APPLIED PHYSICS LETTERS 91, 113104 2007

TiO2 CdSe nanowire arrays showing visible-range light absorption

Jung-Chul Lee and Yun-Mo Sunga
Department of Materials Science & Engineering, Korea University, Seoul 136-713, South Korea

Tae Geun Kim

Department of Electronic Engineering, Korea University, Seoul 136-713, South Korea

Heon-Jin Choi
School of Advanced Materials Science & Engineering, Yonsei University, Seoul 120-749, South Korea

Received 26 April 2007; accepted 18 August 2007; published online 11 September 2007
High-density single crystalline TiO2 nanowires 50 nm diameter were grown on Ti substrates by
chemical vapor deposition, and they were overcoated with the solution containing CdSe
nanocrystals 5 nm diameter and heat treated at 600 C to form TiO2 hetersotructured nanowire
arrays. The TiO2 nanowire arrays showed uniformly distributed CdSe nanocrystals and high
crystallinity of rutile and wurtzite from the TiO2 and the CdSe, respectively. Owing to the
heterostructure of TiO2, they demonstrate almost full visible-range light absorption, and thus
enhanced photocatalytic activity by the charge separation via electron and hole transfers between the
CdSe and the TiO2. 2007 American Institute of Physics. DOI: 10.1063/1.2783229
TiO2 is one of the most important oxide semiconductors
showing distinct photochemical activities due to its unique
energy band gap characteristics. Thus, for many years, it has
been intensively exploited for the purification of contaminated water and air14 and for the generation of renewable
energy.58 Recently, TiO2 nanostructures have attracted a
great deal of interest due to the large surface-to-volume ratio
that is beneficial to most of the TiO2-based devices. As the
surface absorbing the light and reacting with surrounding
substances increases, the photochemical activity can be considerably enhanced.9 However, the poor natural light absorption capability due to its intrinsically large energy band gap
3.2 eV has been significantly limiting the broad applications of the TiO2 nanostructure for photovoltaics and photocatalysts. To overcome this drawback, organic or inorganic
dye-sensitized TiO2 heterostructures have been developed,
and the improvement of their natural light absorption capability has been reported.10,11 Also, the dye-sensitized TiO2
can show active photochemical reactions by charge
separation.12 The free electrons generated in the dye by the
visible light excitation can be injected to the TiO2, and the
holes from the TiO2 can transfer to the dye, which can prevent the electron-hole recombination effectively, and provide
high photovoltaic and photocatalytic efficiencies. Semiconductors such as CdSe, CdS, PbS, etc., have energy band gap
corresponding to the energy of visible-range light and can
serve as the inorganic dye for the TiO2.1315 These inorganic
dyes show the superior thermalstability, photostability, and
chemical stability compared to the organic dyes. It has been
well known that due to the intrinsic energy band gap structure, the CdSe TiO2 is a good combination to obtain high
photoconversion and high photodecomposition efficiencies.
In the TiO2 CdSe heterostructure, prior to the electron-hole
recombination, photogenerated electrons from the CdSe
transfer to the TiO2, while the holes from the TiO2 transfer to
the CdSe.
a

Electronic mail: ymsung@korea.ac.kr

TiO2 nanowire is a desirable structure for both the photovoltaic and photocatalyst applications due to its array
structure on a substrate compared to the common particle
form.1618 Each individual nanowire can supply plenty of
surface area, while the nanoparticles are apt to agglomerate
and loose the surface area. Also, the nanowire can provide
the free electrons with the fast diffusion path between the
two electrodes in dye-sensitized solar cells. Recently, we developed single-crystalline TiO2 nanowire arrays on sapphire
and silica, and Ti substrates, respectively, by chemical vapor
deposition.16 Especially, we could grow the nanowires of
50 nm diameter and 10 m length on Ti substrates at a
very low temperature 700 C within a very short period
of time 10 min due to the seeding effect of the TiO2
rutile layer formed at the surface of Ti substrates. In this
letter, we report the synthesis of TiO2 CdSe nanowire arrays
through the overcoating of the surface of TiO2 nanowires,
grown on Ti substrates, with CdSe nanocrystals. The light
absorption and photocatalytic characteristics of the heterostructure were investigated and compared with those of the
bare TiO2 nanowire arrays.
First, high-density TiO2 nanowire array was prepared on
the Ti substrates by chemical vapor transport of TiCl4 via the
vapor-liquid-solid growth. Au layer was used as a catalyst,
and O2 0.5 SCCM SCCM denotes cubic centimeter per
minute at STP and H2 20 SCCM / Ar 100 SCCM was
used as a reactive and a carrier gas, respectively. The substrate temperature was 700 C, and the time period for the
growth of TiO2 nanowires was 10 min. Next, the CdSe nanocrystals were synthesized using inverse micelles of paraffin
oil and oleic acid. CdO and Se shots were used as precursors
for the CdSe nanocrystals. Rapid injection of Cdoleic acid
solution at 160 C into the Separaffin oil solution at
220 C induces the fast nucleation and slow growth of the
CdSe nanocrystals. The TiO2 nanowires were overcoated by
the CdSe nanocrystal-bearing solution and heat treated at
600 C for 30 min in Ar gas for strong attachment of the
nanocrystals and removal of organic remaining.

0003-6951/2007/9111/113104/3/$23.00
91, 113104-1
2007 American Institute of Physics
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Appl. Phys. Lett. 91, 113104 2007

Lee et al.

FIG. 1. FESEM images of the a bare TiO2 and b TiO2 CdSe nanowires.

Figure 1 shows field-emission scanning electron microscopy FESEM images of the a bare single-crystalline TiO2
and b heterostructured TiO2 CdSe nanowire arrays annealed at 600 C for 30 min, respectively. The FESEM image shows that uniform TiO2 nanowires with a diameter of
50 70 nm and a length of 5 10 m were formed at 700 C
within 5 min. This is a noticeable progress in the vaporphase TiO2 nanowire synthesis compared to the previous
processes conducted at 1000 C for 90 min.1618 These
enhanced kinetics of the nanowire growth can originate from
the seeding effect of the rutile TiO2 layer formed at the surface of the Ti substrates as well as the supplementary Ti
vapor supply from the Ti substrates to the Au catalyst. The
rutile seed layer can decrease the activation energy barrier
for the nucleation of the rutile crystals due to the epitaxy and
in turn significantly enhance the nucleation and growth kinetics of the rutile TiO2 nanowires. The TiO2 CdSe nanowires showed very rough surface due to the attachment of the
CdSe nanocrystals see the inset in Fig. 1b. Quantitative
chemical analysis of the heterostructured TiO2 CdSe nanowires were performed using energy dispersive x-ray spectroscopy, and the results indicated that the average contents
of Ti, O, Cd, and Se were 32.81, 64.42, 1.58, and 1.18 at. %,
respectively.
Detail morphological features and crystallinity of the
bare TiO2 and TiO2 CdSe nanostructures were investigated
using high-resolution transmission electron microscopy HRTEM and selected area electron diffraction SAED analyses, as shown in Fig. 2. HRTEM and SAED of the bare TiO2
nanowire reveal that it is a perfect single crystal rutile with a
diameter of 70 nm. HRTEM image of the TiO2 CdSe
nanostructure shows that the high-density CdSe nanocrystals
are uniformly attached to the surface of the TiO2 nanowire.
SAED on the TiO2 CdSe nanostructure shows the apparent
ring diffraction patterns from the crystallinity of the wurtzite
CdSe nanocrystals as well as spot diffraction patterns from
the rutile TiO2 nanowires.
Figure 3 shows the comparison in the UV-visible light
absorption spectroscopy results of the bare TiO2 and
TiO2 CdSe heterostructured nanowires. The TiO2 nanowires arrays were grown on a large Ti substrate and it was
cut into two pieces, respectively, for the preparation of the
TiO2 and TiO2 CdSe nanowire samples. Thus, we can
safely consider that the density of TiO2 nanowires is almost
identical both in the bare TiO2 and TiO2 CdSe nanowire
samples. The TiO2 CdSe nanowires show apparent increase
in the light absorbance of the visible light ranging from
400 to 700 nm. This much enhanced visible-range light
absorption in the TiO2 CdSe nanowires is attributed to the
excitation of electrons in the CdSe. Since the size distribution of the CdSe nanocrystals attached to the surface of the
TiO2 nanowires was 5 10 nm, the energy band gap of

FIG. 2. Color online HRTEM images and SAED patterns of the a bare
TiO2 and b TiO2 CdSe nanowires. The circles show the locations of the
CdSe nanocrystals.

them ranges from 2.48 to 1.74 eV, according to the following quantum confinement effect,19 and the corresponding
light absorption wavelength ranges from 500 to 714 nm.
Egdot = Egbulk +

1.8e2
h2
.

2m*d2 20d

Here, Egdot is the energy band gap of a nanocrystal quantum dot, Egbulk is the energy band gap of a bulk semiconductor, h is the Planck constant, m* is the reduced mass of
exciton, d is the diameter of a nanocrystal, e is the electron
charge, is the relative dielectric constant, and 0 is the
space dielectric constant. Therefore, almost full visible-range
light can be absorbed by the CdSe nanocrystals, and the exited electrons can be injected into the TiO2. The bare TiO2
and the TiO2 CdSe nanowires show the light absorption
peaks at 335 and 353 nm, respectively, which corresponds to
the energy band gaps of 3.70 and 3.52 eV. Both of the nanostructures show quantum confinement effect, since the pure
rutile possesses the energy band gap of 3.2 eV. The redshift
in the UV-visible light absorption of the TiO2 CdSe nanowires can come from the extension of the electron wave
function of TiO2 into CdSe.20 The TiO2 CdSe nanowires

FIG. 3. Color online Comparison in the UV-visible light absorption spectra of the bare TiO2 and TiO2 CdSe nanowires.
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113104-3

Appl. Phys. Lett. 91, 113104 2007

Lee et al.

FIG. 4. Color online Comparison in the photodecomposition efficiency of

the bare TiO2 and the TiO2 CdSe nanowires.

show the second light absorption peak around 664 nm,

which corresponds to the energy band gap of 1.86 eV and the
average particle size of 8.2 nm of the CdSe nanocrystals.
Photocatalytic efficiency of the TiO2 CdSe nanowires
was evaluated using the degradation of a methylene blue
MB solution, and it was compared with that of the bare
TiO2. The MB solution containing the nanostructures was
irradiated by ultraviolet UV light for photocatalytic reactions. The decrease in the intensity of visible light absorbance peaks at 664 nm, corresponding to the decomposition
of the MB, was monitored according to the UV-light exposure time period. Figure 4 shows the normalized variation in
the absorbance of the MB solutions containing the bare TiO2
and TiO2 CdSe nanowires. The TiO2 CdSe nanowires almost completely decomposed the MB solution within
80 min, while the bare TiO2 nanowires decomposed it within
110 min. It is certain that the visible-light absorption could
contribute to the photodecomposition reaction in the heterostructured TiO2 CdSe nanowires. The possible mechanism
for the enhanced photocatalytic activity even under the
visible-range light irradiation was considered using the energy band diagram for the heterostructured TiO2 CdSe
nanowires, as indicated in the inset of Fig. 4. Absorption of a
unit of the visible-range light, associated with the formation
of a conduction band free electron and a valence band hole,
occurs in the CdSe nanocrystals during the visible-light irradiation, and the migration of the photogenerated electron to
the surface and the transfer to the TiO2 nanowire occurs
subsequently. Since there is very low concentration of holes
to recombine with, therefore the electron has high opportunity to participate in the reduction reaction to form oxygen
radicals, which is a very strong oxidant and can decompose
organic substances effectively. Also, the photogenerated
holes in the CdSe nanocrystals theoretically migrate to the
surface and participated in the oxidation reaction to form
hydroxyl radicals, which is more effective to decompose the
organic substances. The TiO2 nanowire itself can show photodecomposition activity only under the UV-light irradiation

due to the high energy band gap. The holes created by the
UV light irradiation to the TiO2 can transfer to the CdSe, and
the opportunities of the electron-hole recombination can be
substantially reduced.
In this study, the heterostructured TiO2 CdSe nanostructure arrays were achieved through overcoating the surface of the single-crystalline TiO2 nanowires with the CdSe
nanocrystal-containing solution. The TiO2 CdSe nanowires
show the absorption of UV-visible light ranging from
353 to 614 nm. The enhanced visible light absorption in the
TiO2 CdSe is due to the charge separation between the
CdSe and TiO2. Due to the visible-light absorbing capability,
the TiO2 CdSe nanowires show enhanced photocatalytic
efficiency compared to the bare TiO2 nanowires. This
TiO2 CdSe heterostructure can also be a strong candidate
for the dye-sensitized solar cells due to the high quantum
yield from the charge separation under the visible-light irradiation.
This work was supported by the Korea Research Foundation KRF grant by the Korean Government MOEHRD
KRF-2006-311-D00568.
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