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Materials Research Bulletin 37 (2002) 1815±1823

Structure and electrical properties of sodium


tungsten bronzes thin ®lms
I. Chaitanya Lekshmia, Arup Gayena, V. Prasadb,
S.V. Subramanyamb, M.S. Hegdea,*
a
Solid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore 560 012, India
b
Department of Physics, Indian Institute of Science, Bangalore 560 012, India

(Refereed)
Received 24 May 2002; accepted 21 June 2002

Abstract
Highly oriented thin ®lms of NaxWO3 (x ˆ 0:25±0.7) are grown on sapphire (1 1 0 2) and
SrTiO3 (1 0 0) substrates by pulsed laser deposition. The colour of the ®lms changes from blue
through red to bronze yellow on varying the sodium content. The ®lms are composed of particles
less than 100 nm size. As in bulk NaxWO3, the resistivity is found to decrease on increasing the
sodium content, and at around x ˆ 0:25, a non-metal to metal transition is clearly observed. The
conductivity measurement of Na0.25WO3 shows a crossover from temperature-activated
Arrhenius behaviour at high temperatures to a variable range hopping mechanism near
70 K. The metallic samples show linear dependence of resistivity above 50 K. XPS studies
con®rm the presence of sodium in ‡1 and tungsten in ‡5 and ‡6 oxidation states.
# 2002 Elsevier Science Ltd. All rights reserved.

Keywords: A. Thin ®lms; B. Laser deposition; D. Electrical properties

1. Introduction

Tungsten oxide, modi®ed by ion incorporation, exhibits many important proper-


ties, some of which has immense technological application in various ®elds like
sensors, heterogeneous catalysis, active electrodes in electrochromic displays [1,2]
and as mixed electronic and ionic conductors in high-energy density batteries.
Recently tungsten bronzes have also received much attention as they form rigid
*
Corresponding author. Fax: ‡91-80-3601310.
E-mail address: mshegde@sscu.iisc.ernet.in (M.S. Hegde).

0025-5408/02/$ ± see front matter # 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 2 5 - 5 4 0 8 ( 0 2 ) 0 0 8 7 0 - X
1816 I.C. Lekshmi et al. / Materials Research Bulletin 37 (2002) 1815±1823

network structures where alkali-metal ions occupy tunnels or interlayer positions


giving rise to interesting structural and electronic properties [3±5]. Among the
different tungsten bronzes known, the sodium tungsten bronzes have been of great
interest ever since their discovery by WoÈhler [6] in 1824, due to the variation of their
electronic and optical properties [7] with composition. These non-stoichiometric
compounds, NaxWO3 (0 < x  1), exhibit metallic lustre and a variation in colour
from deep blue through red to bronze yellow [8], as the value of x increases. A weakly
activated non-metallic conductivity is exhibited for lower values of x, while at higher
x values they are metallic [7,9,10]. The thin ®lms of these bronzes are of interest for
the above mentioned device applications. Though both crystalline and amorphous
tungsten trioxide ®lms are known in the literature [1], to the best of our knowledge,
there is not much work done on sodium tungsten bronzes thin ®lms, other than those
related to electrochromic devices, deposited electrochemically [2]. Hence, we
considered it worthwhile to make thin ®lms of sodium tungsten bronzes by pulsed
laser deposition (PLD) and study their structure and transport properties. We report
here the oriented growth of sodium tungsten bronzes thin ®lms by PLD in the
composition range of x from 0.25 to 0.7 and show that the system exhibits a non-metal
to metal transition as sodium content is increased above x 0.25. The fabrication of
these ®lms over a wide range of sodium composition is easily achieved using green
pellets of their precursors as target in contrast to the synthesis of bulk NaxWO3 that
involves higher temperatures and longer duration.

2. Experimental

Thin ®lms of sodium tungsten bronzes were prepared by PLD using KrF excimer
laser. The targets were prepared by mixing Na2WO42H2O and WO3 in the required
proportion to give an atomic ratio of x:1 (x varies from 0.25 to 0.7) for Na:W.
x x
Na2 WO4  2H2 O ‡ …1 †WO3 ! Nax WO3 (1)
2 2
The ground mixture was pelletised and sintered in air at 6308C for 3 days. The ®lms
were grown at a substrate temperature of 5508C. The deposition was done in vacuum
of 2  10 5 ±4  10 5 m bar base pressure for compositions x ˆ 0:33±0.7, while
oxygen partial pressures of 80±90 and 280±300 mTorr were used for bronzes with
x ˆ 0:3 and 0.25, respectively. The ®lms grown were of 300 nm thickness and the
substrates used were sapphire (1 1 0 2) and SrTiO3 (1 0 0). The deposition was also
done varying the substrate temperature to study its effect on the crystallinity and
morphology of the ®lms. The growth of the ®lms was characterised by Siemens
D5005 X-ray diffractometer using Cu Ka radiation with Ni ®lter. The surface
morphology of these ®lms was examined by a JEOL 5100 LV scanning electron
microscope (SEM). The electrical resistivity measurements as a function of tem-
perature were done upto 6 K by a standard four-probe con®guration. The carrier
concentration of two of the compositions was determined by Hall measurement using
I.C. Lekshmi et al. / Materials Research Bulletin 37 (2002) 1815±1823 1817

the conventional Van-der Pauw technique. X-ray photoelectron spectroscopy (XPS)


of freshly prepared ®lms (without argon ion etching) were recorded on an ESCA-3
Mark II spectrometer (VG Scienti®c Ltd., UK) using Al Ka radiation (1486.6 eV).

3. Results and discussion

The X-ray diffraction pattern of NaxWO3 ®lms shows a highly oriented growth in
(1 0 0) direction (Fig. 1(a)) for the entire composition range studied. As in bulk
sodium tungsten bronzes [7,11], they show an increase in out-of-plane lattice
parameter with increase in x (Table 1). NaxWO3 (x ˆ 0:25, 0.3, 0.33, 0.46) were
grown on sapphire. However, Na0.7WO3 ®lm could not be grown on the same. This
may be explained by the increasing lattice mismatch between the substrate
(ao ˆ 3:64 A Ê ) and the ®lm as is evident from Table 1. Further, Na0.7WO3 ®lm
was successfully grown on SrTiO3 (1 0 0) [STO, ao ˆ 3:905 A Ê ]. NaxWO3 (x ˆ 0:33,
0.46) were also grown on STO. These ®lms are again oriented in (1 0 0) direction and
show an increase in lattice parameter with increase in x. The out-of-plane lattice
parameters calculated from the XRD pattern for x ˆ 0:3±0.7 are in close agreement
with those obtained using the relation, a ˆ 3:7846 ‡ 0:082x A Ê [7], which holds in the
range of x from 0.3 to 0.85 (cubic) in bulk sodium tungsten bronzes. Considering the
substrate effect, it can be assumed that the composition of these ®lms is closely in
agreement with the nominal composition of their targets. It should also be mentioned
here that the prolonged heating of the targets might reduce the sodium content of the
desired bronze. Since there is not much discrepancy in the observed values of the
measured properties, the loss of sodium content is expected to be minimal. At lower
sodium concentrations, the colour of the ®lm is bright blue (x ˆ 0:25). As the sodium
content is increased, the colour changes from blue-black (x ˆ 0:3, 0.33) to red
(x ˆ 0:46) to bronze yellow (x ˆ 0:7). On annealing the ®lms for 1 h or more in
vacuum, sign of polycrystallinity appears in the X-ray diffraction pattern. Polycrystal-
line ®lms are obtained, when grown at higher substrate temperatures of 6508C
(Fig. 1(c)). The SEM images indicate the ®lms as composed of small particles of
<100 nm size (Fig. 2(a)). The ®lms deposited on STO are much smoother than those

Table 1
Out-of-plane lattice parameter of NaxWO3 ®lms on sapphire and STO. Films for x ˆ 0:25, 0.3 not tried
on STO
Composition (x) Out-of-plane lattice parameter
Ê)
Sapphire (A Ê)
SrTiO3 (A
0.25 3.73 ±
0.3 3.803 ±
0.33 3.828 3.823
0.463 3.835 3.838
0.7 ± 3.852
1818 I.C. Lekshmi et al. / Materials Research Bulletin 37 (2002) 1815±1823

Fig. 1. X-ray diffraction pattern of NaxWO3 ®lms. Na0.33WO3 on sapphire grown at 5508C (a), Na0.7WO3
on SrTiO3 grown at 5508C (b), Na0.46WO3 on sapphire deposited at 6508C (c). At high substrate
temperatures, ®lm turns polycrystalline. `S', in each case, indicates the respective substrates used.

on sapphire are. On annealing the ®lms or on increasing the substrate temperature, the
particles tend to agglomerate as shown in Fig. 2(b) and (c).
We have studied the variation of resistivity of NaxWO3 ®lms as a function of
temperature for different sodium compositions (x ˆ 0:25, 0.3, 0.33, 0.46, 0.7) ranging
I.C. Lekshmi et al. / Materials Research Bulletin 37 (2002) 1815±1823 1819

Fig. 2. SEM images of Na0.46WO3: deposited on SrTiO3 at 5508C (a); deposited on SrTiO3 at 5508C
and annealed at the same temperature in vacuum for 1 h (b); deposited on sapphire at 6508C (c). The
particles tend to agglomerate on annealing the ®lms or when deposited at high substrate temperatures.
1820 I.C. Lekshmi et al. / Materials Research Bulletin 37 (2002) 1815±1823

Fig. 3. Temperature dependence of resistivity of NaxWO3 from x ˆ 0:25 to 0.7. It is evident from the
plot that the metal to non-metal transition takes place as x decreases down to 0.25 (a). Plot of resistivity
vs. sodium content in the metallic region from x ˆ 0:3 to 0.7 (b). ln s vs. T 1/4 plot for x ˆ 0:25. VRH
is obeyed by the system below 70 K (the ®tting is shown by the line with the squares) (c).

from semiconducting to metallic behaviour (Fig. 3(a)). The gradual decrease of


resistivity with increase in sodium content is clearly shown in Fig. 3(b). The resistivity
of these ®lms is close to the corresponding values for the bulk solids (single crystals)
of the same composition [10,12,13], though it is slightly on the higher side. For
example, the resistivity values of the single crystal and the ®lm for x ˆ 0:3 at 300 K
are 326 and 668 mO cm, respectively, and the same for x ˆ 0:46 are 70 and
I.C. Lekshmi et al. / Materials Research Bulletin 37 (2002) 1815±1823 1821

337 mO cm, respectively. The higher value of resistance for the ®lms could be due to
the substrate effect as well as the grain boundary effect [14]. The deviation from the
bulk value is larger with greater lattice mismatch for the metallic ®lms indicative of
the substantial role played by the substrate effect. The fact that the ®lms are largely
contiguous and the substrates are known to effect the properties, it is dif®cult to
estimate the contribution from each of them towards the higher resistance of the ®lm.
The decrease in resistivity can be explained from the fact that the number of charge
carriers increases with increase in the level of sodium doping. This increase in charge
carriers (electrons) is clearly observed in the Hall measurements. Na0.46WO3 is found
to have 8:8  1021 cm 3 charge carriers using a free electron approximation, which is
close to the value of 1:1  1022 cm 3 in bulk Na0.46WO3 solid [8]. Na0.25WO3, on the
other hand, is estimated to have a carrier concentration of only 1  1019 cm 3.
The conductivity of NaxWO3 for x <0.75 varies approximately as Slf, where S is
the area of the fermi surface and lf is the average mean free path at the fermi surface
[15]. If every sodium atom is assumed to contribute one electron to the conduction
band, then both S and lf increase with sodium concentration, resulting in an increase
in the conductivity. We have extrapolated the resistivity values to 0 K to ®nd the
residual resistivity (r0) and have observed that the r0 values are quite high compared
to the conventional metals, in agreement with the previous studies on bulk samples
[12]. Hence, it is not possible to verify the nature of the dependence of resistivity at
low temperature, where it is expected to vary as T 5. The contribution to the residual
resistivity from lattice imperfections and impurities is assumed to be small. The
assumption seems to be valid, since contribution from lattice imperfections and
impurities will not have any de®nite x dependence. But we ®nd that the resistivity at
different temperatures has a strong non-linear x dependence for NaxWO3 (Fig 3(b)).
Hence, the major contribution to the residual resistivity would be from the electron-
sodium vacancy scattering, which decreases with increase of x. At high temperatures,
according to Bloch and Bethe [16], the resistivity (r) of a metal, due to interaction of
the electron with the lattice vibrations, is given by
T
r/ ; (2)
My2
where M is the mass of the electron, T is the absolute temperature and y is the Debye
temperature. In all the metallic bronzes we studied, a good linear behaviour of r with
temperature above 50 K (approximately) is observed. For x ˆ 0:25, the resistivity is
found to increase with decrease in temperature. At higher temperatures, the behaviour
can be explained by a thermally activated transport of Arrhenius type. In the low
temperature region, below 70 K, the behaviour of resistivity is found to follow Mott's
3D variable range hopping mechanism [17] with a hopping exponent of 1/4 (Fig. 3(c)).
In this region, the best linear fit is obtained in ln s (s is the conductivity) versus T 1/4
coordinates. At still lower temperatures, a small deviation from the linear behaviour is
observed.
XPS studies con®rm the presence of sodium in ‡1 oxidation state and that of
tungsten in ‡5 and ‡6 oxidation states. The XPS of W(4f) core level region in
1822 I.C. Lekshmi et al. / Materials Research Bulletin 37 (2002) 1815±1823

Fig. 4. XPS core level region of W(4f) in Na0.3WO3 (a). Valence band spectrum of Na0.3WO3 (b).

NaxWO3 (x ˆ 0:3) is shown in Fig. 4(a). The spectrum can be deconvoluted into two
spin-orbit doublets. Accordingly, W(4f7/2,5/2) peaks at 33.6, 35.8 and 35.9 eV, 38.0 eV
can be attributed to W‡5 and W‡6, respectively, whose relative intensities are 29 and
71%. The small peak at 32.5 eV can be attributed to Na(2p) and the peaks at 39.8 and
41.2 eV are assigned to W‡5 (5p3/2) and W‡6 (5p3/2), respectively [18]. Integrated
intensities of W(4f) and Na(1s) core levels have been taken into account to calculate
the concentration. The ratio of Na to W obtained is 0.36, which is reasonably close to
the nominal composition taken in the green pellet. The valence band spectrum
obtained using Al Ka radiation, given in Fig. 4(b), shows W‡5(5d) band below EF and
O(2p) band peaked at 6.8 eV. Similar spectra are obtained for other compositions,
though the Na to W ratio is slightly less than expected from the nominal composition.
In conclusion, we have grown highly oriented NaxWO3 thin ®lms by PLD on
sapphire and SrTiO3 substrates. The expected variation in colour from blue through
red to bronze yellow on varying the sodium content is clearly observed. In close
agreement with the bulk NaxWO3, the out-of-plane lattice parameter increases with
increase in sodium concentration. With decreasing sodium content a metal to
I.C. Lekshmi et al. / Materials Research Bulletin 37 (2002) 1815±1823 1823

non-metal transition is observed in these ®lms as x approaches 0.25. In metallic


samples, the resistivity is observed to vary linearly with temperature above 50 K. The
transport studies also show evidence of a transition from thermally activated
Arrhenius behaviour to VRH transport for Na0.25WO3 near 70 K. XPS studies reveal
the presence of sodium in ‡1 oxidation state and that of tungsten in ‡5 and ‡6
oxidation states. The tungsten bronzes of other alkali metals can be prepared by
similar method. Potassium tungsten bronzes thin ®lms in the metallic regime are
successfully grown and their structural and transport properties are being investi-
gated.

Acknowledgments

The authors would like to thank Mr. Vijay Kumar Dixit and Prof. H.L. Bhat for
helping us with the Hall measurements. We are grateful to Mr. Parthasarathi Bera for
his useful suggestions in analysing the XPS data. Also, the ®nancial assistance from
the Department of Science and Technology, Government of India is gratefully
acknowledged.

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