J Mater Sci: Mater Electron
DOI 10.1007/s10854-016-4678-z
The preparation and assembly of CdSxSe12x alloyed quantum dots
on TiO2 nanowire arrays for quantum dot-sensitized solar cells
Libo Yu1 • Xuefeng Ren1 • Zirong Yang1 • Yuqi Han1 • Zhen Li1
Received: 6 November 2015 / Accepted: 12 March 2016
Ó Springer Science+Business Media New York 2016
Abstract Highly ordered TiO2 nanowire (NW) arrays
were constructed by hydrothermal process as support
materials for quantum dot sensitized solar cells (QDSSCs).
The CdSxSe1-x alloyed quantum dots (QDs) with tunable
composition have been assembled onto the TiO2 NW
arrays via a facile hydrothermal method to form CdSx
Se1-x/TiO2 NW photoanodes. The light absorption range
of the CdSxSe1-x/TiO2 NW photoanodes can be controlled
by changing the atomic ratio of S to Se. Based on CdSx
Se1-x/TiO2 NW photoanodes, the photovoltaic perfor-
mance of these CdSxSe1-x/TiO2 NW solar cells gradually
improved as the increase of Se content in CdSxSe1-x
alloyed QDs. Among all sample CdSxSe1-x/TiO2 NW solar
cells which were prepared with different feed molar ratio of
S:Se, the CdS0.27Se0.73/TiO2 NW solar cell (prepared with
S:Se = 0:4) produced the highest power conversion effi-
ciency up to 2.46 %. The results of investigation into
optical properties and incident photon-to-current conver-
sion efficiency indicates that the enlarged light absorption
range and effective photo-to-electrical efficiency can be
obtained with Se-rich CdSxSe1-x/TiO2 NW photoanodes,
which contribute to the enhanced photovoltaic performance
of the CdS0.27Se0.73/TiO2 NW solar cell.
Electronic supplementary material The online version of this
article (doi:10.1007/s10854-016-4678-z) contains supplementary
material, which is available to authorized users.
& Zhen Li
lizhen_665@163.com
1 approaches can easily deposited and directly connected
College of Chemistry and Chemical Engineering, Hexi
University, Zhangye City 734000, Gansu Province,
People’s Republic of China
1 Introduction
The huge consuming of fossil fuels soon will force us to
seek environmentally friendly alternative energy resources.
Solar radiation as one of the ideal clean energy resources
can solve the energy crisis but requires new initiatives to
establish cost-effective and high performance photovoltaic
cells due to the traditional crystalline silicon photovoltaic
cells endure expensive cost of manufacturing and instal-
lation [1]. Recent efforts to design semiconductor materials
with ordered nanostructure provide innovative strategies
for developing next generation energy conversion devices
[2]. In the past decade, the quantum dot-sensitized solar
cells (QDSSCs) with low-cost and tunable band gap
have drawn considerable attention and shown great pro-
mise [2–4].
The possibility of capturing hot electrons and generating
multiple charge carriers of narrow-band semiconductor
quantum dots (QDs) opens up new strategy to design solar
cells with QDs as sensitizers [5, 6]. A typical structure of
liquid junction sensitized solar cell is to use sensitizers as
light absorber to sensitize the wide band-gap TiO2 nanos-
tructured film [7]. The commonly used sensitizers in
QDSSCs are single metal chalcogenides such as CdS,
CdTe, CdSe, PbS and PbSe QDs [8–15]. In some cases, co-
sensitization system using more than one of these materials
has also been employed for QDSSCs [16, 17]. Currently,
two technologies are widely used to directly grow single or
co-sensitized QDs onto the TiO2 nanostructured film for
the QDSSCs, which includes successive ionic layer
adsorption and reaction (SILAR) and chemical bath
deposition (CBD) [13, 18, 19]. These two in situ growth
QDs onto the surface of the TiO2 nanostructured film,
which is benefit for the transfer of the photo-excited
123

electrons. However, the QDs acquired by these two
methods lack the precise control of the particle size and
crystallinity. Alternatively, the alloyed QDs, especially the
CdSxSe1-x alloyed QDs whose light absorption range is
tunable with different ratios of S and Se can be employed
to sensitize TiO2 film by the precise control of the QDs size
in QDSSCs. At room temperature, CdS and CdSe are
miscible over a wide range of compositions to form the
CdSxSe1-x (0 B x B 1) alloyed QDs due to the small lat-
tice mismatch [20]. The CdSxSe1-x alloyed QDs have
significant importance in photonics and electronics,
because it has a direct and widely modulated band gap
from 1.73 to 2.44 eV corresponding to the composition
change from CdSe to CdS. Therefore, the CdSxSe1-x
alloyed QDs could be used as sensitizer for the TiO2 film.
The main variety of synthetic methods for CdSxSe1-x
alloyed QDs can be usually classified into two groups:
preparation in organic solvents and in aqueous solution,
which differ in particular according to the capping ligand
employed [21]. For the former, the typical capping ligand
are long chain molecules, which would form a dielectric
barrier layer between QDs and TiO2, hindering the inter-
facial charge transfer at QDs/TiO2 interfaces. For the later,
the aqueous colloidal QDs are usually capped with short
chain thiol stabilizers, which are highly efficient in charge
separation at the interface of QDs and TiO2 [22, 23].
Apart from the selection of QDs, another important factor
which should be seriously considered is the influence of the
supported architectures of the TiO2 film. Recently, the highly
ordered TiO2 nanowire (NW) arrays obtained from the
hydrothermal process have been a focus of investigation in
many fields, such as photocatalysis, water photo-electrolysis,
and dye/QDs sensitized solar cells [9, 24, 25]. The TiO2 NW
arrays can be directly and compactly grown on the surface of
fluorine-doped tin dioxide) FTO glass by a facile hydrother-
mal process [26], which makes the TiO2 NW arrays a superior
nanostructure for developing light harvesting devices. In
particular, the highly ordered nanowire structure is helpful for
separating and directing electrons to the collecting electrode
surface [25]. Hence, the TiO2 nanowire arrays were employed
as the architecture to support the CdSxSe1-x alloyed QDs.
Although much work has been committing to the preparation
of alloyed QDSSCs [22, 27–29], the use of CdSxSe1-x QDs
combining TiO2 nanowire arrays has seldom been reported in
literature. Therefore, in the present study, a series of CdSx
Se1-x alloyed QDs-sensitized TiO2 NW arrays with con-
trolled composition and light harvesting ability were syn-
thesized using hydrothermal method. The composition and
band gap of the CdSxSe1-x alloyed QDs can be modulated by
varying the feed molar ratio of S:Se in precursor solution, thus
the absorption spectrum of the CdSxSe1-x sensitized TiO2
NW arrays can be easily tuned in the range of 480–670 nm
while maintaining the similar particle size. Using the
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J Mater Sci: Mater Electron
CdSxSe1-x alloyed QDs-sensitized TiO2 NW arrays as pho-
toanodes for QDSSCs, the photovoltaic performance of the
QDSSCs has been discussed.
2 Experiments
2.1 Materials
Tetrabutyl titanate (Ti(OC4H9)4, sodium chloride (NaCl),
concentrated hydrochloric acid (HCl, 35–37 wt%), sele-
nium powder (Se), sodium sulfide (Na2SO3), thiourea
(NH2CSNH2), thioglycolic acid (TGA, SHCH2COOH),
cadmium nitrate (Cd(NO3)24H2O), sulfur powder (S),
sodium sulfide (Na2S9H2O), ethanol (CH3CH2OH), ace-
tone (CH3COCH3) were purchased from Aladdin (Shang-
hai, China). The brass sheet (Cu) and fluorine-doped tin
dioxide (FTO) glass were purchased from Opvtech
(Liaoning, China). Deionized water produced by our own
department was also used as starting materials. Unless
otherwise indicated, all these materials were used directly,
without further purification.
2.2 Experimental details
2.2.1 Fabrication of TiO2 NW arrays on FTO glass
The highly ordered TiO2 NW arrays on transparent con-
ductive FTO glass were constructed by a slightly modified
hydrothermal method similar to previous report [26]. Briefly,
the mixture of deionized water (25 mL) and saturated NaCl
aqueous solution (5 mL) was added into the concentrated
hydrochloric acid (30 mL). After magnetic stirring 5 min
under ambient conditions, the tetrabutyl titanate (1 mL) was
added dropwise into the mixture solution to form the trans-
parent TiO2 precursor. Then the TiO2 precursor was trans-
ferred into a Teflon-lined stainless steel autoclave which one
piece of the pre-cleaned FTO glass has been previously
placed at an angle against the wall of the Teflon liner with the
conductive side of the FTO glass facing down. The 80 %
volume of the autoclave was filled with the TiO2 precursor
solution. Subsequently, the autoclave was sealed and placed
in electric oven to conduct the hydrothermal process at the
temperature of 150 °C for 12 h. When the reaction period
was completed, the autoclave was cooled under flowing
water, and the TiO2 NW sample was taken out, rinsed thor-
oughly with ethanol, and then dried in air.
2.2.2 Assembly of CdSxSe1-x alloyed QDs onto TiO2 NW
arrays
The assembly of CdSxSe1-x alloyed QDs onto TiO2 NW
arrays was achieved by one-step hydrothermal process
J Mater Sci: Mater Electron
according to previously reported literature [22] with slight
modification. The CdSxSe1-x precursor solution was pre-
pared by the addition of aqueous Se and S source mixture
into the Cd precursor reaction medium. Cd precursor
solution was prepared by mixing 1.2 mmol of Cd(NO3)2
and 1.2 mmol of TGA (bifunctional linker) in 25 mL of
deionized water under vigorous magnetic stirring for
5 min. The solution was first turbid due to the poor solu-
bility of the Cd-TGA complex, which could be gradually
changed to transparent by addition of NaOH solution (5 M)
into the Cd-TGA solution. The 0.1 M of Na2SeSO3 solu-
tion prepared by refluxing Se powder and Na2SO3 at 96 °C
and 0.1 M thiourea solution were used as Se and S pre-
cursors, respectively. The total amount of thiourea and
Na2SeSO3 was fixed at 0.36 mmol, and the feed molar
ratios of thiourea to Na2SeSO3 (S:Se) were varied from
0:4, 1:3, 2:2 and 3:1–4:0, respectively. The 3.6 mL of the
mixture of Se and S source was added to the Cd-TGA
reaction medium. Subsequently, the mixed precursor
solution was transferred into Teflon-lined stainless auto-
clave in which the TiO2 NW sample was previously placed.
The 80 % volume of the autoclave was filled with the
mixed precursor solution. Then the autoclave was sealed
and placed in an electric oven to conduct a hydrothermal
process at 150 °C for 18 h to complete the growth and
assembly of CdSxSe1-x alloyed QDs on the TiO2 NW
arrays. Finally the autoclave was cooled to room temper-
ature, and the CdSxSe1-x sensitized TiO2 NW arrays
(CdsxSe1-x/TiO2 NW) electrodes were taken out and
washed with ethanol, then dried in air.
2.2.3 Fabrication of counter electrode
Cu2S formed on a brass sheet was employed as counter
electrode for CdSxSe1-x/TiO2 NW QDSSCs. Brass sheet
(0.3 mm thick) was initially immersed in HCl solution at
70 °C for 15 min to expose more copper. Then the brass
sheet was washed with deionized water and dried by air
gun. The polysulfide solution containing 1 M sodium sul-
fide and 1 M sulfur in deionized water was dropped on the
surface of the brass sheet, leading to the formation of black
Cu2S.
For the photovoltaic applications, the prepared CdSx
Se1-x/TiO2 NW photoanodes were assembled with Cu2S
counter electrode in a fashion similar to sandwich. The
space between the two electrodes was filled with polysul-
fide electrolyte as holes scavenger which was consisted of
1 M sodium sulfide and 1 M sulfur aqueous solution.
2.3 Characterization
Field-emission scanning electron microscopy (FESEM)
and transmission electron microscopy (TEM) were carried
out with a Hatachi S-4200 field emission SEM and a
Tecnai G2 F20 TEM, respectively. The crystalline nature
and structure of the samples were analyzed by X-ray
diffraction (XRD, D/MAX-2400, Rigaku) using a Cu Ka
source operated at 40 kV and 30 mA with scanning rate of
4° min-1. The optical absorption of the samples was
recorded using a UV2501PC (SHIMADZU) spectrometer
with an ISR-2200 integrating sphere attachment for diffuse
reflection measurement.
The photocurrent density–voltage (J–V) characteristics
the QDSSCs were conducted under an illumination of a
solar simulator at one sun (AM1.5, 100 mW cm-2), which
was calibrated by standard silicon solar cell. The incident
photon-to-current conversion efficiency (IPCE) was mea-
sured as a function of wavelength from 300 to 800 nm by
employing a 150 W Xe lamp coupled with a computer-
controlled monochromator. A mask with exposure area of
0.25 cm2 was used to cover on the photoanodes when
conducting photovoltaic measurement.
3 Results and discussion
Figure 1a, b present the SEM top-surface images of a
typical as-synthesized TiO2 NW arrays at low and high
magnification, respectively. It can be seen that a highly
ordered and densely packed array of nanowires are uni-
formly grown on the surface of FTO glass in Fig. 1a.
Figure 1b clearly demonstrated that the tops of the nano-
wires possess flat tetragonal crystallographic planes. Fur-
thermore, it can be identified that the lateral dimension, or
width, of the square nanowire lies in the range of
80–130 nm.
Figure 1c is a cross-sectional view of the as-synthesized
TiO2 NW arrays, showing that the nanowires grow almost
perpendicularly from the surface of the FTO glass and the
length of the nanowires are around 2–3 lm. Moreover, a
certain space among the nanowires can be easily observed,
which can provide enough space for the penetration of the
precursor solution to form CdSxSe1-x alloyed QDs. Fig-
ure 1d presents the energy dispersive X-ray (EDX) spec-
trum of the as-synthesized TiO2 NW arrays. Apparently,
the Ti and O are dominant elements in the EDX spectrum,
which indicates that the synthesized nanowire arrays are
composed of TiO2. Other elements are also shown in this
EDX spectrum, but they are in a relatively low level.
Among them, C and N may come from the sample plat-
form, Si and Sn may come from the FTO glass.
The CdSxSe1-x alloyed QDs were assembled onto the
TiO2 NW arrays by a facile hydrothermal process using
TGA as bifunctional molecular linker. Figure 2a and b
shows the top morphology of the CdSxSe1-x sensitized
TiO2 NW arrays (defined as CdSxSe1-x/TiO2 NW)
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Fig. 1 a Top morphology of the TiO2 NW arrays at low magnification, b top morphology of the TiO2 NW arrays at high magnification, c the
cross-section view of the TiO2 NW arrays, d the EDX spectrum of the TiO2 NW arrays
prepared with feed molar ratio of S:Se = 2:2 at low and
high magnification, respectively. Obviously, the CdSx
Se1-x/TiO2 NW arrays have an increased width than and
rougher surface than that of the bare TiO2 NW arrays.
Especially, the surface of the TiO2 NW were covered with
an amount of small nanoparticles as shown in Fig. 2b,
implying that the successful assembly of CdSxSe1-x QDs
onto the TiO2 NW arrays. Figure 2c is the cross-sectional
view of the CdSxSe1-x/TiO2 NW arrays, displaying that the
TiO2 NW arrays became rougher than the bare TiO2 NW in
Fig. 1c after the assembly of CdSxSe1-x QDs. The inset of
Fig. 2c is the local magnified image of the CdSxSe1-x/TiO2
NW arrays cross-sectional view. Clearly, the small
nanoparticles which are composed of CdSxSe1-x QDs can
be observed on the surface of the TiO2 NW walls. In
addition, the ordered nanowire structure still exists and
remains almost perpendicular to the surface of FTO glass,
suggesting that the formation process of CdSxSe1-x alloyed
QDs would not damage the highly ordered TiO2 NW
arrays. Figure 2d shows the EDX spectrum of the CdSx
Se1-x/TiO2 NW arrays prepared with feed molar ratio of
S:Se = 2:2. Apart from Ti and O elements, the appearance
of characteristic peaks of Cd, S and Se elements in the
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J Mater Sci: Mater Electron
EDX spectrum has demonstrated that the CdSxSe1-x
alloyed QDs can be successfully assembled on to the TiO2
NW arrays by hydrothermal process.
The formation of the CdSxSe1-x/TiO2 NW arrays can be
illustrated in Fig. 3. As is shown, with the assistance of
TGA, the CdSxSe1-x alloyed QDs can be assembled onto
the TiO2 NW arrays. Two reasons determine the TGA a
perfect candidate of molecular linker to tether colloidal
QDs to TiO2. Firstly, TiO2 has a strong affinity for the
carboxylate group of the linker molecules, as demonstrated
previously with a variety of sensitizing dyes [30, 31].
Secondly, thiol group of TGA can bind strongly to CdSx
Se1-x QDs through surface Cd2? cations [21, 32]. By
immersing the TiO2 NW arrays in precursor solution, the
CdSxSe1-x precursor solution will penetrate into the space
of the TiO2 nanowires and bind chemically to the TiO2
surface with the assistance of the TGA linker. During the
hydrothermal process, the formation and crystallization of
the CdSxSe1-x alloyed QDs will be completed. The
CdSxSe1-x alloyed QDs would be easier to access more
surface of the TiO2 NW than the pre-synthesized colloidal
QDs owning to the ion-scale dimension of the CdSxSe1-x
QDs precursor favors their easy diffusion within the porous
J Mater Sci: Mater Electron

Fig. 2 a Top morphology of

CdSxSe1-x/TiO2 NW arrays,
b the magnified SEM image of
the CdSxSe1-x/TiO2 NW arrays,
c the cross-sectional view of the
CdSxSe1-x/TiO2 NW arrays, the
inset is local magnified image,
d the EDX spectrum of the
CdSxSe1-x/TiO2 NW arrays.
The sample was prepared with
feed molar ratio of S:Se = 2:2

Fig. 3 The illustration for the

formation of CdSxSe1-x/TiO2
NW arrays by hydrothermal
process with TGA as
bifunctional linker

of TiO2 NW arrays. Therefore, this hydrothermal method is
helpful to assemble of well-covering CdSxSe1-x QDs on
the surface of TiO2 NW.
The TiO2 NW, CdSxSe1-x and CdSxSe1-x/TiO2 NW
were further investigated using TEM. Figure 4a provides
the TEM image of the bare TiO2 NW and its corresponding
selected-area electron diffraction (SAED) patterns, indi-
cating that the TiO2 NW arrays are single crystalline.
Figure 4b presents the TEM image of the CdSxSe1-x/TiO2
NW. Obviously, the observation of CdSxSe1-x alloyed
QDs layer on TiO2 NW clearly shows the successful
assemble of the alloyed QDs by hydrothermal process. The
inset of Fig. 4b is the SAED pattern of the CdSxSe1-x/TiO2
NW, apart from the well-aligned spots which come from
the single-crystalline TiO2 NW, the appearance of
diffraction rings in this SAED pattern implies that the
polycrystalline of CdSxSe1-x has been formed on the TiO2
NW.
Figure 4c shows the typical HRTEM image of the
CdSxSe1-x alloyed QDs prepared with feed molar ratio of

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Fig. 4 a The TEM image of
TiO2 NW and its corresponding
SAED pattern, b the TEM
image of CdSxSe1-x/TiO2 NW
and its corresponding SAED
pattern, c the TEM image of
CdSxSe1-x alloyed QDs, d the
HRTEM image of CdSxSe1-x/
TiO2 NW. The TEM samples
were prepared with feed molar
ratio of S:Se = 0:4
S:Se = 0:4. The hydrothermally synthesized CdSxSe1-x
alloyed QDs display a size distribution around 5 nm.
Moreover, the observed lattice spacing of 0.35 and 0.23 nm
could be ascribed to the (111) and (220) planes of CdSx
Se1-x, respectively. Figure 4d provides the HRTEM image
of the CdSxSe1-x/TiO2 NW. The lattice spacing of 0.33 nm
corresponds to the (110) plane of rutile TiO2, confirming
that the supporter of the QDs is TiO2. In addition, the (111)
and (220) planes of CdSxSe1-x could also be discerned
close to the crystalline edge of TiO2 NW. The results of
HRTEM images further evidenced the successful assembly
of CdSxSe1-x alloyed QDs on TiO2 NW by hydrothermal
process.
The EDX spectra and their corresponding data were
used to estimate the x values of the CdSxSe1-x alloyed
QDs, which are shown in the supplementary materials with
Fig. S1. It should be noted that the calculated results is only
used to provide an approximate x value to understand the
composition of the CdSxSe1-x QDs due to the EDX is only
suitable for semi-quantitative analysis. Before EDX anal-
ysis, the CdSxSe1-x QDs samples have been repeatedly
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J Mater Sci: Mater Electron
precipitated with isopronanol and resuspended in aqueous
solution for five times to reduce the influence of the
excessive TGA. According to the EDX quantitative data of
the CdSxSe1-x elemental content, the component of the
CdSxSe1-x QDs synthesized with S:Se = 0:4, 1:3, 2:2, 3:1
and 4:0 are approximately calculated to be CdS0.27Se0.73,
CdS0.43Se0.57, CdS0.69Se0.31, CdS0.86Se0.14 and CdS1Se0
(approximate to real values), respectively. The composition
of CdSxSe1-x alloyed QDs obtained with different feed
molar ratio of S:Se is listed in Table 1. Figure 5 presents
the relative amount of S in product versus the relative
amount of S in precursor solution. It can be found that an
obvious deviation is between the S/(S ? Se) ratio in the
obtained CdSxSe1-x QDs and the S/(S ? Se) ratio in the
precursor solution. This deviation of S/(S ? Se) between
product and precursor solution indicates that the decom-
position of TGA during hydrothermal process can provide
additional S source to be involved in the synthesis of
CdSxSe1-x QDs, which is evidenced by the formation of
CdS0.27Se0.73 alloyed QDs without adding any S source in
the precursor solution.
J Mater Sci: Mater Electron

Table 1 Composition of
Feed molar ratio of S:Se S/(S ? Se) in products (%) Composition of CdSxSe1-x
CdSxSe1-x alloyed QDs
synthesized with different feed 0:4 27 CdS0.27Se0.73
molar ratio of S:Se
1:3 43 CdS0.43Se0.57
2:2 69 CdS0.69Se0.31
3:1 86 CdS0.86Se0.14
4:0 100 CdS1Se0

Fig. 5 Relation of the relative amount of S in the CdSxSe1-x alloyed

QDs versus the relative amount of S in the precursor solution

Figure 6a shows the XRD pattern of the as-synthesized

TiO2 NW arrays and the XRD pattern of bare FTO glass,
respectively. Apparently, only the rutile structure of SnO2
(JCPDS # 41-1445) can be indexed in the XRD pattern of
the bare FTO glass. After the hydrothermal process, the
XRD pattern of as-synthesized TiO2 NW arrays shows a
tetragonal rutile TiO2 structure (JCPDS # 21-1276), indi-
cating the successful growth of TiO2 NW arrays. The
formation of TiO2 NW arrays on the FTO glass surface can
be ascribed to the small lattice mismatch between FTO and
rutile TiO2, which could promote the epitaxial nucleation
of TiO2 on the surface of FTO glass [33].
Figure 6b depicts the XRD patterns of the CdSxSe1-x
alloyed QDs prepared with different feed molar ratios of Fig. 6 a The XRD patterns of bare FTO glass and as-synthesized
TiO2 NW arrays, b the XRD patterns of the CdSxSe1-x alloyed QDs
S:Se, which were precipitated from aqueous solution with prepared with different feed molar ratio of S:Se
an excess of 2-propanol. With the purpose of comparison,
the standard XRD patterns of cubic CdS (JCPDS # the diffraction peaks of CdS1Se0 (obtained with feed molar
10-0454) and CdSe (JCPDS # 19-0191) are provided. From ratio of S:Se = 4:0) are positioned well with the standard
the XRD patterns, it can be found that all the CdSxSe1-x XRD of cubic CdS. The diffraction peaks of the CdSxSe1-x
alloyed QDs possess a cubic crystal structure, as indicated alloyed QDs are gradually shifted to lower angle with
by the lack of diffraction peaks of (102) and (103) planes, increasing Se feed amount in precursor solution. A dashed
which are characteristic of a hexagonal crystal structure line has been included in Fig. 6b to guide the eye.
[22, 34]. Furthermore, it should be noted that the diffrac- According to Bragg’s law, such downshift of peak position
tion peaks of the CdSxSe1-x alloyed QDs are located indicates an increase in lattice parameter, which is caused
between that of the cubic CdS and CdSe phases, except that by the difference in ionic radius between S and Se.

123

Interestingly, the diffraction peaks of CdS0.27Se0.73 pre-
pared with feed molar ratio of S:Se = 0:4 shift slightly
toward higher angles compared with standard XRD of
cubic CdSe. This phenomenon is caused by the pyrolysis of
TGA during hydrothermal reaction which can generate the
sulfur element to take part in the formation of CdS0.27
Se0.73. More sulfur element incorporated further proves
that the TGA linker can act as the source of sulfur, sup-
plying sulfur monomers to form the CdSxSe1-x alloyed
QDs. The XRD results of the CdSxSe1-x alloyed QDs
demonstrate that the homogeneous formation of alloy
rather than a simple physical mixture of CdS and CdSe due
to the superposition of the reflections from pure CdS and
pure CdSe have not shown in the XRD patterns [20].
The current density–voltage (J–V) performance curves
of the solar cells, which were assembled with CdSxSe1-x/
TiO2 NW photoanodes, Cu2S counter electrodes and
electrolyte based on mixture of 1 M sodium sulfide and
1 M sulfur aqueous solution, are shown in Fig. 7. The
photovoltaic parameters of the CdSxSe1-x/TiO2 NW solar
cells including short circuit current density (Jsc), open
circuit voltage (Voc), fill factor (FF) and power conversion
efficiency (PCE) are also summarized in Table 2. For the
assembled solar cells, the photovoltaic parameters show an
apparent dependence on composition of the CdSxSe1-x
alloyed QDs. The CdS1Se0/TiO2 NW solar cell prepared
with feed molar ratio of S:Se = 4:0 exhibits a Jsc of
4.38 mA cm-2, a Voc of 0.34 V and a FF of 0.36, yielding
a PCE of 0.54 %. With increasing Se content in the
CdSxSe1-x alloyed QDs, the photovoltaic performance of
the CdSxSe1-x/TiO2 NW solar cells are gradually
enhanced. The CdS0.27Se0.73/TiO2 NW solar cell prepared
with feed molar ratio of S:Se = 0:4 shows a Jsc of
Fig. 7 Current density–voltage (J–V) characteristics of solar cells
based on the CdSxSe1-x/TiO2 NW photoanodes prepared with
different feed molar ratio of S:Se
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J Mater Sci: Mater Electron
Table 2 Photovoltaic parameters obtained from the J–V curves using
CdSxSe1-x/TiO2 NW solar cells prepared with different feed molar
ratio of S:Se
Composition Voc (V) Jsc (mA cm-2) FF PCE (%)
CdS1Se0 0.34 4.38 0.36 0.54
CdS0.86Se0.14 0.32 9.26 0.45 1.33
CdS0.69Se0.31 0.35 11.31 0.44 1.74
CdS0.43Se0.57 0.41 12.64 0.42 2.18
CdS0.27Se0.73 0.41 14.62 0.41 2.46
14.62 mA cm-2, a Voc of 0.41 V and a FF of 0.41, pro-
ducing the highest PCE of 2.46 % among the CdSxSe1-x/
TiO2 NW solar cells. The highly improved photovoltaic
performance of the solar cells based on different CdSx
Se1-x/TiO2 NW photoanodes mainly results from the
increase of Jsc which could be attributed to a wider range
absorption of light, a more effective generation of pho-
toexcited electrons, and a more efficient charge separation
efficiency. The specific reasons responsible for the
enhanced photovoltaic performance will be further dis-
cussed later.
Compared with the CdS1Se0/TiO2 NW solar cell, the
solar cells based on CdSxSe1-x/TiO2 NW photoanodes
with different composition possess an improved photo-
electric conversion efficiency due to a broader absorption
of visible light as the increase of Se content in CdSxSe1-x
alloyed QDs. Figure 8a shows the UV–Vis absorption
spectra of the bare TiO2 NW, CdS1Se0/TIO2 NW,
CdS0.86Se0.14/TiO2 NW, CdS0.69Se0.31/TiO2 NW, CdS0.43
Se0.57/TiO2 NW and CdS0.27Se0.73/TiO2 NW photoanodes,
respectively. Their corresponding photographs are also
presented in Fig. 8b, which shows that all the photoanodes
have a homogeneous color distribution across the surface,
implying the formation of CdSxSe1-x alloyed QDs. As
shown in Fig. 8a, the bare TiO2 NW exhibits an absorption
onset at around 390 nm, and its main absorption range
centered on ultraviolet light region. After decoration with
CdS1Se0 QDs, the absorption onset of the CdS1Se0/TiO2
NW red-shifted to around 480 nm, corresponding to the
band gap of 2.58 eV, which is higher than the band gap of
CdS in bulk (2.25 eV), indicating that the CdS1Se0 parti-
cles assembled on TiO2 NW are within the scale of QDs.
Further expanded absorption onset in the visible light
region is demonstrated upon the formation of CdSxSe1-x
alloyed QDs. As the increase of Se relative atomic ratio in
the CdSxSe1-x alloyed QDs, the absorption onset of the
photoanodes is gradually red-shifted to around 535 nm
(CdS0.86Se0.14/TiO2 NW), 580 nm (CdS0.69Se0.31/TiO2
NW), 635 nm (CdS0.43Se0.57/TiO2 NW) and 670 nm
(CdS0.27Se0.73/TiO2 NW), corresponding the band gap of
2.32, 2.14, 1.95 and 1.85, respectively. This enlarged
J Mater Sci: Mater Electron

Fig. 8 a The UV–visible absorption spectra obtained with bare TiO2 NW arrays and CdSxSe1-x/TiO2 NW photoanodes, b the photographs of
the bare TiO2 NW and CdSxSe1-x/TiO2 NW photoanodes

absorption range in visible light region indicates that the

Se-rich composition of CdSxSe1-x alloyed QDs amplify
the photon absorption at the longer wavelength, which
means more photons can be involved in the generation of
photoexcited electrons, resulting in an enhanced light
harvesting efficiency.
The highest Jsc of 14.62 mA cm-2 acquired from
CdS0.27Se0.73/TiO2 NW solar cell can be attributed to the
enlarged absorption range in visible light region. Here, Jsc
is determined by the following equation:
Jsc ¼ qglh ging gcc Io ð1Þ

where q is the elementary charge, Io is the incident photon

flux of light (6.6 9 1016 cm-2 S-1), glh is the light har-
vesting efficiency, ging is the charge injection efficiency
and gcc is the charge collection efficiency [35]. As the
absorption spectra displayed in Fig. 8a, the increase of Se
content in CdSxSe1-x alloyed QDs significantly broadens
the visible light absorption range, which drastically
enhance the glh of the CdS0.27Se0.73/TiO2 NW solar cell,
thus leading to the increment of Jsc.
The IPCE spectra was recorded to compare the pho-
toresponse of CdSxSe1-x/TiO2 NW photoanodes (prepared
with different feed molar ratio of S:Se), which is shown in
Fig. 9. Comparison of these IPCE spectra yields two
interesting observations. The first one is that the photore-
sponse range of these photoanodes can be modulated by
varying composition of S and Se in CdSxSe1-x alloyed
QDs. Similarities between the IPCE spectra and the UV–
Vis absorption spectra confirm the excitation of the CdSx
Se1-x alloyed QDs as the primary event are responsible for
the photocurrent generation. The onset of photocurrent
response gradually shifted to the red region with increasing
Se content in CdSxSe1-x alloyed QDs, which is in agree-
ment with the enlarged absorption at longer wavelengths.
This results further confirm that the light harvesting
Fig. 9 The incident photo-to-current conversion efficiency (IPCE)
spectra of solar cells based on various CdSxSe1-x/TiO2 NW
photoanodes prepared with different feed molar ratio of S:Se
efficiency could be improved by forming Se-rich CdSx-
Se1-x/TiO2 NW photoanodes. The second one is that the
maximum IPCE for different CdSxSe1-x/TiO2 NW pho-
toanode gradually enhanced with the increment of Se
content in CdSxSe1-x alloyed QDs. As a result, the maxi-
mum IPCE increased from 27 % for CdS1Se0/TiO2 NW
photoanode to 53 % for CdS0.27Se0.73/TiO2 NW photoan-
ode. The highest IPCE of 53 % with photocurrent response
onset around 670 nm, which obtained by the CdS0.27Se0.73/
TiO2 NW photoanode, highlights the contribution to the
significant enhancement of Jsc by forming Se-rich CdSx
Se1-x alloyed QDs.
It is well-known that the architecture of TiO2 has an
important effect on the charge separation efficiency, which
can influence Jsc of QDSSCs. Figure 10 shows the photo-
electrical conversion configuration of CdSxSe1-x/TiO2 NW
solar cells. Under irradiation of light, photons are captured

123

Fig. 10 Schematic diagram of the photoelectrical conversion struc-
ture of our CdSxSe1-x/TiO2 NW solar cell
by CdSxSe1-x alloyed QDs, producing electron–hole pairs.
With the assistance of highly ordered TiO2 NW arrays, the
electrons are rapidly separated from holes. Simultaneously,
the remaining holes are scavenged to the Cu2S counter
electrode via a hole transporting redox couple comprising
of polysulfide electrolyte. According to this working
mechanism of the CdSxSe1-x/TiO2 NW solar cell, it can be
seen that the highly ordered TiO2 NW arrays can offer a
direct transport channel for photogenerated electrons to
reduce the recombination between electrons and holes,
which will be beneficial to the enhancement of charge
separation efficiency and improvement of Jsc, resulting in
the enhancement of PCE to 2.46 % for CdS0.27Se0.73/TiO2
NW solar cells.
4 Conclusions
In conclusion, CdSxSe1-x alloyed QDs are successfully
synthesized directly in aqueous solution and simultane-
ously assembled on highly ordered TiO2 NW arrays
to form CdSxSe1-x/TiO2 NW photoanodes via facile
hydrothermal process. The light absorption range of
CdSxSe1-x/TiO2 NW photoanodes is tunable by varying
the feed molar ratio of S source to Se source in precursor
solution. The absorption range of these photoanodes can be
gradually enlarged from 480 nm to 670 nm as the forma-
tion of Se-rich CdSxSe1-x/TiO2 NW photoanodes. Based
on these CdSxSe1-x/TiO2 NW photoanodes, we assembled
the solar cells and investigated their photovoltaic perfor-
mance. The power conversion efficiency of CdSxSe1-x/
TiO2 NW solar cells exhibits a gradual enhancement as the
increase of Se content in CdSxSe1-x alloyed QDs. The
CdS0.27Se0.73/TiO2 NW solar cell shows the power con-
version efficiency up to 2.46 %, which is the maximum
among these sample CdSxSe1-x/TiO2 NW solar cells.
Further investigation demonstrate that the enlarged light
absorption range caused by the formation of Se-rich
CdSxSe1-x QDs and the improved charge separation are
responsible for the significant increase of Jsc, finally lead-
ing to the enhancement of the power conversion efficiency
123
J Mater Sci: Mater Electron
of the CdS0.27Se0.73/TiO2 NW solar cell. This flexibility of
tailoring optical properties of semiconductor materials by
hydrothermal technique makes it a very promising syn-
thetic approach for preparation of TiO2 nanowire-based
heterostructures with custom-designed properties for
photo-electrochemical applications.
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