Solid State Communications 150 (2010) 1041–1044

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Solid State Communications

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Synthesis and study of electrical and magnetic properties of vanadium oxide

micro and nanosized rods grown using pulsed laser deposition technique
N. Rama ∗ , M.S. Ramachandra Rao
Nano Functional Materials Technology Centre and Department of Physics, Indian Institute of Technology Madras, Chennai-600036, India

article info abstract

Article history: Vanadium oxide micro and nanosized rods were grown using pulsed laser deposition technique under
Received 16 April 2009 different oxygen pressures. X-ray diffractogram shows a predominant mixture of vanadium dioxide, VO2
Received in revised form and Magneli phase, V3 O7 . The diameters of the rods were found to increase from 300 nm to 2.3 µm
9 November 2009
with increase in oxygen pressure from 0.1 mbar to 0.5 mbar as seen from high resolution scanning
Accepted 9 January 2010
by M. Wang
electron microscope images. Raman spectra of the rods show peaks at all the characteristic vibrations
Available online 25 March 2010 corresponding to that of VOx phase. The 0.5 mbar oxygen deposited sample shows a semiconducting
behavior from 300 to 77 K and is paramagnetic down to 5 K. Using versatile pulsed laser deposition we
Keywords: have established the tunability of the dimensions of VOx nanorods which can find numerous potential
A. Nanostructures applications in electrochemistry, catalysis, etc.
B. Laser processing © 2010 Elsevier Ltd. All rights reserved.

1. Introduction 2. Experimental techniques

Vanadium oxide is one of the most versatile oxides capable of
existing in various forms such as V2 O5 , VO2 , V3 O5 , V3 O7 , V2 O3 ,
VO, V5 O9 to name a few. Most of these compounds, belong to the
Magneli phase which has a generic formula V2 O3 + (n − 2)VO2 =
Vn O2n−1 , which are structurally related. Among these, the most
well studied are V2 O3 and VO2 because of their sharp metal to
insulator transition [1,2]. These materials are found to have many
uses especially as thermochromic coatings, electromechanical
devices, catalysts etc. [3–5]. In view of the importance of vanadium
oxides in different technological applications, the fabrication of
this material in nanostructured form is a particularly attractive
goal. Nanostructures of vanadium oxides have been grown using
various techniques such as sol–gel route [6,7], hydrothermal
route [8,9], atmospheric pressure chemical vapor deposition with
VOCl3 [10], gas phase synthesis [11] etc. In this paper, we have
grown micro and nanoneedles of vanadium oxide (VOx ) using
pulsed laser deposition (PLD) technique. Though PLD has been
widely used for growing nanostructures of other materials such as
ZnO [12], it has not been used much in these vanadium systems. To
our knowledge, this is the first report on growth of vanadium oxide
based nanorods using PLD and also without using any catalysts or
further heat treatment.
Vanadium oxide (VOx ) nano and microsized rods were grown
using pulsed laser deposition technique with V2 O5 as the target.
An n-type Si (100) was used as the substrate. A frequency tripled
pulsed Nd:YAG laser (wavelength 355 nm, pulse width of ∼19 ns
and repetition rate of 10 Hz) with a fluence of 1.5 J/cm2 was
used for ablation. The substrate temperature was maintained at
635 °C. The target–substrate distance was fixed at 4 cm. The oxygen
pressure (O2pp ) was varied from 0.1 mbar to 0.5 mbar during
deposition. Oxygen pressures below 0.1 mbar were seen to result
in smooth films and above 0.5 mbar in morphologies similar to
that of 0.5 mbar sample. The time of deposition was 20 min, which
yielded an approximate thickness of 2000 Å. Phase analysis was
done using X-ray diffraction (PANalytical, Philips). HRSEM was
used for finding out the surface morphology (FEI, Philips). Room
temperature Raman spectra (Lab Ram Jobin Vyon) was measured
using a He–Ne laser in the range of 100 to 1000 cm−1 . Magnetic
studies were done using a VSM in Physical Property Measurement
System (Quantum Design, USA) in field cooled mode in an applied
field of 1000 Oe while magnetic hysteresis was measured from −7
to 7 T on the 0.5 mbar oxygen pressure grown sample. A home-
made resistivity setup was used to measure resistivity from 400 to
77 K in the linear four probe configuration on the 0.5 mbar oxygen
pressure grown sample.

3. Results and discussions

∗ Corresponding address: Department of Physics, IIT-Madras, Chennai-36, India.
Tel.: +91 44 22575912, +91 44 22574872. X-ray diffraction data of the samples are given in Fig. 1. It can
E-mail address: rama@physics.iitm.ac.in (N. Rama). be seen from Fig. 1, that majority of the peaks could be indexed to
0038-1098/$ – see front matter © 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ssc.2010.01.049
1042 N. Rama, M.S. Ramachandra Rao / Solid State Communications 150 (2010) 1041–1044

e These droplets when further zoomed in (inset in Fig. 2(f)), reveals

d from which the rods begin to grow in both length and width. Upon
c with increase in both length (2.2 µm) and width (1.5 µm). The
b frond like structure with a typical diameter of the rod being 2.5 µm
a interwoven mesh like structure (Fig. 2(e)). Only very few droplets
Fig. 1. X-ray diffractogram of VOx nano and microrods. # corresponds to V3 O7
phase while $ corresponds to VO2 phase.
V3 O7 or VO2 phase, though the presence of other VOx phases cannot
be ruled out with the V3 O7 phase becoming more dominant at
higher oxygen pressures. The XRD pattern of the 0.1 mbar sample
could be indexed to the tetragonal phase of both VO2 and V3 O7
while higher oxygen pressures result in the monoclinic phase. Thus
the system shows a mixed valence of 4+ and 5+ which is useful for
electrochemical applications [13,14] The main advantage of using
PLD is that it does not leave any impurity like the solution based
synthesis method [15] or time consuming like the hydrothermal
synthesis route.
High Resolution Scanning Electron Microscopy images are given
in Fig. 2. It is seen that, as the O2 pp varies, the surface morphology
of the samples varies systematically from that of small tetrahedral
rods for 0.1 mbar to that of interwoven mesh like rods for that
of 0.5 mbar. The length of the rods also increases with increase
in O2 pp. The typical size of the rod for the 0.1 mbar grown
sample was seen to be 300 nm in diameter (Fig. 2(a)) with the
size changing to 620 nm (Fig. 2(b)) upon increasing the O2 pp to
0.2 mbar. Apart from these rods like structures for the 0.2 mbar
sample, circular droplets (Fig. 2(f)) like structures are also seen.
that they are collection of small nanosized rods which are just
beginning to grow. These tend to act like the nucleation centres
further increase of O2pp to 0.3 mbar these rods are seen to begin
to merge with one another with offshoots branching out (Fig. 2(c))
droplets are observed in this case also. For the 0.4 mbar sample,
these offshoots further grow in both length and size resulting in a
(Fig. 2(d)). This sample also shows a large equi-spaced distribution
of droplets interspersed between the nano/microrods. At 0.5 mbar
all the nearby fronds merge with each other resulting in a highly
were seen which implies all the nucleation centres have resulted
in promoting both these micro and nanosized rods which results
in the highly dense mesh like structure.
This variation of the surface morphology of the vanadium oxide
rods with oxygen pressure can be explained as follows: As the laser
hits the target, it gets ablated and due to the presence of oxygen in
the chamber, collisions occur between the oxygen molecules and
the ablated species. This results in the condensation and formation
of nanoparticles in the gas phase [16]. Due to the ad-atom mobility
with the energy supplied via substrate heating, these particles fuse
together to form the small rods or platelets as seen in Fig. 2(a) for
the 0.1 mbar sample. However, not enough nucleation sites are
present for it to increase in length or width. So they remain small in
dimension. As the oxygen pressure becomes higher, the number of
collisions of the ablated species with oxygen molecules increases,
and the plume becomes bigger which results in an increase in
the number of nanoparticles which arrive at the substrate. These
particles then form nucleation centres for the rod growth (similar
to the droplets seen in Fig. 2(f)). These droplets then coagulate with
each other due to the presence of sufficient thermal energy to form
rods. This is also supported by the fact that the density of these
rods decreases with increase in O2pp however with an increase
in dimensions. As we still increase the O2pp , the nucleation sites
formed will be much higher in number and much more reactive
because of their nano size. This results in the fusion of the rods
not only along the length but also along the sides which results
in the branching as seen from 0.3 sample onwards. These rods
still coagulate along all directions further to give microrods with

Fig. 2. HRSEM pictures of the rods grown at (a) 0.1 mbar (b) 0.2 mbar (c) 0.3 mbar (d) 0.4 mbar (e) 0.500 mbar and of droplets (f) in 0.2 mbar. Inset in (f) shows the magnified
picture of the droplets.
 N. Rama, M.S. Ramachandra Rao / Solid State Communications 150 (2010) 1041–1044
Fig. 3. Room temperature Raman spectra of the rods.
interwoven mesh similar to that for the 0.5 mbar sample. This
tunability of the size of the vanadium oxide rods with oxygen
pressure and also their multivalent nature will help in its various
applications where specific dimensions of the rods are required
and in electrochemical applications, catalysis etc.
Raman spectra of our VOx nanorods synthesized by PLD are
shown in Fig. 3. The nanorods show characteristic peaks of
vibrations corresponding to both VO2 phase and V3 O7 phase or in
general the VOx phase. Since the relative concentrations of VO2
and V3 O7 are different in each case because of different oxygen
pressure during growth, the peak intensities are different. It is seen
that in the range of 100 to 1000 cm−1 , the dominant peaks are
at 146, 225, 256, 695 and 944 cm−1 while the peaks at 305, 437,
622, 823 and 992 cm−1 are somewhat less intense. The mode at
992 cm−1 corresponds to the terminal oxygen (V = O) stretching
mode which results from an unshared oxygen [17] while the mode
at 944 cm−1 corresponds to V4+ –O [18]. The mode at 695 cm−1 is
assigned to the double coordinated oxygen (V2 –O) stretching mode
which results from corner shared oxygen’s in common to two
pyramids [19]. The peaks at 256, 437 and 823 cm−1 corresponds to
the Bg modes of VO2 [20] or could be due to the bending vibration
modes of the V3 –O, V2 –O and V = O bonds in a disordered V–O–V
framework. The modes at 225, 305 and 622 cm−1 corresponds to
the Ag modes of VO2 [20]. The lower frequency Raman peak at
146 cm−1 is assigned to the stretching mode of (V2 O2 )n which
correspond to the chain translation [19]. The fact that all the
observed peaks could be identified implies that the samples do
not contain any other contamination and are only because of VOX
phase.
Electrical resistivity of the 0.5 mbar oxygen partial pressure
deposited sample was measured from 400 to 80 K and is shown
in Fig. 4(a). It was seen that sample was highly resistive and shows
a semiconducting behavior through out the measured temperature
range. Similar behavior was observed in other samples also,
with the samples being too resistive to measure. The high
resistance value could be due to the fact that these rods are
not interconnected (as seen from Fig. 2) with each other and so
inter rod scattering is expected to be high. Since the sizes of the
rods are much smaller than this sample in other cases, the inter
rod scattering is expected to be higher resulting in such large
resistances. However it is interesting to note that it does not show
TMI corresponding to VO2 (TMI = 340 K) even though VO2 phase is
present albeit in small proportion compared to V3 O7 . This can be
explained as follows: The TMI in VO2 is thought to occur because
of a first order structural transition from a monoclinic structure
1043
a c
Fig. 4. (a) Temperature variation of electrical resistivity. (b) Temperature variation
of magnetization in field cooled mode of 1000 Oe. (c) Magnetic hysteresis from
−7 kOe to +7 kOe at 6 K.
to a rutile tetragonal structure. The transition occurs because of
the displacement of V atoms perpendicular to the C axis [21].
This structural transition is disrupted due to the presence of other
phases like V3 O7 . A similar behavior was reported by Okimura et al.
in VO2 thin films [22]. This is also corroborated from our Raman
data where modes corresponding to a disordered V–O–V network
are seen.
Magnetization and magnetic hysteresis of the sample deposited
at 0.5 mbar is shown in Fig. 4(b) and (c). V3 O7 is paramagnetic and
semiconducting down to 5 K [23] while VO2 is paramagnetic above
340 K and diamagnetic below [24,25]. It is seen from Fig. 4 that
the 0.5 mbar sample shows a paramagnetic behavior up to 5 K. For
the other samples the signals were very weak and therefore noisy.
The hump like behavior around 350 K and 50 K could be due to
the presence of other vanadium oxide phases like V4 O7 and V7 O13
which have Neel temperature around that region [26]. Magnetic
hysteresis at 6 K shows that the magnetic moment does not even
saturate at 7 T showing that it is a robust paramagnet.
In conclusion we have grown micro and nanosized VOx rods
using pulsed laser deposition method under different oxygen
partial pressures. Raman spectra shows all modes which corre-
spond to VOx groups. Electrical resistivity measurement shows
that the samples are highly resistive. Magnetic measurements on
the 0.5 mbar grown show that they are in a robust paramagnetic
state down to 5 K.
Acknowledgements
NR would like to thank the Department of Science and
Technology (DST), SERC, New Delhi for the award of a project under
the Scheme for Young Scientists (SR/FTP/PS-16/2006). MSR would
like to thank the Department of Science and Technology for the
project ‘‘Establishment of Nano Functional Materials Technology
Center’’ at IIT-Madras.
References
[1] N.F. Mott, Metal-Insulator Transitions, Taylor & Francis, London, 1990.
[2] M. Imada, A. Fujimori, Y. Tokura, Rev. Modern Phys. 70 (1998) 1039.
[3] P. Jin, G. Xu, M. Tazawa, K. Yoshimura, Appl. Phys. A 47 (2003) 455;
G.C. Granqvist, Sol. Energy Mater. Sol. Cells 91 (2007) 1529.
[4] L.Q. Mai, W. Chen, Q. Xu, J.X. Zheng, M.Z. Ke, Mater. Rev. 16 (2002) 39.
[5] N. Magg, J.B. Giorgi, M.M. Frank, B. Immaraporn, T. Schroeder, M. Baumer,
H.J. Freund, J. Am. Chem. Soc. 126 (2004) 3616.
[6] Sudip Mukherjee, Arun Kumar Pal, J. Phys.: Condens. Matter 20 (2008) 255202.
[7] G.T. Chandrappa, N. Steunou, S. Cassaignon, C. Bauvais, P.K. Biswas, J. Livage,
Sol-Gel Sci. Technol. 26 (2003) 593.
1044 N. Rama, M.S. Ramachandra Rao / Solid State Communications 150 (2010) 1041–1044
[8] F. Sediri, N. Gharbi, Mater. Lett. (2008), doi:10.1016/j.matlet.2008.08.022.
[9] Beibei Li, Xiaomin Ni, Fu Zhou, Jing Cheng, Huagui Zheng, Mingrong Ji, Solid
State Sci. B 8 (2006) 1168.
[10] U. Qureshi, T.D. Manning, I.P. Parkin, J. Mater. Chem. 14 (2004) 1190.
[11] O.P. Vinogradova, A.I. Sidorov, V.A. Klimov, E.B. Shadrin, A.V. Nashcheki,
S.D. Khanin, V.Yu. Lyubimov, Phys. Solid State 50 (2008) 1227.
[12] D. Valerini, A.P. Caricato, M. Lomascolo, F. Romano, A. Taurino, T. Tunno,
M. Martino, Appl. Phys. A 93 (2008) 729.
[13] P. Barboux, N. Baffier, R. Morineau, J. Livage, Solid State Protonic Conductors
III, Odense University Press, Paris, 1985, p. 173.
[14] J. Livage, Mater. Res. Soc. Symp. Proc. 32 (1984) 125.
[15] Guicun Li, Kun Chao, Hongrui Peng, Kezheng Chen, Zhikun Zhang, Inorg. Chem.
46 (2007) 5787.
[16] R.Q. Guo, J. Nishimura, M. Matsumoto, D. Nakamura, T. Okada, Appl. Phys. A 93
(2008) 843.
[17] J.H. Clark, The Chemistry of Titanium and Vanadium, Elsevier Press, New York,
1968.
[18] Se-Hee Lee, Hyeonsik M. Cheong, Maeng Je Seong, Ping Liu, C. Edwin Tracy,
Angelo Mascarenhas, J. Roland Pitts, Satyen K. Deb, Solid State Ionics 165
(2003) 111.
[19] C. Juloen, G.A. Nazri, O. Bergstrom, Phys. Stat. Solidi B 201 (1997) 319.
[20] P. Schilbe, D. Maurer, Mater. Sci. Eng. A 370 (2004) 449.
[21] A. Zylbersztjen, N.F. Mott, Phys. Rev. B 11 (1975) 4383.
[22] Kunio Okimura, Naotaka Kubo, Thin Solid Films 515 (2007) 4992.
[23] Michel Bayard, Jean-Claude Grenier, Michel Pouchard, Paul Hagenmuller,
Mater. Res. Bull. 9 (1974) I137.
[24] M. Abbate, Braz. J. Phys. 24 (1994) 785.
[25] H. Abe, M. Terauchi, M. Tanaka, S. Shin, Y. Ueda, Jpn. J. Appl. Phys. 36 (1997)
165.
[26] A.C. Gossard, J.P. Remeika, T.M. Rice, H. Yasuoka, Phys. Rev. B 9 (1974) 1230.