ARTICLE IN PRESS

Journal of Crystal Growth 256 (2003) 8388

Growth of TiO2 nanorods by metalorganic chemical

vapor deposition
Siddhartha K. Pradhan*, Philip J. Reucroft, Fuqian Yang, Alan Dozier
Department of Chemical and Materials Engineering, University of Kentucky, 177 Anderson Hall, Lexington, KY 40506, USA
Received 27 November 2002; accepted 6 May 2003

Abstract
The growth of TiO2 nanorods on a WCCo substrate by metalorganic chemical vapor deposition has been observed
by SEM and TEM. The nanorods diameter and length were about 50100 nm and 0.52 mm, respectively. Nanorod
growth was observed at 500 C, while mostly particles were deposited at 600 C and a thin coating was formed at 400 C.
It appears that the presence of cobalt catalyzes the directional growth of TiO2 and NH3 enhances this growth behavior.
In the presence of NH3, thinner and longer nanorod growth was observed.
r 2003 Elsevier B.V. All rights reserved.
PACS: 61.46.+w; 61.82.Rx; 81.20.Ka; 83.80.Pc
Keywords: A3. Metalorganic chemical vapor deposition; B1. Nanorods; B1. Nanowires; B1. Titanium oxide

1. Introduction
Nanoscaled materials are of great interest for
their unique structure and properties [13]. The
observation of carbon nanotubes in 1991 [2] and
the rapid development of carbon nanotube studies
since then have resulted in increased interest in the
study and processing of other nano-structured
materials [1,4,5]. Nanowires and nanorods of
various compositions have been synthesized for
potential use as quantum wires in nanodevices, as
photocatalysts, as mesoporous structures, and for
other functional applications [5,6]. Commonly
used methods for the synthesis of nanomaterials
*Corresponding author. Tel.: +1-(859)-4205211; fax: +1(859)-3231929.
E-mail address: skprad0@engr.uky.edu (S.K. Pradhan).

include solgel, hydrothermal synthesis, vaporphase transport, electrochemical synthesis, arc

discharge, laser ablation and CVD [79].
There are many potential applications of TiO2
nanorods/nanowires, including use as a photocatalyst [6], a catalyst support [10], a gas and
humidity sensor [11], and in a photochemical solar
cell [12]. There is also a report that TiO2 nanowire
has a strong photoluminescence band in the bluegreen wavelength range [13]. Currently, TiO2
nanowires have been processed by a hydrolysis
method using TiCl3 [14], by a TiO2 nanoparticlesolution method [13], and a highly ordered TiO2
nanowire array has been prepared by a solgel
method on an alumina membrane [15]. So far there
is no report of TiO2 nanowires or nanorods
synthesized by CVD methods, even though the
CVD process has been used to synthesize

0022-0248/03/$ - see front matter r 2003 Elsevier B.V. All rights reserved.
doi:10.1016/S0022-0248(03)01339-3

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nano-structures and nanowires of various materials [16,17].

In this communication, the synthesis of TiO2
nanorods by a metalorganic chemical vapor
deposition (MOCVD) process is described. TiO2
nanorods were grown on WCCo substrates with
and without the presence of NH3. Titanium-tetraisopropoxide (TTIP) was used as the metalorganic
precursor for this process. In the following
sections, details of the experimental procedure,
characterization of the samples, and discussion of
the results will be presented.

2. Experimental procedure
TTIP, purity 97%, supplied by Alfa Aesar,
Ward Hill, MA, was used as a precursor. Argon
was bubbled through TTIP liquid, maintained in a
stainless steel bubbler at 60 C, to carry TTIP
vapor to the reactor. Low pressure MOCVD was
conducted in a cold wall, vertical reactor with a
graphite susceptor to hold the WCCo substrate.
The substrates, model CNMA433 NOHONE
KC9120, were used as-received from Kennametal
Inc., Latrobe, PA, i.e., without polishing or
chemical treatment. The substrate to be coated
was dipped in acetone and then ultrasonically
cleaned in DI water prior to the deposition
experiment. The total deposition time for each
experiment was 90 min. A Hitachi S-3200 scanning
electron microscope was used for SEM and EDS
work and a Jeol-2000fx transmission electron
microscope was used for TEM analysis. Samples
were sputter-coated with AuPd for SEM work to
reduce electrostatic charging. For the TEM
analysis, deposited material was scraped directly
onto a carbon coated 300 mesh copper grid.

3. Results and discussion

Fig. 1ac shows the morphologies of deposited
TiO2 on WCCo substrates at three different
substrate temperatures. Growth of TiO2 nanorod
was observed at 500 C, but particle-like growth
was observed at 600 C and a thin coating was
deposited at 400 C. It appears that there is a

temperature window for the growth of TiO2

nanorods under the given process conditions300 sccm TTIP carrier ow, 0800 sccm NH3 ow,
500800 sccm argon ow and 50 Torr system
pressure. From the micrographs in Figs. 13, the
estimated diameter and length of the nanorods are
about 50100 nm and 0.52 mm, respectively.
These nanorods are anatase TiO2, which is a
stable TiO2 phase at low temperature. A TiO2
nanorod and the corresponding selected area
electron diffraction (SAED) pattern are shown in
Figs. 2d and e, respectively. Fig. 2e ts the anatase
TiO2 [0 0 1] zone axis SAED pattern. The pattern
in Fig. 2e is indexed in accordance with the Cerius2
software package, supplied by Accelrys, San
Diego, CA. The SAED pattern in Fig. 2e clearly
shows the tetragonal symmetry of the anatase
lattice.
In a preliminary study it was found that the
presence of NH3 inuences the growth of the TiO2
nanorods. Fig. 2a shows nanorod growth when
NH3 gas is introduced to the system. The inset in
Fig. 2a shows a SEM image of an isolated
nanorod. TEM images of TiO2 nanorods are
shown in Figs. 2b and c; these images show
clusters of nanorods and nanoparticles, agglomerated during TEM sample preparation. Comparing
the micrographs in Fig. 2a to those in Figs. 1d and
e (deposition without NH3), it appears that when
NH3 is used there is an increase in length and a
decrease in diameter. There is also increase in
growth density of the TiO2 nanorods. However, an
increase in NH3 ow rate, from 300 to 800 sccm,
does not affect the growth process. The introduction of NH3 has not resulted in incorporation of
nitrogen atoms into the structure, as conrmed by
EDS, which is shown in Figs. 2f and g. The effect
of NH3 on nanostructure growth is not unusual.
Jung et al. [18] have grown carbon nanotubes by a
CVD method in a NH3 environment. They have
reported that activated nitrogen atoms affect the
growth kinetics on a Ni or Co catalyst surface.
Also there has been a report of increased ZnO
nanowire growth when H2 gas treatment was
conducted at 525575 C [7]. It seems that a
reducing environment, such as NH3 or H2,
enhances the one-dimensional nanostructure
growth in a vapor deposition process. In a separate

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85

Fig. 1. Growth morphology of TiO2 deposits on WCCo substrate at 600 C (a), 500 C (b), and 400 C (c). The processing parameters
were: 300 sccm TTIP carrier gas ow, 300 sccm NH3 ow, 500 sccm argon ow, and 50 Torr system pressure. (d) A cluster of TiO2
nanorods, and (e) an isolated TiO2 nanorod. The processing paprameters for these samples were: 300 sccm TTIP carrier gas ow,
500 sccm argon ow, and 50 Torr system pressure.

study, it was found that variation in the total ow

rate affected the nanorod growth morphology. As
shown in Fig. 3, when the ow rate of argon
(diluent gas) decreased from (a) 800 to (b)
500 sccm, the nanorod length and growth density
decreased.
In all the experiments, it was observed that the
nanorod growth density was higher on cobalt rich
areas on the substrate surface. An EDS analysis of
a high density growth area, shown in Fig. 2f,
revealed that there was a more intense titanium

and oxygen signal when there was a signal from

cobalt. There was a reduced signal from titanium,
oxygen and no signal from cobalt when a deserted
area was analyzed, as shown in Fig. 2g. Also, when
a single nanorod was analyzed in the TEM, the
EDS spectrum showed the presence of cobalt
along with oxygen and titanium. Cobalt thus
appears to play an important role in the growth
of 1-D TiO2. This is consistent with reports [19,20]
on the use of cobalt as a catalyst for the growth of
other nanostructures, such as carbon nanotubes.

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86

(b)

(a)

(c)

(e)

360
340
320
300
280
260
240
220
200
180
160
140
120
100
80
60
40
20
0

(f)

W
O Co

Au

Counts

Counts

(d)

C
Pd
Ti

0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2 2.2 2.4 2.6 2.8 3 3.2 3.4 3.6 3.8 4 4.2 4.4 4.6

Energy (keV)

400
380
360
340
320
300
280
260
240
220
200
180
160
140
120
100
80
60
40
20
0

(g)

W
W

Au
C

Pd
Ti

0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2 2.2 2.4 2.6 2.8 3 3.2 3.4 3.6 3.8 4 4.2 4.4 4.6

Energy (keV)

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87

Fig. 3. SEM micrograph of TO2 nanowires deposited without NH3 at 500 C; (a) with 800 sccm argon ow, and (b) with 500 sccm
argon ow. The processing parameters were: 300 sccm TTIP carrier gas ow and 50 Torr system pressure.

4. Conclusions
The growth of TiO2 nanorods by a MOCVD
process on a WCCo substrate at 500 C is
described. The diameter and length of the nanorods are about 50100 nm and 0.52 mm, respectively. The use of NH3 results in thinner, longer
TiO2 nanorods. It appears that the presence of
cobalt catalyses the 1-D growth of TiO2 nanorods.

Acknowledgements
A research assistantship provided by the Center
for Robotics and Manufacturing Systems
(CRMS), University of Kentucky, is acknowledged by Siddhartha K. Pradhan. Help in SEM

work by Larry Rice is appreciated. Thanks are due

to Dr. Pankaj Mehrotra, Kennametal Inc., for
providing WCCo tool bits.

References
[1] M. Terrones, W.K. Hsu, H.W. Kroto, D.R.M. Walton,
Top. Curr. Chem. 199 (1999) 190.
[2] S. Iijima, Nature 354 (1991) 56.
[3] A.M. Morales, C.M. Lieber, Science 279 (1998) 208.
[4] G. Timp (Ed.), Nanotechnology, Springer, New York,
1999.
[5] J.T. Hu, T.W. Odom, C.M. Lieber, Acc. Chem. Res. 32
(1999) 435.
[6] Z.-R. Tian, W. Tong, J.-Y. Wang, N.G. Duan,
V.V. Krishnan, S.L. Suib, Science 276 (1997) 926.
[7] M.H. Huang, Y. Wu, H. Feick, N. Tran, E. Weber,
P. Yang, Adv. Mater. 13 (2001) 113.

Fig. 2. (a) SEM micrographs of TiO2 nanorods deposited with NH3 at 500 C; the inset shows an isolated TiO2 nanorod. (b) and (c),
TEM images of clustered TiO2 nanorods and nano-particles. The processing parameters were: 300 sccm TTIP carrier gas ow, 300 sccm
NH3 ow, 500 sccm argon ow, and 50 Torr system pressure. (d) and (e) show a TEM images of a nanorod and the corresponding
anatase TiO2 [0 0 1] zone axis SAED pattern, respectively. (f) and (g) show EDS spectra from a high-density growth area and a deserted
area, respectively. The Au and Pd signals in the EDS spectra are from the conducting coating applied to reduce charging during SEM
observation.

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[8] Y.Q. Zhu, W.K. Hsu, M. Terrones, N. Grobert, H.

Terrones, J.P. Hare, H.W. Kroto, D.R.M. Walton,
J. Mater. Chem. 8 (1998) 1859.
[9] Y.Q. Zhu, W.B. Hu, W.K. Hsu, M. Terrones, N. Grobert,
J.P. Hare, H.W. Kroto, D.R.M. Walton, H. Terrones,
J. Mater. Chem. 9 (1999) 3173.
[10] S. Matsuda, Appl. Catal. 8 (1983) 149.
[11] Y.C. Yeh, T.T. Tseng, D.A. Chang, J. Am. Ceram. Soc. 73
(1990) 1992.
[12] B. ORegan, M. Gratzel, Nature 353 (1991) 737.
[13] Y.X. Zhang, G.H. Li, Y.X. Jin, Y. Zhang, J. Zhang, L.D.
Zhang, Chem. Phys. Lett. 365 (2002) 300.
[14] Y. Lei, L.D. Zhang, J.C. Fan, Chem. Phys. Lett. 338
(2001) 231.

[15] Y. Lei, L.D. Zhang, G.W. Meng, G.H. Li, X.Y. Zhang,
C.H. Liang, W. Chen, S. Wang, Appl. Phys. Lett. 78
(2001) 1125.
[16] N.M. Hwang, W.S. Cheong, D.Y. Yoon, D.-Y. Kim,
J. Crystal Growth 218 (2000) 33.
[17] S.R. Qi, X.T. Huang, Z.W. Gan, X.X. Ding, Y. Cheng,
J. Crystal Growth 219 (2000) 485.
[18] M. Jung, K.Y. Eun, Y.-J. Baik, K.-R. Lee, J.-K. Shin,
S.-T. Kim, Thin Solid Films 398399 (2001) 150.
[19] J.S. Lee, G.H. Gu, H. Kim, J.S. Suh, I. Han, N.S. Lee,
J.M. Kim, G.-S. Park, Synth. Met. 124 (2001) 307.
[20] C.J. Lee, J. Park, J.A. Yu, Chem. Phys. Lett. 360 (2002)
250.