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Formation and photoluminescence of single-crystalline rutile TiO2 nanowires synthesized by

thermal evaporation

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2006 Nanotechnology 17 105
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INSTITUTE OF PHYSICS PUBLISHING

NANOTECHNOLOGY

Nanotechnology 17 (2006) 105109

doi:10.1088/0957-4484/17/1/017

Formation and photoluminescence of

single-crystalline rutile TiO2 nanowires
synthesized by thermal evaporation
Jyh-Ming Wu1 , Han C Shih1,3 and Wen-Ti Wu2
1

Department of Material Science and Engineering, National Tsing-Hua University,

101 Section 2, Kuang Fu Road, Hsinchu 300, Taiwan
2
Energy and Resource Laboratories, Industrial Technology Research Institute, Building 64,
195 Section 4, Chung Hsing Road, Chutung, Hsinchu 310, Taiwan
E-mail: jmwu@itri.org.tw

Received 16 August 2005, in final form 10 October 2005

Published 1 December 2005
Online at stacks.iop.org/Nano/17/105
Abstract
Uniform nanowires were grown over a selected area of a TiO2 /sapphire
substrate using a horizontal furnace system with a radio frequency (RF)
heater. The growth of the nanowire was governed by a catalyst-free
vapoursolid (VS) mechanism. The x-ray diffraction pattern showed that the
nanowires comprised TiO2 in the pure rutile phase. The size of the TiO2
nanowires was verified using field emission scanning electron microscopy
(FESEM), which showed that the diameters were in the range 50100 nm
and the lengths were in the range 12 m. The nanowire growth direction
and its crystalline structure were examined using high-resolution
transmission electron microscopy (HRTEM), indicating that these
nanowires had a single-crystalline structure and grew along the [110] axis.
A blue emission peak at 380 nm was obtained under examination by
photoluminescence (PL), which revealed only single-crystalline rutile TiO2
nanowires, and thus indicated that the single-crystalline TiO2 nanowire
could be a candidate for use in optoelectronic devices.
1. Introduction
One-dimensional (1D) nanostructure materials, such as
ZnO [1], TiO2 [2, 3], MnO2 [4] and WO3 [5] among
others, have recently attracted significant attention, because
they provide a fundamental nanodevice technology. TiO2
nanostructures have various applications such as gas
sensors [6], optical devices [7, 8], photocatalysis [9]
and photoelectrochemical conversion [1012].
This
material provides a strong scientific incentive for ongoing
research [13, 14]. The application of TiO2 nanostructure
material in semiconductor devices with favourable optical
properties depends on crystalline characteristics and a direct
build-up on the substrate. Thermal evaporation has commonly
been utilized to fabricate highly crystalline nanowires to be
applied to micro-electronic devices. However, titanium (Ti)
is a refractory metal with a high melting point, so the use of
the vapour transfer process (physical vapour deposition, PVD)
3 Author to whom any correspondence should be addressed.

0957-4484/06/010105+05$30.00 2006 IOP Publishing Ltd

to synthesize the TiO2 nanostructure is currently difficult.

Consequently, various schemes, such as the solgel process,
hydrothermal synthesis and electrochemical synthesis have
been developed to fabricate TiO2 nanostructures [1518].
Although TiO2 nanostructures have often been synthesized
chemically, the process requires further heat treatment
to improve their crystallinity. Furthermore, the process
cannot easily be applied with substrates intended for use in
semiconductor devices.
In our previous studies [19], rutile phase TiO2 nanowires
with strong crystalline properties were successfully fabricated
by two-step thermal evaporation using an RF frequency heater.
However, the two-step process takes a long time and large
nanowires could not be grown on the substrate. This work
proposes the pre-deposition of a TiO2 layer, which was
experimentally found to promote the growth of TiO 2 nanowires
beyond that achieved using bare sapphire substrate [20].
Accordingly, the selected-area growth of TiO2 nanowires was
achieved.

Printed in the UK

105

J-M Wu et al

surface area of the nanowires was determined using

a BrunauerEmmettTeller analyser (BET, Quantachrome
Instrument Autosorb-1). A Jobin Yvon-Spex fluorolog-3
spectrophotometer was also used to conduct PL studies.

3. Results and discussion

Figure 1. Schematic illustration of the synthesis system.

The photoluminescence (PL) characteristics include a

sharp emission peak at 380 nm (3.26 eV) only from
single-crystalline rutile TiO2 nanowires. No outstanding
peak was obtained from the bulk rutile TiO2 . Through
our characterization, the sharp emission peak is because the
nanowires are strongly crystalline. The intrinsic luminescence
makes single-crystalline TiO2 nanowires a candidate for use in
optoelectronic devices.

2. Experimental details
A radio frequency (RF, 350 kHz) heater (coil) was used as
a horizontal quartz tube furnace system in the experiment, as
presented in figure 1. The sapphire substrates were coated with
a Ti layer with a thickness of 200 nm by DC sputtering. The
Ti layer fully transitions into a TiO2 layer after the substrate
temperature is over 450 C. 1.5 g of the source material (Ti
powder, purity 99.9%, Alfa Aesar) was placed in the front of
the graphite boat, which was surrounded by the RF coil, and the
as-prepared substrate (TiO2 /sapphire) was placed in the rear
half of the graphite boat. When the heater system was turned
on, the front of the graphite boat was heated directly and was
hotter than the rear of the graphite boat. Therefore, the front of
the graphite boat was called the high-temperature (HT) zone
and the rear part was called the low-temperature (LT) zone.
Before the heating was turned on, the quartz reactor was first
evacuated to a pressure of around 105 Torr to ensure that
the system was sufficiently clean. The system pressure was
maintained at 1 Torr at all times using an automatic pressure
controller with a throttle valve. The flow rate of the argon gas
introduced throughout the process was 20 sccm (Ar, purity:
99.99%). The system was heated until the temperature of the
HT zone was 1100 C (the temperature of the substrate was
controllable, i.e., 850 C) with a ramp of 200 C per minute,
then that temperature was held for 1 h. At the same time,
1 sccm of oxygen (O2 , purity 99.99%) was added until the end
of the experiment.
The structure of the sample was analysed using a thinfilm x-ray diffractometer (Philips PW3710) and a highresolution transmission electron microscope (HRTEM, JEOL
JEM-2000FX, operated at 200 kV). The morphology and
size distribution were characterized using a field emission
scanning electron microscope (FESEM, JEOL 7000, operated
at 10 keV). The composition of the nanowire was analysed
by energy dispersive x-ray spectroscopy (EDS). The specific
106

The titanium (Ti) vapour pressure was theoretically calculated

to be 103 Torr when the process temperature exceeded
1600 C [21, 22], making fabrication of TiO2 nanostructure
materials by vapour transfer difficult. This challenge has
already been overcome using a two-step thermal evaporation
process with a radio frequency heater [20]. In this work, a
similar process of the pre-deposited (TiO 2 ) layer was employed
to promote the growth of TiO2 nanowires, instead of a two-step
process. The purpose is to form TiO2 seeds (layer) with a high
surface energy on the substrate. Then, the resultant vapour
phase and the supersaturation factor in these TiO2 seeds (layer)
are properly controlled to yield a 1D nanostructure by the VS
mechanism [23, 24]. The TiO2 layer provides more nucleus
sites for the growth of TiO 2 nanowires, so TiO2 nanowires were
grown over a selected area, as experimentally determined, and
will be discussed later.
The influence of reaction time on the temperature of
synthesis at 850 C has been elucidated in our earlier
study [25]. The effect of the temperature of synthesis on
the reaction time (1 h) is now considered in this work.
Figures 2(a)(c) reveal the various temperatures of synthesis of
the nanowires. The temperature of synthesis was varied among
500, 850 and 1050 C for 1 h, respectively. Figure 2(d) presents
the corresponding x-ray diffraction patterns. Figure 2(a) shows
that only nanoparticles were deposited on a TiO 2 layer/sapphire
substrate when the temperature was controlled at 500 C for
1 h. The image in the inset in figure 2(a) presents nanoparticles
with a diameter of around 4080 nm. Conversely, nanowires
with lengths of about 12 m were grown uniformly at high
density throughout the entire TiO2 /sapphire substrate when
the temperature was controlled at 850 C for 1 h, as shown in
figure 2(b). The image in the inset in figure 2(b) shows that
the diameters of the nanowires are in the range 50100 nm.
Figure 2(c) presents a rod-like and irregular morphology,
obtained at a temperature of synthesis at 1050 C for 1 h.
Figure 4(d) displays the corresponding x-ray diffraction pattern
of the nanowires formed at various temperatures. Clearly,
only the nanoparticles formed at 500 C comprised TiO2
anatase with a little rutile phase, because the transformation
temperature of TiO2 from anatase to rutile was 750 C [26].
Therefore, the XRD pattern was dominated by the anatase
phase obtained following synthesis at 500 C. At synthetic
temperatures from 850 to 1050 C, a TiO2 pure rutile phase
was formed. This phase has a body-centred tetragonal structure
with lattice parameters a = b = 0.459 33 nm and c =
0.295 92 nm (JCPDS 21-1276) [27]. The nanowires presented
a different morphology between the temperature of synthesis
at 850 C and 1050 C. The reason for this is not clear yet.
There were no metal catalysts in our work, so the growth
of the nanowires was dominated by the vapoursolid (VS)
mechanism. Figure 3 shows that the TiO2 nanowires were
selectively grown only on the TiO2 /sapphire substrate, and no
nanowire appeared on the bare substrate. When no Ti powder

Formation and photoluminescence of single-crystalline rutile TiO2 nanowires synthesized by thermal evaporation

Figure 2. The FESEM images and the corresponding XRD patterns showing the effect of the temperature of synthesis (500, 850 and
1050 C) on the reaction time for 1 h: (a) 500 C for 1 h; only nanoparticles was deposited on the TiO2 layer; the inset in (a) shows
nanoparticles with a diameter of 4080 nm; (b) 850 C for 1 h; the nanowires are grown all over the TiO2 /sapphire substrate with the
length of 12 m; the inset in (b) shows that the nanowires have diameters of 50100 nm; (c) 1050 C for 1 h; rod-like and irregular
nanowires are present; (d) the corresponding XRD patterns.

Figure 3. The nanowires were selected-area grown on

TiO2 /sapphire substrate.

was placed in the front of the graphite boat, no TiO2 nanowire

grew on the TiO2 /substrate [20], because, according to the
phase diagram of Ti and O [28], the Ti layer cannot provide
the Ti vapour species required for the growth of the TiO2
nanowires. The Ti layer fully transitions into a polycrystalline
TiO2 layer when the substrate temperature exceeds 450 C. We
therefore suggest that the Ti powder in the HT zone provides the
Ti vapour species required for the growth of TiO2 nanowires.
This finding is consistent with the report of Xia et al [29].
The TiO2 layer exhibited more growing sites than the bare
sapphire substrate, so nanowires were grown over a selected
area. This selected-area growth can be explained by using
the thermodynamic mechanism of Porter et al [30] and Jean
et al [31]. Porter et al suggested that the impurities or
strained regions of a lattice enable the nuclei to be formed

(heterogeneous nucleation) with a much smaller free energy of

activation than that of homogeneous nucleation. Accordingly,
the activation energy of the nucleus sites on the TiO2 layer was
much lower than that on the bare sapphire substrate. This fact is
consistent with the authors earlier findings [20]. We therefore
suggest that the TiO2 layer has more growth sites than the bare
substrate. Moreover, Jena et al proposed that polycrystalline
structures (TiO2 layer) generally include dislocations, grain
boundaries, strain energy and interface energy, and so may
have a positive free energy. Therefore, these structures further
act as high-energy sites for initiating the transformation, and
promoting the rapid transportation of components. In order
to reduce the energy as low as possible in such an area, the
mobile species of Ti and/or TiO2 were accommodated on highenergy sites for longer than on low-energy sites. Hence, vapour
species preferred to accumulate on TiO2 /sapphire substrate
rather than the bare sapphire in our work. Additionally, the
high-energy sites of the TiO2 layer provided the nucleation
sites for the growth of the nanowires, especially when the most
thermally stable crystalline plane (110) was present and the 1D
morphology thus formed. Figure 4 displays the preferential
growth of nanowires on the TiO2 layer.
The TEM cross-section image in figure 4(a) presents an
individual nanowire grown on the polycrystalline TiO2 layer;
the grain and grain boundary are clearly observed. The
inset in figure 4(a) shows the lattice image of a TiO2 grain,
indicating a lattice spacing of 0.32 nm, which corresponds
to the (110) plane of the TiO2 rutile structure. Figure 4(b)
is the high magnitude image from figure 4(a), which is
marked by the white circle. The corresponding selected-area
diffraction (SAD) pattern in the inset figure 4(b), recorded
perpendicular to the long axis of the lattice image, reveals
that [110] is the favoured direction of growth of rutile TiO2
107

J-M Wu et al

nanowires. The (110) plane is the most thermodynamically

stable in the TiO2 rutile structure [32], so the growth of the
TiO2 crystal is faster in the plane (110) than the other plane.
Thus one-dimensional structure was formed. Figure 4(c)
depicts the epitaxial process of nanowires discussed above.
The composition of the nanowire was analysed by energy
dispersive x-ray spectroscopy (EDS). Figure 4(d) confirms that
the nanowires were composed of Ti and O with an atomic
ratio of about 1:2. The copper (Cu) and carbon (C) peaks in
the EDS spectrum originate from the carbon-coated grid of
the TEM specimen. The as-prepared TiO2 nanowires were
analysed using the BrunauerEmmettTeller (BET) analyser.
The specific surface area of the as-synthesized TiO2 nanowires
was about 86 m2 g1 .
The photoluminescence properties of single-crystalline
TiO2 nanowires were compared with bulk TiO2 (rutile sintered
pieces, Alfa Aesar, purity 99.9%). The spectrum (at exc =
254 nm) of the single-crystalline TiO2 nanowires displays an
outstanding peak at 380 nm (3.26 eV) while no peak was
obtained from the bulk TiO2 , as shown in figure 5. The PL
spectrum of bulk TiO2 with no peaks has also been observed
by some other groups [20, 33]. Regarding the emission peak,
Grabner et al [34] have reported that excitation of the bandgap
in the TiO2 rutile structure leads to the emission of a free
exciton if the crystal is sufficiently pure. Additionally, Tang
108

Intensity (Arb. Unit)

Figure 4. (a) TEM-cross section image indicating that an individual nanowire was grown on the TiO2 grain; inset (a) reveals the lattice
image of the TiO2 layer; (b) HRTEM image showing an individual TiO2 nanowire grown along the [110] direction; inset (b) shows the
corresponding SAD pattern; (c) schematic diagram depicting nanowires grown on a TiO2 layer via the epitaxial process; (d) EDS analysis of
the TiO2 nanowires.

Wavelength (nm)

Figure 5. PL spectra showing an outstanding emission peak at

approximately 380 nm.

et al [35] explained that single-crystalline rutile TiO2 emits

free excitons, because in this structure the coordination number
(two edges and eight corners) is the largest of all. We therefore
believe that the luminescence behaviour (bandgap excitation)
of single-crystalline rutile TiO2 nanowires was attributable to

Formation and photoluminescence of single-crystalline rutile TiO2 nanowires synthesized by thermal evaporation

free exciton emission [36]. The broadening of the peak in the

range 550600 nm is ascribed to the oxygen vacancies or the
defect state in nanowires [37, 38]. The very weak emission
near the green band is almost negligible, further implying a
low oxygen defect concentration. Simply, this phenomenon
demonstrated that nanowires are strongly crystalline.
Additionally, we found the outstanding peak was at
3.26 eV, in contrast to that of the common rutile TiO2 bandgap
at 3.0 eV, indicating a blue-shift phenomenon appears in our
single-crystalline nanowires. Liang et al and Takagahara et al
[39, 40] reported that this is attributable to the size effect.
This work experimentally elucidates that the singlecrystalline rutile TiO2 nanowires have luminescence properties
and can be selected-area synthesized on the substrate easily.
Additionally, the electronic properties of rutile TiO2 exhibit a
wide direct bandgap [41]. Therefore, it would be an attractive
subject to study the applications of single-crystalline rutile
TiO2 nanowires for optoelectronic devices.

4. Conclusions
Single-crystalline rutile TiO2 nanowires were synthesized
using an RF heater and TiO2 /sapphire substrates. Nanowires
with diameters in the range 50100 nm and lengths 1
2 m were grown in the most thermodynamically stable
[110] direction. The pre-deposited TiO2 layer promotes
the growth of TiO2 nanowires, so selected-area growth was
achieved. Single-crystalline rutile TiO2 nanowires exhibit a
sharp emission peak at 380 nm under PL tests. For the
property, the single-crystalline TiO2 nanowires should be a
candidate of optoelectronic devices.

Acknowledgment
The authors would like to thank the National Science Council
of the Republic of China for financially supporting this research
under contract No NSC 92-2120-E-007-002. The Ministry of
Economic Affairs in Taiwan through project No F446CA1131
is also appreciated.

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