Vacuum 82 (2008) 821826

The effect of heating time on growth of Na

x
WO
3
nanowhiskers
R. Azimirad
a
, M. Goudarzi
a
, O. Akhavan
a
, A.Z. Moshfegh
a,b,
a
Department of Physics, Sharif University of Technology, P.O. Box 11155-9161, Tehran, Iran
b
Institute for Nanoscience and Nanotechnology, Sharif University of Technology, P.O. Box 14588-89694, Tehran, Iran
Received 8 July 2007; received in revised form 27 November 2007; accepted 27 November 2007
Abstract
A simple method for synthesis of Na
x
WO
3
nanowhiskers on tungsten thin lms with 40 nm thickness sputtered on soda lime substrate
as a source of sodium atoms has been reported for the rst time. After heat treatment of the W thin lms at 650 1C in N
2
ambient for
different times (15, 80 and 180 min), crystalline Na
x
WO
3
nanowhiskers with [0 0 1] direction were obtained. scanning electron microscopy
(SEM), X-ray diffractometry (XRD), X-ray photoelectron spectroscopy (XPS) and optical transmission/reection measurements were
employed to determine various properties of the grown nanowhiskers. Experimental results revealed that size and density of
nanowhiskers were dependent on the annealing time and found that the 80-min heat treatment was a proper time for the growth of
sodium-doped tungsten oxide nanowhiskers, in our experimental conditions. According to SEM observations, the synthesized
nanowhiskers have 70300 nm in width and 110 mm in length. It was also observed that by increasing the heating time to 180 min
resulted in diffusion of the nanowhiskers into the substrate.
r 2007 Elsevier Ltd. All rights reserved.
PACS: 81.07.b; 81.16.Hc
Keywords: Na
x
WO
3
; Nanowhiskers; SEM; XRD
1. Introduction
As a fully oxidized tungsten oxide compounds with
different structures, tungsten bronzes (M
x
WO
3
) have
drawn considerable attention in recent decades for their
unique properties such as the successive phase transition
over the range of temperatures, high electrical conductivity
and some interesting magnetic properties [1,2]. Tungsten
bronzes have found technological applications in electro-
chromic devices, humidity sensors, solid fuel cells, second-
ary batteries, ion sensitive electrodes, etc. Among different
known tungsten bronzes, the sodium tungsten bronzes
have been of great interest ever since their discovery by
Wo hler [3], due to variation of their electronic and optical
properties with composition. It is known that Na
x
WO
3
are
n-type semiconducting for xo0.25 but metallic for
x40.25; meanwhile, colors range from blue to violet to
coppery then to yellow-gold as x changes from 0.4 to 0.98.
In addition, the crystalline structure of Na
x
WO
3
is strongly
dependent on the x values [4].
Recent advances in the eld of nanotechnology have led
to the synthesis and characterization of a class of quasi-
one-dimensional (Q1D) structures. Nanowires, nanorods,
nanowhiskers and nanobelts constitute an important
class of Q1D nanostructures, which provide models to
study the relationship between electrical transport, optical
and other properties with dimensionality and size conne-
ment. In recent years, a variety of inorganic materials
nanowhiskers has been synthesized and characterized as
active components in future devices. In this regard,
nanowhiskers of elements, oxides, nitrides, and carbides
have been produced by employing various strategies [5,6].
Among these various classes of materials, tungsten oxides
have been applied to photocatalysis, photochromic and
electrochromic devices, as well as gas sensors for many
years. For improvement in the device performance, the
nanostructured tungsten oxides may also potentially be
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doi:10.1016/j.vacuum.2007.11.012

Corresponding author at: Department of Physics, Sharif University of

Technology, P.O. Box 11155-9161, Tehran, Iran. Tel.: +98 21 6616 4516;
fax: +98 21 6607 2636.
E-mail address: moshfegh@sharif.edu (A.Z. Moshfegh).
used for these technological applications [79]. Recently,
different methods for growing Q1D nanostructure of
tungsten oxide doped with potassium [1012], lead [13],
molybdenum [14] and boron [15] were reported. More-
over, Cao et al. [16] recently published a hydro-
thermal synthesis of sodium tungstate nanorods and
nanobundles. To the best of our knowledge, there was no
report about growing of Q1D nanostructure of sodium-
doped tungsten oxide with vaporliquidsolid (VLS)
method, yet.
In this paper, for the rst time, we have studied the
effects of heating time on growth of sodium-doped
tungsten oxide nanowhiskers from sputtered W thin lms
by using the sodium existing in soda lime substrates. The
grown samples containing sodium-doped tungsten oxide
nanostructures were characterized and analyzed by scan-
ning electron microscopy (SEM), X-ray diffractometry
(XRD), X-ray photoelectron spectroscopy (XPS) and
UVvis spectrophotometry.
2. Experimental
Initially, thin lms of tungsten were deposited on soda
lime substrates by using DC magnetron sputtering
technique. The base pressure and Ar (99.999%) sputtering
pressure were 2 10
6
and 5 10
3
Torr, respectively.
Before the deposition process, a pre-sputtering was
performed for about 2 min. The discharge power to grow
W thin lms was about 22 W which resulted in a deposition
rate of 8.5 nm/min. Thickness of the deposited lms was
kept about 40 nm monitored in situ by a quartz crystal
oscillator and measured by an optical technique. The
distance between the target in down position and the
substrate in up position was 40 mm. Some details of the
sputtering system arrangement were schematically reported
elsewhere [17]. The reaction of nanowhisker growth was
carried out in a furnace with horizontal quartz tube at
650 1C for different heating times namely: 15, 80 and
180 min. The deposited samples were placed on an alumina
boat located in the center of the furnace. After heating the
samples in N
2
(99.999%) environment with a constant ow
rate of 400 standard cubic centimeters per minute (sccm)
for different times, the furnace was cooled down to room
temperature rapidly.
Surface morphological characteristics of the lms were
observed by SEM. Phase formation and crystallographic
orientation of the samples were investigated by XRD using
Cu K
a
radiation source. XPS with Al K
a
anode and X-ray
incident energy of 1486.6 eV was employed to characterize
the atomic composition and chemical state of the samples
at the surface. All binding energy values were determined
by calibrating the C(1s) core level to 285.0 eV as a reference
point. Optical transmission and reection measurements of
the prepared samples were performed in a range of
3001100 nm wavelength using an UVvisible spectro-
photometer with resolution of 1 nm.
3. Results and discussion
The SEM images of the W lms after the thermal
annealing at 650 1C for different times (15, 80 and 180 min)
are shown in Fig. 1 as compared to the as-deposited lm.
As can be seen in Fig. 1(a), the as-deposited W thin lm
has a smooth surface without any nanostructures. After
annealing the W lm for 15 min, low-density nanowhiskers
with dimensions of 70 nm in width and 1 mm in length
grew horizontally on the surface (Fig. 1(b)). As illustrated
in Fig. 1(c), density of the grown whiskers in different
orientations as well as their width and length increased
after heat treatment for 80 min. Meantime, as shown in
Fig. 1(d), there are still the nanowhiskers with dimensions
similar to those that were observed for the 15-min
annealing time. However, by further increasing the heating
time to 180 min (Fig. 1(e)), these characteristics were not
mainly changed and only the whiskers diffused into
substrate due to its softening (softening point of soda lime
substrate is about 726 1C).
To determine the surface chemical composition of
the synthesized nanostructures, XPS technique was used.
Fig. 2(a) shows XPS survey scans of the samples annealed
at 650 1C for different times as compared to the spectrum
of the as-deposited W lm (0 min). It can be seen from
the gure that only tungsten and oxygen peaks with a trace
amount of surface physisorbed carbon and nitrogen are
present on the surface. No other impurities exist on the
surface for the as-deposited lm. After the annealing
process for 15 min, nitrogen peak, N(1s), disappeared
(because WO
3
is not a nitrogen getter as compared to W
metal) while sodium peak, Na(1s), appeared. The latter
peak is related to sodium existing in the substrate which
out-diffused to the surface after annealing the sample. In
addition, after the heat treatment, silicon peaks from the
substrate was also observed in the XPS spectra. The molar
concentration of O, W, Na and Si for the samples annealed
for the different times was measured from O(1s), W(4f),
Na(1s) and Si(2p) XPS core level peaks and that they have
been presented in Fig. 2(b). It is seen that by increasing the
heat treatment time, the molar concentration of sodium
and silicon increased on the surface which was related to
softening soda lime substrate and diffusion of these
elements onto surface.
Fig. 2(c) shows W(4f) core level of XPS spectrum of the
thin lm after the annealing process for different times in
the binding energy range of 4130 eV. It is well established
that the binding energy of W(4f
7/2
) core level for metallic
W
0
, W
4+
, W
5+
and W
6+
states are 31.4, 32.7, 34.1 and
35.8 eV, respectively. In this range, there are also W(4f
5/2
)
peaks for all these chemical states with 2.15 eV spinorbit
separation and 0.75 area ratio, relative to the correspond-
ing W(4f
7/2
) peaks [18]. As can be seen from Fig. 2(c), for
the as-deposited thin lm (0 min), the tungsten is mainly
in the metallic state, and there are some different oxides
states related to formation of native oxide on the surface
after the deposition. By increasing the heating time, the
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R. Azimirad et al. / Vacuum 82 (2008) 821826 822
metallic state disappeared and the amount of the surface
tungsten in the W
6+
chemical state increased.
XRD technique was also performed to analyze and
identify phase formation and crystallographic structure of
the samples. Fig. 3 illustrates XRD spectra of the samples
after the heat treatment at 650 1C for different annealing
times as compared to the as-deposited sample (0 min). In
our case, due to presence of (2 1 1) plane, the crystalline
structure of the as-deposited lm is identied as b-W
phase with the equilibrium bcc structure with 0.52 nm
lattice parameter. It is important to note that residual
stresses in monolithic W lm are sensitive and exhibit
thickness dependence, especially for tungsten thickness less
than 260 nm and in the low lm thicknesses, the b-W phase
is favorable state [19]. In addition, Chen et al. [20] showed
that, based on the experimental conditions, the lattice
parameter of b-W varies from 0.496 to 0.518 nm, so that
our obtained value is in agreement with their results.
According to the Scherrer equation, the crystalline size of
the tungsten lm was estimated about 20 nm. After the
annealing process and out-diffusion of sodium, the
observed diffraction peaks are attributed to the cubic
structure of Na
x
WO
3
phase. The Na content (x) in the
cubic Na
x
WO
3
can be calculated from the experimentally
measured lattice parameter a
0
using the following reported
relation [21,22]:
a
0

A 3:7845 0:0820x. (1)
The values of x in the Na
x
WO
3
nanostructures for the
samples annealed at different temperatures, calculated
from the above equation, have been listed in Table 1. It
should be noted that this equation is correct in the range of
0.3pxp0.85.
As can be seen from Fig. 3, (0 0 1) is the intensive peak
for the annealed samples because [0 0 1] is the major growth
orientation for Q1D nanostructures [10,23,]. Moreover,
remaining b-W (2 1 1) phase after 15 min heat treatment
shows that the lm was partially oxidized and the metal
tungsten still exists. But, this peak disappeared after 80 min
heat treatment indicating the tungsten lm was completely
oxidized under these conditions.
The optical transmission and reection spectra of the
as-deposited (0 min) and annealed lms for different
times in a range of 3001100 nm wavelength have been
shown in Fig. 4. It is seen that, the transmittance and
reectance of the as-deposited lm is lower than 8% and
around 30%, respectively. In addition, the transmittance
decreases linearly in visible range and becomes zero at
348 nm. These optical properties are in agreement with
metallic property of tungsten thin lms [24,25]. By
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Fig. 1. SEM images of sodium-doped tungsten oxide nanowhiskers after heat treatment in N
2
atmosphere at 650 1C for different times:
(a) 0 (as-deposited), (b) 15, (c) 80, (d) 80 with a higher magnication and (e) 180 min.
R. Azimirad et al. / Vacuum 82 (2008) 821826 823
increasing the heating time, the transmittance increased
while the reectance decreased. Moreover, the absorption
edge is shifted toward blue and it was determined at 320 nm
for the annealed lms. The increase of transmittance and
the occurrence of the blue-shift for the absorption edge are
associated to surface oxidation of the lms and tungsten
oxide formation. It is to note that a pure WO
3
thin lm is
highly transparent with 470% transmittance [26,27]. The
low transmittance of the annealed samples even for 180 min
ones is related to presence of sodium [21]. However, the
reduction of the reectance is attributed to rise of surface
roughness after growth of the nanowhiskers.
Finally, to understand the role of sodium in growth of
tungsten oxide nanowhiskers, a sample was prepared under
the similar growth conditions and parameters, but on a
different substrate. SiO
2
/Si(1 0 0) system (the oxidized Si
layer was prepared in O
2
ambient at 900 1C for 120 min)
was used as a substrate instead of the soda lime for growing
tungsten layer by using the same sputtering conditions.
After the annealing process for 80 min, only nanoparticles
and microparticles were observed by using SEM, without
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15 20 25 30 35 40 45 50
I
n
t
e
n
s
i
t
y

(
a
.
u
.
)
(
0
0
1
)
(
0
0
2
)
(
1
1
1
)

-
W
(
2
1
1
)
(
0
1
1
)
a)
c)
b)
x20
d)
2 (deg.)
Fig. 3. XRD spectra of tungsten thin lms after heat treatment at 650 1C
for different times: (a) 0 (as-deposited), (b) 15, (c) 80 and (d) 180 min.
0
10
20
30
40
50
60
70
80
90
0
M
o
l
a
r

c
o
n
c
e
n
t
r
a
t
i
o
n

(
%
)
O
W
Na
Si
0
I
n
t
e
n
s
i
t
y

(
a
.
u
.
)
W
(
4
f
)
W
(
4
d
)
C
(
1
s
)
W
(
4
p
3
/
2
)
O
(
1
s
)
O
(
A
u
g
e
r
)
N
a
(
1
s
)
N
a
(
A
u
g
e
r
)
S
i
(
2
p
)
S
i
(
2
s
)
0 min
15
80
180
0 min
15
80
180
40 37 34 31
Binding Energy (eV)
W
6+
W
5+
W
4+
W
0
1200 1000 800 600 400
Binding energy (eV)
200
Time (min.)
50 100 150 200
Fig. 2. (a) XPS survey spectra, (b) molar concentration of O, W, Na and Si at the surface and (c) W(4f) core level XPS spectrum of the tungsten thin lms
after heat treatment at 650 1C for different times.
Table 1
XRD peak position, lattice parameter and Na content in the Na
x
WO
3
(0 0 1) phase synthesized at 650 1C for different heating times
Annealing time (min) 2y (1) a
0
(A

) x
15 23.177 3.8350 0.61
80 23.042 3.8572 0.89
180 23.179 3.8347 0.61
R. Azimirad et al. / Vacuum 82 (2008) 821826 824
any nanowhiskers on the surface for this sample. In
addition, XPS survey spectrum of this sample determined
no sodium peaks on the surface. Therefore, it can be
concluded that diffusion of sodium from soda lime
substrate toward the surface of the lm and so its presence
on the surface plays a key role for the growth of tungsten
oxide with Q1D nanostructures. This is similar to the role
of potassium in formation of Q1D nanostructure of
tungsten oxide as reported recently [1012].
It is known that melting point of pure WO
3
is 1473 1C.
Thus, for the growth of Q1D nanostructure of WO
3
by
vaporsolid (VS) method in atmospheric pressure a high
temperature (T41000 1C) is usually needed. But, addition
of sodium as an impurity to tungsten oxide decreases the
melting point to a lower value of 698 1C for Na
2
WO
4
. We
propose a growing procedure based on the VLS mechanism
that agrees well with our experimental observations. The
VLS crystal growth mechanism was proposed by Wagner
and Ellis in 1964 for silicon whisker growth [28] and has
been widely used to guide the growth of various kinds of
one-dimensional nanostructures [29]. In our system, the
source of W is clearly the W lm, and the source of Na is
from the soda-lime substrate. It is reasonable to expect that
at the growth temperature, tiny droplets of low melting
point liquid containing Na, W and O can be produced from
the diffusion of sodium on surface of W metal and
oxidation from residual O
2
in the ambient. These tiny
droplets act as the seeds or templates for nanowhisker
growth. If more WO
3
were dissolved in the droplet to reach
the supersaturating state, solid Na
x
WO
3
would precipitate
from the droplet in the form of nanowhiskers. Continuous
feeding of WO
3
and Na into the liquid droplet sustains the
growth of the nanowhiskers. Finally, when the temperature
of the system is slowly lowered to room temperature, the
growth process was stopped. Recently, we have shown the
heat treatment of the W thin lm at 750 1C for 15 min
resulted in growth of sodium-tungsten oxide nanobelts
with U-shape cross section on the surface [30].
4. Conclusions
In conclusion, we have reported here a simple and novel
method to synthesize horizontal sodium-doped tungsten
oxide nanowhiskers on soda lime substrates at a relatively
low temperature (650 1C). This method is much simpler
than other methods reported before and can be easily
scaled up to prepare a larger amount of the material.
Annealing process for 80 min was determined as the proper
time for growing Na
x
WO
3
nanowhiskers on the surface.
Furthermore, it is determined that sodium from the soda
lime substrate diffuses toward the surface of the annealed
samples and this diffusion plays an important role in
growth and formation of the nanowhiskers.
Acknowledgments
The authors wish to thank Research Council of
Sharif University of Technology for nancial support of
the project. The assistance of Dr. M. Fathipour and
Mr. Sohrabi for SEM imaging is greatly acknowledged.
References
[1] Sharma S, Choudhary RNP. Ferroelectrics 1999;234:129.
[2] Lake B, Cowley RA, Tennant DA. J Phys: Condens Matter
1997;49x:1051.
[3] Wo hler F. Ann Chim Phys 1824;43:29.
[4] Sharpe AG. Inorganic Chemistry. London: Longman; 1981.
[5] Rao CNR, Deepak FL, Gundiah G, Govindaraj A. Prog Solid State
Chem 2003;31:5.
[6] Lu JG, Chang P, Fan Z. Mater Sci Eng R 2006;52:49.
[7] Wei X, Shen PK. Electrochem Commun 2006;8:293.
[8] Kim YS, Ha S-C, Kim K, Yang H, Choi S-Y, Kim YT, et al. Appl
Phys Lett 2005;86:213105.
[9] Wang G, Ji Y, Huang X, Yang X, Gouma P-I, Dudley M. J Phys
Chem B 2006;110:23777.
[10] Hong K, Yiu W, Wu H, Gao J, Xie M. Nanotechnology
2005;16:1608.
[11] Qi H, Wang CY, Liu J. Adv Mater 2003;15:411.
[12] Gillet M, Delamare R, Gillet E. J Crystal Growth 2005;279:93.
[13] He X, Cao M. Nanotechnology 2006;17:3139.
[14] Michailovski A, Krumeich F, Patzke GR. Chem Mater 2004;16:1433.
[15] Liu Z, Bando Y, Tang C. Chem Phys Lett 2003;372:179.
[16] Cao G, Song X, Yu H, Fan C, Yin Z, Sun S. Mater Res Bull
2006;41:232.
[17] Moshfegh AZ, Akhavan O. J Phys D: Appl Phys 2001;34:2103.
[18] Azimirad R, Naseri N, Akhavan O, Moshfegh AZ. J Phys D: Appl
Phys 2007;40:1134.
[19] Liu MX, Huang YL, Ma F, Xu KW. Mater Sci Eng B 2007;139:99.
ARTICLE IN PRESS
0
5
10
15
20
25
300 1100
T
r
a
n
s
m
i
t
t
a
n
c
e

(
%
)
0
5
10
15
20
25
30
35
40
400 800 1000
R
e
f
l
e
c
t
a
n
c
e

(
%
)
0 min
15
80
180
0 min
15
80
180
500 700 900
Wavelength (nm)
600
Fig. 4. (a) Optical transmittance and (b) optical reectance of the tungsten
thin lms after heat treatment at 650 1C for different times.
R. Azimirad et al. / Vacuum 82 (2008) 821826 825
[20] Chen GS, Yang LC, Tian HS, Hsu CS. Thin Solid Films 2005;484:83.
[21] Brown BW, Banks E. J Am Chem Soc 1954;76:963.
[22] Lekshmi IC, Gayen A, Prasad V, Subramanyam SV, Hegde MS.
Mater Res Bull 2002;37:1815.
[23] Klinke C, Hannon JB, Gignac L, Reuter K, Avouris P. J Phys Chem
B 2005;109:17787.
[24] Dong JW, Liang GQ, Chen YH, Wang HZ. Opt Express
2006;14:2014.
[25] Smith BW. US Patent Specication 6,368,755 B1.
[26] Azimirad R, Akhavan O, Moshfegh AZ. J Electrochem Soc
2006;153:E11.
[27] Naseri N, Azimirad R, Akhavan O, Moshfegh AZ. J Phys D: Appl
Phys 2007;40:2089.
[28] Wagner RS, Ellis WC. Appl Phys Lett 1964;4:89.
[29] Pan Z, Dai Z, Ma C, Wang ZL. J Am Chem Soc 2002;124:
1817.
[30] Azimirad R, Goudarzi M, Akhavan O, Moshfegh AZ, Fathipour M.
J Crystal Growth, 2007, doi:10.1016/j.jcrysgro.2007.11.133.
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