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A New Approach to Solar Hydrogen Production: a
ZnO–ZnS Solid Solution Nanowire Array Photoanode
Hao Ming Chen, Chih Kai Chen, Ru-Shi Liu,* Ching-Chen Wu, Wen-Sheng Chang,
Kuei-Hsien Chen, Ting-Shan Chan, Jyh-Fu Lee, and Din Ping Tsai
Due to increasing global demand for energy and environ-
mental concerns, energy resources and conversion pathways to
replace the burning of fossil fuels are urgently being sought.
Hydrogen produced by water splitting using solar energy
clearly represents an attractive direction for the production of
clean energy.[1] Numerous attempts have been made to con-
struct suitable architecture for metal- and semiconductor-based
nanostructured devices.[1–5] One innovative study used titanium
dioxide in the photoelectrochemical splitting of water.[6] Many
investigations have been conducted to develop photocatalytic
materials or photoelectrochemical cells for hydrogen genera-
tion.[7–17] With respect to photoelectrochemical cells for water
splitting, metal oxide photoelectrodes with wide bandgaps, such
as ZnO and TiO2, are severely limited by their poor absorption
of visible light. Various schemes have been adopted to increase
absorption in the visible region, including doping with impuri-
ties and sensitization with quantum dots (QDs).[12,16,18,19] Semi-
conductor quantum dots, such as CdS, CdSe, CdTe, and InP,
have been assembled on metal oxide semiconductor nanos-
tructures as sensitizers of photoelectrodes.[11,12,14,16,18] However,
little work has been done on solid solution as a photocatalytic
material and sensitizer in photoelectrochemical devices. Zinc
oxide is a multifunctional semiconductor material with a direct
bandgap of approximately 3.2 eV; furthermore, the addition
of impurities frequently causes dramatic changes in its elec-
trical and optical properties. The formation of a solid solution
in ZnO–ZnS (ZnOS) is expected to modify the electrical and
Dr. H. M. Chen, C. K. Chen, Prof. Dr. R.-S. Liu
Department of Chemistry
National Taiwan University
Taipei, Taiwan
E-mail: rsliu@ntu.edu.tw
Dr. C.-C. Wu, Dr. W.-S. Chang
Green Energy & Environment Research Laboratories
Industrial Technology Research Institute
Hsinchu, Taiwan
Prof. Dr. K.-H. Chen
Institute of Atomic & Molecular Sciences Academia Sinica
Taipei, Taiwan
Dr. T.-S. Chan, Dr. J.-F. Lee
National Synchrotron Radiation Research Center
Hsinchu, Taiwan
Prof. Dr. D. P. Tsai
Department of Physics
National Taiwan University
Taipei, Taiwan
DOI: 10.1002/aenm.201100246
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optical properties because of the large differences between the
electronegativities and sizes between S and O atoms.[20–23] The
energy bandgap of an S-doped ZnO film, fabricated by pulse
laser deposition, reportedly shifted to a lower level as sulfur
was incorporated,[24] leading to the effective harvest of sun-
light in visible region. Herein, we address a novel sensitiza-
tion approach of ZnO–ZnS solid solution on ZnO nanowires
array for hydrogen generation with considerably enhanced
photocurrent.
Figure 1a shows a schematic of the fabrication steps for ZnOS
nanowire array photoanode. ZnO nanowire arrays were synthe-
sized over the entire surface of an SnO2:F (FTO) glass substrate
using the hydrothermal method. ZnS QDs were deposited in a
chemical bath on ZnO nanowire array, and following thermal
treatment made the formation of ZnO–ZnS solid solution.
Scanning electron microscopy (SEM) and transmission electron
microscopy (TEM) were utilized to further characterize specific
nanostructures of a series of samples. SEM images revealed the
growth of dense and vertically aligned ZnO nanowires on an
FTO substrate, with a typical diameter of around 150 nm, and
TEM image of ZnO nanowires demonstrated that they have
uniform diameter (Figure 1b). The corresponding selected-
area electron diffraction pattern is characteristic of ZnO single
crystal wurtzite structures (spots pattern). Figure 1c shows
ZnO nanowires after deposition of ZnS QDs, which verified
that individual ZnO nanowires were covered with nanoparticle
aggregated with diameters of about 10–30 nm. Interestingly,
the selected area electron diffraction pattern is characteristic of
the two component crystalline natures. The set of spot pattern
can be indexed to the ZnO wurtzite structure along the [ 2 1 1 0 ]
zone axis, which shows a single crystalline nature. The set of
rings revealed a typical face-centered-cubic polycrystalline struc-
ture corresponding to ZnS, and probably associated with the
large amount of ZnS QDs on the surface of the ZnO nanowires.
The high-resolution TEM shows the lattice spacing between
the (111) planes of 0.311 nm is in agreement with that of ZnS
bulk cubic crystal (insert in Figure 1c). The spatial distribution
of the compositional elements within the ZnO–ZnS solid solu-
tion nanowire is obtained from scanning transmission electron
microscope (STEM)-EDX line scans in the radial direction of the
nanowires (indicated by the red arrow in Figure 1d). The spec-
trum verified that the nanowire comprised Zn, O, and S. Most
of the O signals are confined in the cores of the nanowires,
while the shell region yields a more intense S signal. Because
of the random orientation of ZnO nanowire and random depo-
sition of ZnO QDs, the compositional profiles had an asym-
metric nature. Since ZnS QDs randomly attached to the surface
of ZnO nanowire during the deposition process, this indicates
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Figure 1. a) Schematic of the fabrication of ZnOS nanowire photoanode. b) SEM and TEM images, and corresponding SAED of pristine ZnO nanowires.
c) TEM image of ZnO nanowires with deposition of ZnS QDs. d) Elemental profile extract from STEM in direction of nanowires (indicated by arrow
in TEM).

that ZnS QDs exhibited a non-uniform covering on the ZnO
wires. Thus, the S signals present an asymmetric profile due
to the contribution of ZnS QDs to the sulfur signals. Inter-
estingly, the compositional profile of O exhibited a significant
signal outside the edge position, indicating that inter-diffusion
between S and O occurred upon the surface of the nanowires.
This observation verifies the formation of ZnO–ZnS solid solu-
tion on the surface of ZnO nanowires. To examine the struc-
tural properties of these ZnO–ZnS solid solution nanowires,
X-ray diffraction (XRD) studies were conducted (Figure 2a).
All of the samples yielded similar diffraction patterns. The
indexing of the patterns reveals that all of the diffraction peaks
are consistent with the wurtzite ZnO structure with lattice
constants of a = 3.250 Å and c = 5.207 Å. The high intensity
of the (002) diffraction peaks in Figure 2a indicates that reflec-
tions from the (002) plane in ZnO nanowires are stronger than
those from other planes because of the [00L] oriented growth
of nanowires. In Figure 2a, no observable change in the ZnO
nanowires was observed after ZnS QD sensitization, which
meant that sensitization of ZnS QDs did not affect the struc-
ture of ZnO (ZnO@ZnS QDs). In the case of ZnO–ZnS solid
solution, a clear shift forward to low diffraction angle position
could be found, indicating the occurrence of lattice modifica-
tion. Since the oxygen in the ZnO nanowire were substituted
by sulfur, which lead to a lattice expansion owing to the larger
radius of sulfur atoms. Furthermore, no diffraction peak from
ZnS QDs was obtained, implaying most of ZnS QDs formed
solid solutions with ZnO nanowires. The UV-vis absorption
spectra powerfully revealed the optical properties of ZnO–ZnS
solid solution. The Kubelka-Munk remission function F(R)
relates the reflectivity R of a sample to an absorption coefficient
α and a scattering coefficient S, as follows:

(1 − R)2 "
(a) (b) F (R) =
2R
=
S
(002)

(101)

(102)

Based on the assumption of a constant

(F(R)xhν) (a. u.)

ZnO-ZnS solid solution scattering coefficient S, F(R) is proportional

a. u.)

ZnO-ZnS solid solution ZnO to α and represents the absorbance of the

Intensity (a

sample. The absorption spectra of the sam-

ZnO@ZnS QDs ples were calculated using the Kubelka-Munk
function. The bandgap of the samples was
calculated by fitting the absorption band edge
ZnO rod
of the spectra as:

30 35 40 45 50 2.8 3.0 3.2 3.4 h<"(<) = B(h<−bg)1/2

Energy (eV)
2 θ (degree) Since F(R) is proportional to R, the linear
Figure 2. a) X-ray diffraction patterns of ZnO, ZnO nanowires sensitized with ZnS QDs, and portion of a plot [F(R) hν]2 (for ZnO) as a
ZnO-ZnS solid solution nanowires. b) bandgap plots of (F(R)hν)2 for ZnO and ZnO–ZnS solid function of hν intercepts the abscissa at hν =
solution nanowires. bg (bandgap), and such a plot is commonly

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adopted in estimating the bandgap energy of semiconductors.

A model for direct bandgap transitions was used, and good ZnO-ZnS solid solution (a)
linear fits were obtained, as displayed in Figure 2b. It should 1.5 ZnO@ZnS QDs
be noted that there was no significant changes in bandgap ZnO
value (approximately 3.19 eV) in pristine ZnO nanowires. The Dark scan
bandgap of the case of ZnO–ZnS solid solution sample shifted

j / mAcm-2
to a lower energy (approximately 3.10 eV) due to a bowing 1.0
effect in the bandgap.[24] When a S atom is incorporated into
the ZnO lattice, the potential energy of the top of the valence
band that is formed by O2p atomic orbitals (i.e., O2p–S3p repul-
0.5
sion), narrowing the bandgap for ZnO–ZnS solid solution.[24–26]
This reveals that ZnO–ZnS solid solution sensitization can sig-
nificantly reduce the bandgap and absorb visible region from
sunlight. 0.0
To obtain the photocurrent for the photoactivity under light
illumination, photoelectrochemical (PEC) studies were car-
ried out in a 0.5 M Na2S and K2SO3 solution (pH = 11) as the -0.5 0.0 0.5
supporting electrolyte medium, which operated as sacrificial
Potential / V vs Ag/AgCl
reagents.[9] The photocatalytic reaction is carried out in an
aqueous solution including sacrificial reagents, hole scaven-
25 ZnO-ZnS solid solution
gers (sulfide ions) – photogenerating holes that react with the ZnO@ZnS QDs (b)
sacrificial reagents instead of water. Figure 3a displays a set of ZnO
linear-sweep voltammograms that were recorded on pristine 20
ZnO nanowires and ZnO–ZnS solid solution nanowire arrays.
ZnO–ZnS solid solution nanowire arrays showed a pronounced
IPCE / %

15
photocurrent starting at around –0.7 V and continuing to
increase to 1.5 mA cm−2 at +1.0 V under illumination. In
comparison to pristine ZnO nanowires, the photocurrent den- 10
sity of ZnS–ZnO solid solution nanowire arrays was approxi-
mately two times greater (around 0.88 mA cm−2) than the
value for pristine ZnO nanowires (around 0.45 mA cm−2) 5
at 0 V, which suggests that the formed ZnS–ZnO solid solu-
tion harvested solar light more effectively than the pristine 0
nanowires. The two most important metrics associated with a 300 350 400 450 500 550 600
photocurrent are the plateau current and the onset potential. Wavelength / nm
The value of the plateau current depends mainly on the photo-
generated holes/electrons that reach the semiconductor/liquid
junction and react with water, rather than recombining.[15] In 5 ZnO-ZnS solid solution (c)
determining the onset potential, the overpotential must be ZnO@ZnS QDs
H2 evolved (mmol)

taken into account. A large overpotential is caused mainly by 4 ZnO

the slow kinetics of water oxidation, and causes holes/electrons
to accumulate at the surface; subsequent surface recombina-
tion occurs until sufficiently positive potentials are applied. 3
Modification of the electrode surface lowers the kinetic barrier
to interfacial charge transfer, reducing the required overpoten-
tial and shifting the curve to the left.[15] The onset potentials of 2
ZnO nanowires sensitized with ZnS QDs or ZnO–ZnS solid
solution are more negative than that of pristine ZnO, with both 1
samples exhibiting identical behavior, suggesting that their
surfaces are similar (as shown in Figure S1 in the Supporting
Information). Notably, the plateau current of the ZnO sensitized 0
with ZnS QDs is close to that of pristine ZnO nanowires, which 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
means that ZnS QD sensitization cannot markedly improve the
plateau photocurrent. This phenomenon further reveals that Time (h)
solid solution structure can lead to a better enhancement effect
Figure 3. a) Linear-sweep voltammograms from ZnO nanowires, ZnO
in photoactivity than traditional quantum dot sensitization. The nanowires with sensitization of ZnS QDs, and ZnO–ZnS solid solution
improvement in the plateau current is caused by the formation nanowires. b) IPCE spectra of ZnO, ZnO nanowires with sensitization of
of ZnS–ZnO solid solution, which means the solid solution can ZnS QDs, and ZnO–ZnS solid solution nanowires at a potential of 0.5 V
harvest sunlight to generate more photoelectrons. To evaluate versus Ag/AgCl. c) H2 production upon illumination of each samples.

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the PEC performance, incident photon-to-current-conversion
efficiency (IPCE) measurements were made to determine the
photoresponses of the pristine ZnO nanowires and ZnO–ZnS
solid solution nanowire arrays as functions of incident light
wavelength (Figure 3b). The IPCE shows a clear enhancement
at around 380 nm, which can be attributed to the presence of
ZnS. The IPCE curve of the ZnO–ZnS solid solution sample
demonstrates substantial photoactivity in the visible light region
from 400 to 480 nm in addition to strong photoresponse in the
near-UV region, which implies that the ZnS–ZnO solid solu-
tion can significantly enhance the IPCE. This phenomenon is
consistent with the observation of the UV-vis spectra (Figure S2
in the Supporting Information), which may be due to the modi-
fication of electronic structure and orbital coupling derived
from the formation of ZnO–ZnS solid solution (vide infra).
Figure 3c shows the amount of H2 that was produced by ZnO,
ZnO nanowires with sensitization of ZnS QDs, and ZnO–ZnS
solid solution photoelectrodes (3 × 2 cm2) upon solar simulator
illumination (300–900 nm, 100 mW cm− 2, spectral peak at
500 nm). The ZnO–ZnS solid solution photoelectrodes
exhibited a significant enhancement in hydrogen generation
compared to both ZnO nanowires and ZnO nanowires with
sensitization of ZnS QDs.
Although XRD has demonstrated the lattice expansion
caused by sulfur incorporation in ZnO–ZnS solid solution,
little structural information with respect to the zinc is revealed.
Extended X-ray absorption fine structure (EXAFS) is a short-
range probe of structure and yielded results concerning local
correlations around the absorbing atom, specifically the
nearest neighbor interatomic distances and coordination num-
bers.[27–29] EXAFS was conducted to obtain better evidence of
the structural parameters of ZnO–ZnS solid solution nanowire
arrays. Figure 4 shows the Zn K-edge of ZnO and ZnO–ZnS
(a)
(b)
Figure 4. a) EXAFS spectra of Zn K-edge for ZnO and ZnO-ZnS solid solution nanowires. b) Wurtzite structure of ZnO and each scattering shell modes
of central Zn atom. c) XANES spectra of Zn K-edge for ZnO nanowires, ZnO@ ZnS QDs, and ZnO–ZnS solid solution nanowires.
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solid solution nanowire arrays. A strong peak at around 1.85 Å
was observed in the Fourier transform (FT) of the Zn K-edge
EXAFS spectrum of the ZnO nanowires with phase correction,
suggesting that central Zn atoms were surrounded by O atoms
in first shell scattering. Another strong peak at around 3.2 Å
was obtained with phase correction, indicating that the second
shell around the Zn atoms included neighboring atoms of Zn
atoms (as shown in the insert of Figure 4). This result reveals
that the ZnO nanowires are consistent with the wurtzite ZnO
structure. In the case of ZnO–ZnS solid solution, the peak scat-
tered from first shell atoms slightly shifted to longer distance,
which indicates that the first shell around the Zn atoms may
be affected by incorporation of S atoms and including neigh-
boring atoms of two elements (O and S). To better reveal this
structural transformation, the strong first peak possesses two
deconvoluted peaks occurring at 1.85 and 2.0 Å, corresponding
to Zn–O and Zn–S, respectively. The peak at 1.85 Å is assigned
to single scattering by O atoms within ZnO wurtzite structure
and other peak at 2.0 Å corresponds to single scattering by
the S atoms. It was worth noting that second shell scattering
(around 3.2 Å) around central Zn atoms was identical in both
of ZnO and ZnO–ZnS solid solution nanowire arrays, this
could be attributed to the existence only of Zn atoms in the
second scattering shell. This phenomenon demonstrated that
ZnO–ZnS solid solution nanowire arrays exhibited a primary
wurtzite crystal structure while ZnO and ZnS formed a solid
solution phase. This crystalline nanostructure is able to provide
the additional potential advantage of improved charge transport
over a traditional doping approach, which results in a dramatic
increase in the plateau current.[15] Moreover, since O2p and Zn4p
orbitals involved the conduction band of ZnO nanowires, X-ray
absorption near edge structure (XANES) of the Zn K-edge could
be utilized to reveal the conduction band structure of ZnO–ZnS
(c)
ZnO-ZnS solid solution
Normalized Absorbance (a. u.)
ZnO@ZnS QDs
ZnO
0
9650 9675 9700
Energy (eV)
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Figure 5. Sketch of nanostructure of ZnO–ZnS solid solution nanowires. The lower part displays pathways of electrons for generating hydrogen, and
a relative energy diagram.
solid solution (1s to 4p transition). Figure 4c shows the
XANES spectra of pristine ZnO and ZnO–ZnS solid solution
nanowires. Features A and B reflect dipole transition from Zn
1s to 4pπ (along the c axis) states.[30] To compare with pristine
ZnO nanowire, the electronic transition to p state along the c
axis increased with the formation of ZnO–ZnS solid solution,
indicating that orbital coupling occurred in c axis direction of
ZnO nanowire. Accompanying the formation of the ZnO–ZnS
solid solution, the conduction band was derived from S3p, O2p,
and Zn4p orbitals, the coupling of S3p orbital dominated unoc-
cupied states of c axis direction. As a result, ZnO–ZnS solid
solution nanowires array was characteristic of a “hetero-coor-
dination zinc” nanostructure, which modified the conduction
band derived from O2p and Zn4p orbitals. Orbital coupling of
S3p with O2p and Zn4p leads to an increase in the number of
conduction band unoccupied state and enhances the transition
probability from the valence band to the conduction band. This
enhancement in transition probability may contribute to the
photoelectrochemical response.
Furthermore, a simple relationship is satisfied when
both ZnO and ZnS are randomly distributed in the
nanowires:[27,31]
N ZnO = (X ZnO / X ZnS )N ZnS
NZnO is the coordination number of the O atoms around
the Zn atoms, and NZnS is the coordination number of the S
atoms around the Zn atoms. XZnO and XZnS denote the frac-
tions of ZnO and ZnS in the sample, respectively. Notably,
the coordination number determined from the EXAFS spectra
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of the ZnO–ZnS solid solution nanowires satisfied the afore-
mentioned relationship (S/O = 23/77 from elemental analysis,
Figure S3 in the Supporting Information), indicates that the
nanowires formed a solid solution phase. Based on the above
observations, we propose a model of the ZnO–ZnS solid
solution nanowires. Figure 5 presents a model of the ZnO–
ZnS solid solution nanowires array photoelectrode for solar
hydrogen generation. The EXAFS and XRD results revealed
that ZnO and ZnS formed a solid solution in this study. How-
ever, the STEM-EDX line scans spectra exhibited a signifi-
cant asymmetric distribution, implying that S incroporation
dominated on the surface rather than core part of nanowires.
Consequently, ZnS QDs are utilized as a source of sulfur to
form a solid solution which leads to a narrow bandgap and
increases the number of conduction band unoccupied states.
The energy level diagram in Figure 5 indicates that the conduc-
tion bands (CB) of the ZnS–ZnO solid solution are higher than
that of ZnO, allowing the efficient transfer of photoexcited
electrons from ZnS–ZnO solid solution to ZnO nanowires
(determination of the detail of band position is described in
the Supporting Information) When electrons are transported
to the cathode, generating hydrogen in a PEC device, the holes
are consumed in an oxidation reaction at the anode/electrolyte
interface.
In conclusion, we have demonstrated significant improve-
ment in the ZnO–ZnS solid solution sensitization, which
results in a dramatic increase in the plateau photocurrent, as
well as a substantial shift in the onset potential. This study is
the first demonstration of sensitization using ZnO–ZnS solid
solution. A photocurrent of 0.88 mA cm−2 at 0 V was observed
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and it was more than 195% greater than that of pristine ZnO
nanowires. The STEM results demonstrated the interdiffu-
sion between S and O, and sulfur atoms became incorporated
into the lattice of ZnO nanowires to form the solid solution of
ZnO–ZnS. ZnO–ZnS solid solution nanowires array was char-
acteristic of a “hetero-coordination zinc” nanostructure, which
modified the conduction band derived from O2p and Zn4p
orbital. The enhancement in photoactivity can be attributed to
the increase of O2p+S3p and Zn4p unoccupied states. This solid
solution structure can deliver a better enhancement effect in
photoactivity than traditional quantum dot sensitization, and
also reveals hydrogen generation. Although this investigation
was concerned with the ZnO–ZnS system, we believe that this
strategy can be extended to other solid solution systems.
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
The authors gratefully acknowledge the financial support of the Institute
of Atomic & Molecular Sciences Academia Sinica (Contract No. AS-98-
TP-A05) and the National Science Council of Taiwan (Contracts Nos.
NSC 97-2113-M-002-012-MY3 and NSC 100-2120-M-002-008).
Received: May 10, 2011
Revised: June 22, 2011
Published online: August 16, 2011
[1] A. J. Bard, M. A. Fox, Acc. Chem. Res. 1995, 28, 141.
[2] H. M. Chen, R. S. Liu, J. Phys. Chem. C 2011, 115, 3513.
[3] U. Ozgur, Y. I. Alivov, C. Liu, A. Teke, M. A. Reshchikov, S. Dogan,
V. Avrutin, S. J. Cho, H. Morkoc, J. Appl. Phys. 2005, 98.
[4] L. E. Greene, B. D. Yuhas, M. Law, D. Zitoun, P. D. Yang, Inorg.
Chem. 2006, 45, 7535.
[5] L. Vayssieres, Adv. Mater. 2003, 15, 464.
[6] A. Fujishima, K. Honda, Nature 1972, 238, 37.
[7] M. A. Alpuche-Aviles, Y. Y. Wu, J. Am. Chem. Soc. 2009, 131, 3216.
Adv. Energy Mater. 2011, 1, 742–747 © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advenergymat.de
COMMUNICATION
[8] F. Gartner, B. Sundararaju, A. E. Surkus, A. Boddien, B. Loges,
H. Junge, P. H. Dixneuf, M. Beller, Angew. Chem., Int. Ed. 2009, 48,
9962.
[9] A. Kudo, Y. Miseki, Chem. Soc. Rev. 2009, 38, 253.
[10] X. Yang, A. Wolcottt, G. Wang, A. Sobo, R. C. Fitzmorris, F. Qian,
J. Z. Zhang, Y. Li, Nano Lett. 2009, 9, 2331.
[11] H. M. Chen, C. K. Chen, Y.-C. Chang, C.-W. Tsai, R.-S. Liu, S.-F. Hu,
W.-S. Chang, K.-H. Chen, Angew. Chem., Int. Ed. 2010, 49, 5966
[12] J. Hensel, G. M. Wang, Y. Li, J. Z. Zhang, Nano Lett. 2010, 10, 478.
[13] A. I. Hochbaum, P. D. Yang, Chem. Rev. 2010, 110, 527.
[14] T. Nann, S. K. Ibrahim, P. M. Woi, S. Xu, J. Ziegler, C. J. Pickett,
Angew. Chem., Int. Ed. 2010, 49, 1574.
[15] S. D. Tilley, M. Cornuz, K. Sivula, M. Gratzel, Angew. Chem., Int. Ed.
2010, 49, 6405
[16] G. M. Wang, X. Y. Yang, F. Qian, J. Z. Zhang, Y. Li, Nano Lett. 2010,
10, 1088.
[17] Z. G. Yi, J. H. Ye, N. Kikugawa, T. Kako, S. X. Ouyang,
H. Stuart-Williams, H. Yang, J. Y. Cao, W. J. Luo, Z. S. Li, Y. Liu,
R. L. Withers, Nat. Mater. 2010, 9, 559.
[18] Y. L. Lee, C. F. Chi, S. Y. Liau, Chem. Mater. 2010, 22, 922.
[19] S. D. Chavhan, R. S. Mane, W. Lee, S. Senthilarasu, S. H. Han,
J. Lee, S. H. Lee, Electrochim. Acta 2009, 54, 3169.
[20] J. V. Foreman, J. Y. Li, H. Y. Peng, S. J. Choi, H. O. Everitt, J. Liu,
Nano Lett. 2006, 6, 1126.
[21] S. G. Hussain, D. M. Liu, X. T. Huang, S. Ali, M. H. Sayyad, J. Phys.
Chem. C 2008, 112, 11162.
[22] M. W. Murphy, P. S. G. Kim, X. Zhou, J. Zhou, M. Coulliard,
G. A. Botton, T. K. Sham, J. Phys. Chem. C 2009, 113, 4755.
[23] J. Geng, B. Liu, L. Xu, F. N. Hu, J. J. Zhu, Langmuir 2007, 23, 10286.
[24] Y. Z. Yoo, Z. W. Jin, T. Chikyow, T. Fukumura, M. Kawasaki,
H. Koinuma, Appl. Phys. Lett. 2002, 81, 3798.
[25] C. Y. Moon, S. H. Wei, Y. Z. Zhu, G. D. Chen, Phys. Rev. B 2006,
74.
[26] C. Persson, C. Platzer-Bjorkman, J. Malmstrom, T. Torndahl,
M. Edoff, Phys. Rev. Lett. 2006, 97.
[27] H. M. Chen, C. F. Hsin, P. Y. Chen, R. S. Liu, S. F. Hu, C. Y. Huang,
J.-F. Lee, L.-Y. Jang, J. Am. Chem. Soc. 2009, 131, 15794.
[28] H. M. Chen, C. F. Hsin, R. S. Liu, J.-F. Lee, L. Y. Jang, J. Phys. Chem.
C 2007, 111, 5909.
[29] H. M. Chen, R. S. Liu, K. Asakura, L.-Y. Jang, J.-F. Lee, J. Phys. Chem.
C 2007, 111, 18550.
[30] E. Y. M. Lee, N. Tran, J. Russell, R. N. Lamb, J. Appl. Phys. 2002, 92,
2996.
[31] H. M. Chen, R. S. Liu, K. Asakura, J.-F. Lee, L.-Y. Jang, S. F. Hu, J.
Phys. Chem. B 2006, 110, 19162.
wileyonlinelibrary.com 747