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Bandgap-graded ZnO/(CdS)1x (ZnS) x coaxial nanowire arrays for semiconductorsensitized solar cells

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2014 Mater. Res. Express 1 015021
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Bandgap-graded ZnO/(CdS)1x(ZnS)x coaxial

nanowire arrays for semiconductor-sensitized solar
cells
Liang Chu, Luying Li, Waqar Ahmad, Zhen Wang, Xianli Xie, Jiangyu Rao,
Nishuang Liu, Jun Su and Yihua Gao
Center for Nanoscale Characterization & Devices (CNCD), Wuhan National Laboratory for
Optoelectronics (WNLO)-School of Physics, Huazhong University of Science and Technology
(HUST), Wuhan 430074, Peoples Republic of China
E-mail: gaoyihua@hust.edu.cn
Received 24 October 2013, revised 16 December 2013
Accepted for publication 31 December 2013
Published 31 January 2014
Materials Research Express 1 (2014) 015021
doi:10.1088/2053-1591/1/1/015021

Abstract

Bandgap-graded ZnO/(CdS)1x(ZnS)x (0 x 1) coaxial nanowire arrays on

transparent conducting oxide substrates have been successfully fabricated by a
facile two-step-approach, combining hydrothermal method and successive ion
exchange reactions. Energy-dispersive x-ray spectroscopy elemental analysis
suggests that the shells are composed of (CdS)1x(ZnS)x double-layer structures,
which are thoroughly and tightly synthesized on the ZnO cores, and play the role
of sensitizers. The as-prepared ZnO/(CdS)1x(ZnS)x coaxial nanowire arrays are
demonstrated to be controllably adjusted in their optical absorption from ultraviolet to green via compositional effect, and are promising electrodes for
semiconductor-sensitized solar cells. The photoelectrode based on the ZnO/CdS
coaxial nanowire array shows good performance with power conversion efciency of 2.093%, a short-circuit current density 7.733 mA cm2, and an opencircuit voltage 0.536 V.
S Online supplementary data available from stacks.iop.org/MRX/1/015021/
mmedia
Keywords: bandgap grading, ion exchange reaction, coaxial nanowire arrays,
semiconductor-sensitized solar cells

Materials Research Express 1 (2014) 015021

2053-1591/14/015021+12$33.00

2014 IOP Publishing Ltd

Mater. Res. Express 1 (2014) 015021

L Chu et al

1. Introduction

Bandgap grading has attracted considerable attention for several decades for tuning electric and
optoelectronic properties of semiconductors in optoelectronic devices [13]. Particularly,
bandgap grading in one-dimensional semiconductor nanostructures show tremendous promise
as direct pathways for charge transport. Furthermore, one-dimensional coaxial nanowires are
extensively studied since the corresponding bandgap can be easily modulated by the shell size
and composition of the systems. Therefore, these nanostructures have found remarkable
applications in solar cells [4, 5], light-emitting diodes [6], eld-effect transistors [7], and
photodetectors [8].
Semiconductor-sensitized solar cells (SSSCs) serve as promising alternatives to dyesensitized solar cells (DSSCs). Semiconductors are a great substitute for the dye molecules as
photon-absorbing material due to some special advantages: easy bandgap-tailoring by the
quantum connement effect [9], a large extinction coefcient from quantum connement and
large intrinsic dipole moments [10], multiple exciton generation from one single photon due to
impact ionization [11], high theoretical power conversion efciency (PCE) of 44% [12], etc.
However, the PCE of SSSCs is typically lower than that of DSSCs. The low performances of
SSSCs are mainly attributed to low quantum-dot loading density [13, 14], low adhesion
between the semiconductors and photoanodes [15], aggregation [16], interface defect states
[17], and so on. Coreshell nanowire-array-structures as photoanodes and sensitizers for SSSCs
are reported, where the shells can be thoroughly deposited on the core by the successive ionic
layer adsorption and reaction deposition method [18, 19]. However, the adhesion force between
the core and shell is not strong, and the sensitizers may easily peel off the photoanodes.
ZnO (Eg = 3.37 eV) is an interesting photoanode material due to its superior properties
such as comparable energy band structure to TiO2 (Eg = 3.2 eV), high electron mobility, huge
exciton binding energy and simple surface transformation. The surface layer of ZnO nanowires
can be replaced with the corresponding anion and cation via ion exchange reactions for the
comparatively large solubility product constant of ZnO (6.8 1017). For ZnO/(CdS)1x(ZnS)x
(0 x 1) coaxial nanowire arrays, (CdS)1x(ZnS)x (0 < x 1) can act as the sensitizer and the
its bandgap may be graded between 2.4 eV (CdS) [20] and 3.62 eV (ZnS) [21]. Moreover,
because the formation of ZnS and CdS is fullled by the substitution of S on O sites in ZnO and
Cd on Zn sites in ZnS, respectively, the bindings between different layers are relatively tighter
than those directly grown layers. From the above perspective, the ZnO/(CdS)1x(ZnS)x
(0 x 1) coaxial nanowire arrays could realize bandgap grading and tightly bound layers.
In the present work, we prepare ZnO/(CdS)1x(ZnS)x coaxial nanowire arrays via ion
exchange reactions to fabricate SSSCs. The optical absorption of the arrays can be controllably
tuned to cover the optical range from ultraviolet to green via compositional effect. These coaxial
nanowire arrays were demonstrated as photoelectrodes for SSSCs, showing excellent
performance under AM 1.5 irradiation (100 mW cm2).
2. Experimental procedure
2.1. Synthesis of ZnO nanowire arrays

ZnO nanowire arrays were directly assembled on uorine-doped tin oxide (FTO, ~7 cm2)
substrates by a seed-assisted hydrothermal method. The FTO glasses were initially washed with
2

Mater. Res. Express 1 (2014) 015021

L Chu et al

laundry soap and sonicated in acetone, ethanol, and deionized water for 20 min, respectively.
After drying under nitrogen stream, the cleaned FTO substrates were deposited with the
solution containing 0.6 M zinc acetate (Zn(CH3COO)2, 99.5%) and 0.6 M diethanolamine
(DEA, 98%) in ethanol by spin coating at 2000 rpm for 30 s [22]. Then, the coated substrates
were annealed in a mufe furnace under air condition at 400 C for 0.5 h to form a seed layer of
ZnO nanoparticles. Afterward, the seeded-FTO substrates were immersed into a glass bottle,
wherein there was 80 ml reaction solution containing 20 mM zinc nitrate hexahydrate (Zn
(NO3)3 6H2O, 99%), 20 mM hexamethylenetetramine ((CH2)6N4, 99%), and 3.5 ml
ammonia solaution (NH3, 25 ~ 28 wt%). The seeded-FTO substrates were suspended face-down
in the aqueous and heated at 95 C for 12 h. Finally, the substrates with ZnO nanowire arrays
were rinsed with deionized water several times to remove the residuals and dried at 80 C.
2.2. Synthesis of ZnO/ZnS coaxial nanowire arrays

Anion exchange reactions were adopted to fabricate ZnO/ZnS coaxial nanowire arrays based on
as-synthesized ZnO nanowire arrays. ZnO nanowire arrays on FTO substrates were immersed
into 50 mM thiacetamide (99%) aqueous solution at 90 C for 3.5 h in an oven. The nal
substrates were washed with deionized water for several times to eliminate the impurities and
dried at 80 C.
2.3. Synthesis of ZnO/(CdS)1x(ZnS)x coaxial nanowire arrays

Cation exchange reaction was adopted to fabricate ZnO/(CdS)1x(ZnS)x coaxial nanowire arrays
based on as-synthesized ZnO/ZnS coaxial nanowire arrays. The substrates with ZnO/ZnS
coaxial nanowire arrays were immersed into 50 mM cadmium chloride (CdCl2, 99%) aqueous
solution at different temperatures (50 C, 90 C, 140 C) for 12 h. The nal substrates were
washed with deionized water several times and dried in air. For stoichiometric analysis, (CdS)1
x(ZnS)x shells were obtained by immersing the as-products into 5 w% acetic acid solution for
about 0.5 h to remove the ZnO cores.
2.4. Fabrication of SSSCs

For SSSCs application, Pt counter electrodes were deposited by magnetron sputtering on a

precleaned FTO substrate. The substrate with ZnO/(CdS)1x(ZnS)x (50 C, 90 C and 140 C)
coaxial nanowire arrays as electrodes and Pt as counter electrodes were separated by a
polypropylene spacer, and the internal space of the cells was injected with liquid electrolyte,
which was composed of 0.6 M 1-methyl-3-propylimidazolium iodide (PMII, Alfa), 0.05 M LiI
(Alfa, >99.99%), 0.03 M I2 (Alfa, >99.999%), 0.1 M guanidinium thiocyanate (GuSCN,
>98%), and 0.5 M tert-butylpyridine (TBP) in acetonitrile and valeronitrile (V: V = 85 : 15). The
active area of the solar cell was 0.15 cm2 with a mask.
3. Measurement and characterization

The crystal structure and chemical information of the as-prepared samples were characterized
by x-ray diffraction (XRD, PANalytical B.V. The Netherlands) with Cu Ka radiation, scanning
electron microscope (FESEM, FEI NOVA NanoSEM 450), transmission electron microscope
(TEM, FEI Tecnai G2 20 UTwin), and Probe corrected transmission electron microscope (FEI
3

Mater. Res. Express 1 (2014) 015021

L Chu et al

Titan G2 60300). Absorption spectra were recorded with a UV-Vis absorption spectrometer
(UV-2550, Shimadzu). The current densityvoltage curves were studied under AM 1.5 G
(100 mW cm2, calibrated with a Si photodiode) using a solar simulator illumination (Newport,
USA) and an Autolab electrochemic workstation (modelAUT84315, The Netherlands).

4. Results and discussion

The solubility product constant of ZnO, Ksp = 6.8 1017, is much larger than those of ZnS
(2 1025) and CdS (8 1028), which implies that the ZnO nanowire arrays can be used as
sacricial templates to synthesize more stable ZnS by anion exchange. The latter could further
be converted into CdS nanostructure by cation exchange to form ZnO/CdS coaxial nanowire
arrays. The formation of ZnO/(CdS)1x(ZnS)x coaxial nanowire arrays is illustrated by a
schematic diagram as shown in gure 1. Herein, ZnO/(CdS)1x(ZnS)x coaxial nanowire arrays
were prepared by surface suldization of ZnO nanowires with S2 ions from thiacetamide
hydrolyzes to form ZnO/ZnS core/shell nanostructure, followed by partial conversion of the asobtained ZnS shell to CdS through ion replacement of Zn2+ by Cd2+ at different temperatures
(50 C, 90 C and 140 C).
X-ray diffraction (XRD) measurement was employed to characterize phase purity and
structures of the as-synthesized ZnO nanowire arrays, ZnO/ZnS coaxial nanowire arrays, and
ZnO/(CdS)1x(ZnS)x coaxial nanowire arrays grown at 50 C, 90 C and 140 C, as shown in
gure 2. The diffraction peaks of pure ZnO nanowire arrays can be indexed as (100), (002),
(101), (102), (110) and (103) (marked as green) of the wurtzite ZnO phase, respectively
(PCPDFWIN le No.80-0075). The predominant (002) peak suggests that the ZnO nanowires
mostly grow along their c-axes [23]. The XRD spectrum taken from the ZnO/ZnS coaxial
nanowires exhibit additional diffraction peaks marked by the dotted red lines corresponding to
(104) and (205) planes of the wurtzite ZnS structure (PCPDFWIN le No. 72-0162), which
conrms the formation of ZnS. However, the data from the ZnO/(CdS)1x(ZnS)x coaxial
nanowire arrays grown at 140 C doesnt show any obvious peaks of ZnS, which may
preliminarily indicate that the ZnS shell has been thoroughly converted into CdS. If the reaction
temperature is 130 C for exchange of Cd, there are also ZnS peaks in XRD data (gure S1 in
the supplementary data available from stacks.iop.org/MRX/1/015021/mmedia). The analysis of
ZnO/CdS nanowires show that the diffraction peaks marked by the triangles can be indexed as
the (100), (002), (101), (110) and (112) planes, respectively, of the wurtzite CdS phase
(PCPDFWIN le No.77-2306), demonstrating the existence of CdS.
Figure 3(a) shows a typical scanning electron microscopy (SEM) image of ZnO nanowire
array at cross-sectional view, which illustrates that the length of the ZnO nanowire array is
estimated to be about 11.5 m. Figures 3(b)(f) shows the evolution of the ZnO/(CdS)1x(ZnS)x
coaxial nanowire arrays, whose surface becomes rougher with increasing temperature. A layer
of nanoparticles is uniformly and compactly covered on the surface of ZnO nanowires as shown
in gure 3(f).
The structures of the ZnO/(CdS)1x(ZnS)x coaxial nanowires were further characterized by
conventional transmission electron microscopy (TEM), high-resolution transmission electron
microscopy (HRTEM) as well as energy-dispersive x-ray spectroscopy (EDS) techniques, as
shown in gure 4. Figure 4(a) shows a ZnO nanowire, with corresponding selected area electron
diffraction (SAED) pattern as an inset. The lattice spacing of 0.26 nm in the HRTEM image
4

Mater. Res. Express 1 (2014) 015021

L Chu et al

Figure 1. Schematic illustration of the formation process of ZnO/(CdS)1x(ZnS)x

coaxial nanowire arrays.

Figure 2. XRD pattern recorded from the arrays of bare ZnO nanowires (i), ZnO/ZnS
coaxial nanowires (ii), and ZnO/(CdS)1x(ZnS)x coaxial nanowires grown at 50 C (iii),
90 C (iv) and 140 C (v).

(gure 4(b)), combined with the SAED pattern in gure 4(a), conrms that the ZnO nanowire is
of single crystallinity and grows along [002] direction. In gure 4(c), the polycrystalline ZnS
shell layer was synthetized on the ZnO core. The fringe spacings of 0.306 nm, 0.280 nm, and
0.256 nm in gure 4(d) match well with the interplanar spacings of (103), (106) and (108)
planes, respectively, of wurtzite ZnS (PCPDFWIN le No. 72-0162). Figure 4(e) shows the
corresponding SAED pattern with polycrystal rings of (106) and (200) of wurtzite ZnS, which
further conrms the single-crystalline ZnO core/polycrystalline ZnS shell structure. Figure 4(f)
shows the TEM image of a ZnO/(CdS)1x(ZnS)x coaxial nanowire (90 C). The surface of the
shell is very rough after reaction. The corresponding HRTEM image (gure 4(g)) shows

Mater. Res. Express 1 (2014) 015021

L Chu et al

Figure 3. SEM images of cross-sectional ZnO nanowire arrays (a), top view of ZnO
nanowire arrays (b), ZnO/ZnS coaxial nanowire array (c), and ZnO/(CdS)1x(ZnS)x
prepared by reacting ZnO/ZnS coaxial nanowires with Cd2+ at 50 C (d), 90 C (e) and
140 C (f), respectively.

additional interplanar spacing of 0.357 nm, which matches well with the (100) of wurtzite CdS
(PCPDFWIN le No.77-2306). In comparison with the core region, O was substituted by S to
form a shell layer, as shown in the EDS elemental maps of a single ZnO/(CdS)1x(ZnS)x coaxial
nanowire (90 C) in gure 4(h). Moreover, the Zn2+ ions in the inner shell regions close to the
ZnO core were mostly substituted by Cd2+, while in the outer shell regions, there are much
more Zn2+ than Cd2+. The (CdS)1x(ZnS)x double-layer-shell structure is further veried by the
elemental line proles in gure 4(i), and can be explained by the graded concentration of Cd2+
from the nanowire surface to the inner shell regions at the beginning of the reactions (since the
reaction is taking place in the Cd2+ solutions), which could act as the driving force for the
process of ion exchange, and form a stable inner shell layer of CdS to nalize the reaction.

Mater. Res. Express 1 (2014) 015021

L Chu et al

Figure 4. TEM image of a ZnO nanowire, inset: corresponding SAED pattern (a),

HRTEM image of the ZnO nanowire (b), TEM image of a ZnO/ZnS coaxial nanowire
(c), corresponding HRTEM image (d) and SAED pattern (e), TEM image of a ZnO/
(CdS)1x(ZnS)x nanowire (90 C) (f), corresponding HRTEM image (g), TEM of
another ZnO/(CdS)1x(ZnS)x nanowire (90 C) and its corresponding high-angle
annular-dark-eld image with the EDS elemental maps (h) as well as line-scans (i)
for Zn, O, Cd and S. The region used for line-scan proles was labeled by a red line in
the middle of the maps.

Mater. Res. Express 1 (2014) 015021

L Chu et al

Figure 5. EDS spectra collected from ZnO nanowires (a), ZnS shells (b), and
(CdS)1x(ZnS)x shells prepared at 50 C (c), 90 C (d), and 140 C (e). There are some
additional peaks of O and Sn located at 0.53 keV and 6.61 keV, respectively, from the
substrate of FTO.

The (CdS)x(ZnS)1x shells were analyzed by EDS analysis, as shown in gure 5. For pure
ZnO nonowires, the atomic ratio of Zn to O is estimated to be ~56.30 : 43.70 based on the EDS
spectrum in gure 5(a). The slight non-stoichiometric ratio of ZnO is attributed to oxygen
vacancies and Zn ions integrated in interstitial locations creating intrinsic defects in ZnO
nanowires [24]. As for ZnS nanotubes, the atomic ratio of Zn to S is 57.51 : 42.49 as shown
in gure 5(b), which is almost the same as that of ZnO nanowires. For the nanotubes of
(CdS)1x(ZnS)x obtained from the samples reacted at 50 C and 90 C, the ratios of Zn: Cd: S
are 50.24 : 6.51 : 43.25 and 30.02 : 24.83 : 45.14, respectively. Interestingly, the atomic ratios
of the sum of Zn and Cd to S always maintain the same value. For the nanotubes obtained from
the sample reacted at 140 C for cation exchange, the corresponding EDS spectrum (gure 5(e))
shows no Zn peak, which implies that the ZnO/ZnS coaxial naowire arrays were thoroughly
transformed to ZnO/CdS nanostrctrue at 140 C for cation exchange, which conrms the XRD
results. From the above compositional analysis, the x values in the (CdS)1x(ZnS)x shells are
obtained to be 0.88, 0.55 and 0 for the samples grown at 50 C, 90 C and 140 C, respectively.
The inset of gure 6(a) shows photographs of the ZnO nanowires, ZnO/ZnS coaxial
nanowires, ZnO/(CdS)0.12(ZnS)0.88, ZnO/(CdS)0.45(ZnS)0.55, and ZnO/CdS on FTO substrates.
The colors of ZnO and ZnO/ZnS core-shell nanowires are gray, which then change to faint
yellow, yellow and nally deep yellow. The absorption spectra of the corresponding samples
are shown in gure 6(a), which cover the range from ultraviolet to green. The absorption of
ZnO core is eliminated and those of the shells are shown as dashed lines in gure 6(a), which
almost coincide with the corresponding core-shell samples. The bandgaps of the shells were
determined using the following equation [25, 26]:

Mater. Res. Express 1 (2014) 015021

L Chu et al

Figure 6. (a) UV-vis absorption spectra of the ZnO nanowire array (i) ZnO/ZnS (ii),
ZnO/(CdS)0.12(ZnS)0.88 (iii), ZnO/(CdS)0.45(ZnS)0.55 (iv), and ZnO/CdS (v) coaxial
nanowire arrays (solid lines) and the corresponding shells (dotted lines) of ZnS,
(CdS)0.12(ZnS)0.88, (CdS)0.45(ZnS)0.55, and CdS. (b) plots of (h) versus h from the
samples of the ZnS (ii), (CdS)0.12(ZnS)0.88 (iii), (CdS)0.45(ZnS)0.55 (iv), and CdS (v)
shells. (c) The bandgaps of ZnxCd1xS follows a quadratic with content of Zn, and the
the bandgaps of (CdS)0.12(ZnS)0.88 and (CdS)0.45(ZnS)0.55, are shown as pentagrams.
(d) The schematic diagram of energy band structure of ZnO/(CdS)1x(ZnS)x.

h = A h Eg

(1)

where is the optical absorption coefcient, h is Plancks constant, is the frequency of light, A
is a constant, Eg is the bandgap energy, and n = 2 for indirect transition or 1/2 for direct
transition. The direct bandgaps of 3.446, 2.633, 2.487, and 2.384 eV, respectively, are obtained
for the shells of ZnS, (CdS)0.12(ZnS)0.88, (CdS)0.45(ZnS)0.55, and CdS, as shown in gure 6(b).
The above dependence of bandgap on composition is quite different from that of ZnxCd1xS
[27, 28], changes quadratically with content of Zn approximatively, as a curved line shown in
gure 6(c), where the bandgaps of (CdS)0.12(ZnS)0.88 and (CdS)0.45(ZnS)0.55, are deviated from
the curve. The (CdS)1x(ZnS)x shell consists of CdS and ZnS, not like ternary alloy ZnxCd1xS.
CdS and ZnS both absorb light, but the interfaces of CdS and ZnS and the relative
composition of CdS and ZnS affect the absorption. Therefore, the bandgaps of (CdS)1x(ZnS)x
shells can be tuned from 2.384 eV (CdS) to 3.446 eV (ZnS). The energy band struture of
ZnO/(CdS)1x(ZnS)x is exhibited in the schematic diagram of gure 6(d), and form a type II
structure.
Figure 7(a) shows that the ZnO/(CdS)0.12(ZnS)0.88, ZnO/(CdS)0.45(ZnS)0.55, and ZnO/CdS
coaxial nanowire arrays are used as photoanodes to fabricate SSSCs. The current densityvoltage characteristics of the SSSCs are exhibited in gure 7(b), and the detailed photovoltaic
9

Mater. Res. Express 1 (2014) 015021

L Chu et al

Figure 7. (a) schematic diagram of the SSSCs based on the anodes of ZnO/
(CdS)0.12(ZnS)0.88, ZnO/(CdS)0.45(ZnS)0.55, and ZnO/CdS coaxial nanowire arrays. (b)
The corresponding current densityvoltage characteristics of the SSSCs.
Table 1. Photovoltaic parameters of the SSSCs based on the ZnO/(CdS)0.12(ZnS)0.88,

ZnO/(CdS)0.45(ZnS)0.55, and ZnO/CdS coaxial nanowire arrays.

Sensitizers
(CdS)0.12(ZnS)0.88
(CdS)0.45(ZnS)0.55
CdS

Jsc (mA cm2)

Voc (V)

FF

PCE (%)

1.333
3.507
7.733

0.583
0.565
0.536

0.390
0.307
0.505

0.303
0.608
2.093

parameters are listed in table 1, under the standard AM 1.5 (100 mW cm2). The current density
(Jsc) and PCE are both increasing with increasing CdS content in the shells. The increase of Jsc
is mainly attributed to the expanded absorption spectrum coverage of the ZnO/(CdS)1x(ZnS)x
coaxial nanowires with increasing CdS. However, the open-circuit voltage (Voc) decreases with
the increase of CdS shells, which may be due to the higher conduction band of ZnS as
compared to ZnO [29]. The higer conduction band of ZnS would raise the conduction band of
ZnO, resulting in increased Voc, as the Voc is determined by the offset between the Fermi level
of ZnO and the redox potential of the electrolyte [30]:

Voc = (E Fermi )ZnO Eelectrolyte

(2)

where (EFermi)ZnO is the Fermi level of ZnO, and Eelectrolyte is the redox potential of the
electrolyte. The ZnO/CdS coaxial nanowire array as photoanode shows an optimized
performance with the PCE of 2.093%, current-density of 7.733 mA cm2 and open-circuit
voltage of 0.536 V.
5. Conclusion

ZnO/(CdS)1x(ZnS)x (0 x 1) coaxial nanowire arrays with modulations of the shell

composition have been fabricated by a facile approach combining hydrothermal method and
successive ion exchange reactions. The shells of (CdS)1x(ZnS)x (0 x 1) are thoroughly and
tightly synthesized on the ZnO cores, and play the role of sensitizers. The simple fabrication
process can be extended to other systems with similar solubility constants to the ZnO/(CdS)1x
(ZnS)x system. The optical absorptions of the coaxial nanowire arrays can be controllably tuned
10

Mater. Res. Express 1 (2014) 015021

L Chu et al

to cover the optical range from ultraviolet to green via changing relative compositions of ZnS
and CdS. The SSSCs based on the anodes of these ZnO/(CdS)1x(ZnS)x coaxial nanowire arrays
reveal increased PCE and current-density, while the corresponding open-circuit voltage
decreases with increasing CdS composition. The photoelectrode based on ZnO/CdS coaxial
nanowire array shows an optimized performance of 2.093% PCE with short-circuit
photocurrent density of 7.733 mA cm2 and open-circuit voltage of 0.536 V.
Acknowledgments

The current work was supported by the 973 Program of China (2011CB933300), the National
Natural Science Foundation of China (11074082, 11204093), and the Fundamental Research
Funds for the Central Universities (HUST: 2012QN114, 2013TS033).
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