photoanodes in QDSSCs. The
CdS/CdSe/TiO2 NW/NT cells showed better cell performance than
single CdS or CdSe QDs sensitized TiO2 NW/NT solar cells. A maximum power conversion efciency up to 2.41% has been achieved
with the CdS(9)/CdSe(6)/TiO2 NW/NT solar cell under simulated
AM 1.5G irradiation of 100 mW/cm2 , a 78.5% increase in power
conversion efciency comparing with that of CdS(9)/CdSe(6)/TiO2
NT cell (1.35%). The reasons for enhanced efciency are that the
hierarchical structure of TiO2 NW/NT leads to sufcient QDs loading. Our CdS/CdSe QDs co-sensitized translucent TiO2 NW/NT lm
photovoltaic cells have shown a potential value in designing high
efciency QDSSCs.

[15]

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[20]

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[22]

[23]

Acknowledgment
The authors gratefully acknowledge the support for this work
from the Key Project of Tianjin Sci-Tech Support Program (No.
08ZCKFH01400).
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