Characteristics of CeOxVO

2
composite thin lms synthesized
by solgel process
Linwei Song

Wanxia Huang

Yubo Zhang

Danxia Li

Qiwu Shi

Shuping Zheng

Na Li

Yuanjie Xu
Received: 29 March 2013 / Accepted: 29 April 2013 / Published online: 7 May 2013
Springer Science+Business Media New York 2013
Abstract Pure vanadium dioxide (VO
2
) and CeOxVO
2
(1.5\x \2) composite thin lms were grown on muscovite
substrate by inorganic solgel process using vanadium
pentaoxide and cerium(III) nitrate hexahydrate powder as
precursor. The crystalline structure, morphology and phase
transition properties of the thin lms were systematically
investigated by X-ray diffraction, Raman, X-ray photoelec-
tron spectroscopy, FE-SEM and optical transmission mea-
surements. High quality of the VO
2
and CeOxVO
2
composite lms were obtained, in which the relative fractions
of ?4 valence state vanadium were above 70 % though the
concentrations of cerium reached 9.77 at %. However, much
of cerium compounds were formed at the edge of grains and
the addition of cerium resulted in more clearly dened grain
boundaries as shown in SEM images. Meanwhile, the com-
posite lms exhibitedexcellent phase transitionproperties and
the infrared transmittance decreased fromabout 70 to 10 %at
k = 4 lm bellow and above the metalinsulator phase tran-
sition temperature. The metalinsulator phase transition
temperatures were quite similar with about 66 C of the pure
VO
2
and CeOxVO
2
composite thin lms. But hysteresis
widths increased with more addition of cerium, due to the
limiting effect of grain boundaries on the propagation of the
phase transition. Particularly, the CeOxVO
2
composite lm
with an addition of 7.82 at % Ce showed a largest hysteresis
width with about 20.6 C. In addition, the thermochromic
performance of visible transmittance did not change obvi-
ously with more addition of cerium.
1 Introduction
The fascinating properties and wide range applications of
vanadium dioxide (VO
2
), especially in thin lm form, have
attracted much of considerable interest [1, 2]. It can be used
in many technological applications, such as electro-optical
device, terahertz (THz) wave device and especially intel-
ligent energy conserving windows [36]. Vanadium diox-
ide is well known as a transition-metal oxide that
undergoes a reversible rst order phase transition nearly
68 C accompanied by a crystallographic transition from a
low-temperature monoclinic form to high-temperature
tetragonal phase [7, 8]. Recently, it has been observed that
this phase transition can be triggered by not only temper-
ature, but also electric eld, light and pressure [9, 10].
Doping studies have shown that changes in transition
temperature (either increase or decrease), visible or infra-
red transmittance and hysteresis width can be achieved by
inserting metal ions as dopants into VO
2
lattice [11, 12].
Up to now, lots of doped VO
2
lms have been studied to
improve their performance. Particularly, many elements
have been researched to change the metalinsulator tran-
sition temperature (Tt). It has been found that most effec-
tive metal in raising the transition temperature for VO
2
is
titanium [13]; and for lowering transition temperature,
doping of VO
2
lms with W, Mo, Au, F and Mg have been
reported by several groups [1416]. Among these, tungsten
L. Song W. Huang (&) Y. Zhang D. Li Q. Shi
S. Zheng N. Li Y. Xu
College of Materials Science and Engineering, Sichuan
University, Chengdu 610064, Sichuan, Peoples Republic
of China
e-mail: huangwanxiascu@yahoo.com.cn
Y. Zhang
Sichuan Engineering Technical College, Deyang 618000,
Peoples Republic of China
S. Zheng
Analytical and Testing Center, Sichuan University, Chengdu
610064, Peoples Republic of China
1 3
J Mater Sci: Mater Electron (2013) 24:34963503
DOI 10.1007/s10854-013-1275-2
is the most efcient dopant with Tt lowering of 27 C per 1
at % doping [17] and the reversible phase transition occurs
in the room temperature regime. Furthermore, the width of
hysteresis loop can be reduced with titanium and the
optical transmittance could be also increased by doping of
magnesium and uorine in previous research [13, 1820].
The studies of doping elements for VO
2
lms are mainly
concentrated on transition metals, while a few studies were
focused on the inuence of thermochromic performance for
rare-earth-doped VO
2
lms according to the previous
research. The CeO
2
VO
2
double-layered lms were pre-
pared by RF sputtering method [21]. The results indicated
that CeO
2
layer insured a good chemical protection to VO
2
lms. In addition, VO
2
/CeO
2
multifunctional nanocompos-
ite thin lms had been deposited by hybrid chemical vapour
and aerosol assisted deposition method [22]. The tests shown
that the lms were multifunctional, in which they were
thermochromic and had signicant photocatalytic activity.
Several methods including reactive sputtering, chemical
vapor deposition and solgel method have been used to
deposit VO
2
lms [2, 8, 23, 24]. Among these methods, the
solgel process is regarded as a quite promising and impor-
tant method because of its low cost, easy coating of large-
scale surface, exible control of lm thickness, and many
other advantages. Our research team has discussed the Ce-
doped VO
2
lms with doped concentrations not more than
2 at % by solgel method, for special chemical and physical
properties of rare earth element [25]. The doped ions entered
into VO
2
lattice replacing part of V atoms and existed in the
forms of Ce
4?
and Ce
3?
. And nally formed CexVO
2
-x
phase maintained excellent thermochromic performance.
However, it is usually difcult to obtain high concentration
of Ce-doped VO
2
composite lms by an inorganic solgel
process, for the process of doped sol with high concentration.
In this study, we prepared CeOx-VOx sol that could be
remained stable for a long time even though the addition of
concentration reached 9.77 at % by a low cost inorganic
solgel method. And then a high quality CeOxVO
2
composite thin lm was obtained with the technically
straightforward method on muscovite substrate followed by
an annealing process. The CeOxVO
2
composite thin lms
exhibited excellent thermochromic properties with more
addition of cerium. This method ought to be generally
applicable for the production of CeOxVO
2
composite thin
lms.
2 Experiments
2.1 Preparation of sol
For the deposition experiments, the V
2
O
5
sol with more
addition of cerium was prepared by using a method
described in the previous paper [17, 23, 26]. The stoichi-
ometric ratio Cerium (III) nitrate hexahydrate (Ce(NO
3
)
3

6H
2
O[99.0 % pure) was used as additive to introduce
doping ions into the lms. And then the mixture powder of
Ce(NO
3
)
3
6H
2
O and 5 g V
2
O
5
([99.9 % pure) were used
as precursor. After that, the powder precursor were heated
to 850 C in a crucible for about 30 min, and then the
molten mixture poured into 300 ml deionized water at
room temperature, in which the melting V
2
O
5
underwent
hydrolysis and polycondensation reaction to form a colloid.
After vigorous stirring for 4 h, a deep brownish sol was
made and then the sol evolved toward the formation of
inorganic network (gel) [27]. The PH of the V
2
O
5
sol was
tested as a value in the range of 1.01.5, which means a
strong acid.
2.2 Preparation of sample
The muscovite slices (40 mm 9 30 mm 9 0.1 mm) were
sequentially pre-treated by HCl and NH
3
H
2
O for remov-
ing organic contaminations and cations on the cleavage
surfaces. The precursor lms were deposited on muscovite
substrate with a withdraw speed of 2 mm/s by dip coating
method. And then dried at 80 C for 5 min in the oven. The
process was repeated once a time to increase the thickness.
And therefore, the lms were obtained with same substrate
and coating technology that led to the same thickness
approximately. According to our previous research, the
thickness of the lms was about 60 nm [28].The binding of
V
2
O
5
gel with muscovite substrate includes two approa-
ches: a direct adsorption and a chemical linker, which was
similar to the phenomena reported in Ref [29]. The
chemical linker provided a nearly covalent-strength bond
between the gel and the surface due to the hydroxylation of
muscovite interface.
In order to obtain VO
2
lms, the lms were heated in a
tube furnace at 500 C for 1.5 h with a heating rate of
8 C/min under a static atmosphere of nitrogen
([99.999 % pure). And then the tube furnace was left to
cool to the room temperature in owing nitrogen. A
schematic ow chart was presented in Fig. 1.
2.3 Characterizations
The structures of the lms were determined by X-ray dif-
fraction (XRD) using v Pert (Philips) diffractometer with
Cu Ka (k = 0.15406 nm) radiation at a grazing angle of
1.5. Raman spectroscopy was performed using a 514 nm
laser on a Raman microscope spectrometer (inVia Reex)
(Renishaw, England) with a laser energy of 34 mW. The
morphologies of lms were described by scanning electron
microscopy (JSM-7500F) (JEOL Japan) with an acceler-
ating voltage of 5 kV. The concentration of the doping ions
J Mater Sci: Mater Electron (2013) 24:34963503 3497
1 3
was determined by X-ray photoelectron spectroscopy
(XPS) (Kratos, England) with Mg Ka (hm = 1,253.6 eV)
exciting source. The infrared optical property of the lms
was determined by Tensor 27 (Bruke, Germany) spectro-
photometer to analyze the transmittance of the lms in the
middle infrared range below and above the phase transition
temperature. The temperatures were measured with an
appended temperature sensor in contact with the lms and
it was controlled via a temperature controlling unit. And
then the transmittance of the lms at different temperatures
was measured at approximately 2 C intervals during the
heating and cooling. Furthermore, Hysteresis loops were
received by collecting the transmittance of the lms at a
xed wavelength (4 lm) for different temperatures. The
visible spectrum ranging from 400 to 1,100 nm was
recorded via a UVVis spectrometer (Jena Specord 200,
Germany), and the composite lm was heated in a situ
heating unit.
3 Results and discussion
3.1 XRD
XRD patterns for the pure and composite CeOxVO
2
thin
lms at room temperature were shown in Fig. 2. The
covered lms were so thin that the diffraction peaks of the
muscovite substrate appeared. It could be seen that all
samples exhibited three diffraction peaks at 2h = 17.87,
2h = 26.45, 2h = 45.69 assigned to muscovite substrate
(JCPDF Card no. 07-0042) [26]. Only one distinguished
diffraction peak, excepting the peaks of muscovite sub-
strate at about 2h = 27.91, is identied to be the (011)
diffraction peak of monoclinic VO
2
(JCPDS Card no.
09-0142) [23]. Therefore, it indicates that the lm has a
strong orientation relation to the muscovite substrate,
which is the most stable low-index face with the lowest
energy of the monoclinic phase [28]. Furthermore, no clear
diffraction peaks for other vanadium oxides (such as V
6
O
13
and V
2
O
5
) were detected. However, the peak of CeO
2
was
observed only in the pattern of 7.82 at % composite CeOx
VO
2
lm. The diffraction peak at 2h = 47.33 corresponds
to the (022) plane of CeO
2
(JCPDF Card no. 65-2975). The
full width at half maximum (FWHM) of the (022) peak is
narrow with a value of 0.23, implying high crystallinity of
the CeO
2
particle. The cerium compounds are maldistri-
bution in the CeOxVO
2
composite lms as seen in SEM
images (to be discussed later) and the enriched cerium
compound is tested by XRD spectrum only in 7.82 at %
composite CeOxVO
2
lm.
3.2 Raman spectroscopy
Raman spectroscopy is also an extremely useful tool to
identify the evolution of the crystalline structures of VO
2
lms [30]. As shown in Fig. 3, the black line is the Raman
spectrum of pure muscovite substrate, the red line is the
pure VO
2
lm and blue line corresponds to composite
CeOxVO
2
lm. Both of the pure VO
2
and composite
CeOxVO
2
lms showed Raman shifts at around 143, 193,
223, 260, 307, 388, 499 and 616 cm
-1
, indicating that the
dominant phase is VO
2
(M1) [31]. No Raman shifts for
other kinds of vanadium oxides (V
6
O
13
, V
2
O
5
) were
detected, in which the result corresponds well with the
XRD patterns. In addition, the shifts of substrate cannot be
identied both in the pure VO
2
and composite CeOxVO
2
Fig. 1 Schematic ow chart
outlines the synthesis
procedures for composite lm
3498 J Mater Sci: Mater Electron (2013) 24:34963503
1 3
lms on muscovite substrate, for the surface detection to
lms by Raman spectroscopy. Moreover, no other shifts
were observed for cerium compounds because of the
nonuniform distribution of cerium compounds in VO
2
lms
as seen in SEM images (to be discussed later).
3.3 SEM
SEM images introduce the surface morphologies of the
pure VO
2
(Fig. 4a) and composite CeOxVO
2
(Fig. 4b, c,
d) lms. The images show that lms obtained via solgel
method are quite homogeneous, continuous, and particulate
with a high surface coverage. The grains are particulate
with grain size of about 100 nm. But some small pores
appear between the boundaries of large grains in all lms,
due to the wetting properties between the substrate and
precursor sol [32].Particularly, the pure lm show a at
surface that formed by packing closely connected nano-
particles and fuzzy boundaries can be seen. Obviously, the
addition of Ce depresses the growth of VO
2
particles,
which can be explained by the heterogeneous nucleation
mechanism of VO
2
particles during annealing [33].
The addition of cerium resulted in more clearly dened
grain boundaries that cause a relatively large thermal
hysteresis for composite CeOxVO
2
lms (to be discussed
later) [34]. In addition, some extremely small particles are
formed at the edge of grains for composite CeOxVO
2
lms, in which some of these are noted by elliptical mark.
The small particles were cerium compound that precipi-
tated from the VO
2
crystal particles during an annealing
process. Furthermore, some dark sticks ranging from 200 to
600 nm can be identied in the composite CeOxVO
2
lms, especially in Fig. 4b, c.
3.4 XPS
The lms were further analyzed with XPS to verify surface
composition and elemental oxidation states. Due to
observed charging effects during XPS analysis, the binding
energy scale was calibrated using adventitious carbon.
Valence analyses of the pure VO
2
and composite CeOx
VO
2
lms were shown in Fig. 5. The result of XPS is
average of multiple spots. All the XPS spectrums clearly
show the intense peaks of V and O. Particularly, the
spectrum of composite CeOxVO
2
lm in Fig. 5a exhibit
weak peak of Ce, in which indicates the incorporation of
Ce atoms in the VO
2
lms. Figure 5c and d present the
high resolution scanning of V2p peaks for the composite
CeOxVO
2
and pure VO
2
lms, respectively. The peaks
position of V2p and Ce3d were tted using a Shirley
function with the XPS PEAK 4.1 software. Usually, the
phase of vanadium oxide can be determined by the char-
acteristic V2p3/2 peak position because it is the most
sensitive to phase change [35]. For the composite CeOx
VO
2
and pure VO
2
lms, two valence states of vanadium,
V
4?
valence (with a binding energy of 515.93 and
515.98 eV) and V
5?
valence (with a binding energy of
517.21 and 517.17 eV) were detected. Both of the binding
energy for two valence states of vanadium were in agree
with the reported VO
2
lms [36, 37]. To obtain the relative
concentration of atom in a homogeneous system, one
simply divides each atoms peak intensity and takes the
ratio [38]. Therefore, the relative fractions of V
4?
valence
state have been evaluated as 71.68 and 72.19 % for the
composite CeOxVO
2
(Fig. 5c) and pure VO
2
(Fig. 5d)
lms, respectively. The results indicate that high quality of
VO
2
lms were obtained by inorganic solgel process for
not only the pure lm but also composite CeOxVO
2
lm.
Figure 5b shows the high resolution scans of the Ce3d
peak for the composite CeOxVO
2
lm. According to the
standard binding energy and the conclusion of Fig. 5b, the
doping ions exist in the form of Ce
4?
(with a binding
energy of 881.74 eV) and Ce
3?
(with a binding energy of
Fig. 2 XRD patterns of the pure and composite CeOxVO
2
lms on
the muscovite subtract at room temperature
Fig. 3 Raman patterns for mica, pure VO
2
and composite CeOxVO
2
lms
J Mater Sci: Mater Electron (2013) 24:34963503 3499
1 3
885.56 eV). And the relative fraction of the Ce
4?
valence
state has been evaluated as 48.55 %. Moreover, the con-
centrations of the Ce ions in the VO
2
lms are determined
by the deconvolution of the Ce range spectrum. Mean-
while, the areas for the peaks of Ce3d and V2p are
measured, taking account of the atomic sensitive factors
(ASF) of cerium and vanadium. The Ce concentrations are
estimated by comparing the product of the area at the Ce3d
peaks divided by the cerium ASF to that of the area at the
V2p peak divided by the vanadium ASF [39]. Therefore,
Fig. 4 SEM images of the pure VO
2
and composite CeOxVO
2
lms a pure b 6.52 at % Ce c 7.82 at % Ce d 9.77at % Ce
Fig. 5 a XPS spectrum of the
pure VO
2
and composite CeOx
VO
2
lms on muscovite
substrate. b, c High-resolution
scans of the Ce3d and V2p
peaks for the composite CeOx
VO
2
lm. d High-resolution
scans of the V2p peak for the
pure VO
2
lm
3500 J Mater Sci: Mater Electron (2013) 24:34963503
1 3
the concentrations of Ce are found to be 9.75 at % for the
composite CeOxVO
2
lm. This result is much consistent
with the initial molar ratio (to be 9.77 at %).
3.5 FT-IR in VO
2
thin lms
The IR transmittance of VO
2
lms on muscovite substrate
are measured as a function of temperature by applying
heating and cooling cycles. Transmittance hysteresis
curves were deduced by measuring the transmittance at a
xed wavelength of 4 lm for all VO
2
lms as shown in
Fig. 6. The black line is the transition temperature change
of heating process and red line corresponds to cooling. To
evaluate the MIT characteristics of the lms, a derivative
[-dTr/dT] of the infrared transmittance of heating and
cooling curves have been calculated as shown the insert
gure in Fig. 6. Each of the -dT
r
/dT - T curves has been
analyzed with a Gaussian function using the single peak
tting module of OriginPro 8.0 software. T
1
and T
2
rep-
resent the MIT temperature of heating and cooling process
where infrared transmittance of lms changes dramatically.
The MIT temperature and hysteresis width are dened as
(Tt) = (T
1
? T
2
)/2 and (Tw) = T
1
- T
2
, respectively.
From the gures, all lms exhibit excellent thermochro-
mic performance with a transmittance of about 6571 % at
room temperature and 810 % above the phase transition
temperature. The transmittance change of the composite
CeOxVO
2
lm is relatively larger than that of VO
2
/CeO
2
multifunctional nanocomposite lm reported by Warwick
et.al [22], due to the thickness of the CeOxVO
2
lmis about
60 nm. According to our previous study [25], the Tt
decreased with increasing of the Ce doping concentrations
when the concentrations were not more than 1.68 at %. The
particle size reducing led to transition temperature decrease
with parts of V replaced by Ce atoms while the doped con-
centrations are low. But fromthis article, the metalinsulator
phase transition temperature of all samples are quite similar
with 66.7 C [pure (Fig. 6a)], 66.1 C [6.52 at % Ce
(Fig. 6b)], 66.4 C [7.82 at % Ce (Fig. 6c)] and 67.0 C
[9.77 at % Ce (Fig. 6d)]. The tendency of phase transition
temperature is similar with the reported study [22]. In addi-
tion, the particle size does not change signicantly for an
addition of high concentration of cerium contrasting to pure
VO
2
lm in this article as shown in SEM gure (Fig. 4). In
contrast, many of cerium compounds were formed at the
verge of grains and in the gaps among grains.
Moreover, the signicant changes in hysteresis width are
shown in Fig. 6 with the addition of Ce. The Tw are 10.3,
12.9, 20.6 and 15.7 C for the pure (Fig. 6a), 6.52 at % Ce
(Fig. 6b), 7.82 at % Ce (Fig. 6c) and 9.77 at % (Fig. 6d),
respectively. The hysteresis width become larger with
addition of cerium compared to the pure lm. This ten-
dency is similar with the VO
2
/CeO
2
multifunctional
nanocomposite lm reported by Warwick et.al [22]. In
addition, the compactness among grains is believed to
determine elementary hysteresis loops. From the SEM
images, the grains of composite CeOxVO
2
lms exhibits
loose distribution on the muscovite substrate that cause a
Fig. 6 Comparison of the
optical hysteresis at 2,500 cm
-1
(4 lm) obtained from the
temperature dependence of
optical transmittance for VO
2
lms. a pure b 6.52 at % Ce
c 7.82 at % Ce d 9.77at % Ce
J Mater Sci: Mater Electron (2013) 24:34963503 3501
1 3
relatively large thermal hysteresis, due to the limiting
effect of grain boundaries on the propagation of the phase
transition as shown in Fig. 4bd [34, 40]. The inuence
among adjacent grains changes weak, for the formed
Cerium compounds in the gap among grains. In this case,
7.82 at % composite CeOxVO
2
lm (Fig. 6c) showed the
largest Tw for the loosest grain distribution in all lms.
3.6 The visible properties in VO
2
lms
Figure 7 presents the transmittance of the pure VO
2
and
composite CeOxVO
2
lms in the wavelength range of
4001,100 nm below and above the phase transition tem-
perature. The black line is the transmittance of pure lm
and red, blue and green lines correspond to 6.52, 7.82 and
9.77 at % CeOxVO
2
composite lms, respectively. The
results show that the visible transmittance of all VO
2
lms
is similar and the transmittance decreases with the tem-
perature increasing. Moreover, the thermochromic perfor-
mance of visible transmittance does not change obviously
for addition of high concentration of cerium during the
metalinsulator phase transition, which is signicant for
the practical application.
4 Conclusions
In summary, the pure VO
2
and composite CeOxVO
2
thin
lms were obtained by inorganic solgel process using cer-
ium(III) nitrate hexahydrate and vanadium pentaoxide
powder as precursor. The effect of cerium on structural,
microstructure and thermochromic performance has been
systematically studied. The investigations reveal that high
quality of VO
2
lms are obtained, in which the relative
fractions of ?4 valence state vanadium are above 70 %
though the concentration of cerium reached 9.77 at %. The
grain size does not change with more addition of cerium.
However, the addition of cerium in CeOxVO
2
thin lm
leads to form CeO
2
and other cerium compounds at edge of
grains as shown in SEM images. Therefore, the addition of
cerium results in more clearly dened grain boundaries that
causes a relatively large thermal hysteresis, due to the lim-
iting effect of grain boundaries on the propagation of the
phase transition. The composite CeOxVO
2
lm with an
addition of 7.82 at % cerium showed the largest hysteresis
width, for the loosest grain distribution in all lms. Mean-
while, the composite lms exhibit excellent phase transition
properties, with a decrease of infrared transmittance from
about 70 to 10 % at k = 4 um bellow and above the metal
insulator phase transition temperature. The metalinsulator
phase transition temperature are quite similar with about
66 C both of the pure VO
2
and composite CeOxVO
2
thin
lms. In addition, the thermochromic performance of visible
transmittance does not change obviously during the metal
insulator phase transition with more addition of cerium,
which is signicant for the practical application. The results
of this research indicate that the inorganic solgel method
could be an effective process for fabricating composite
CeOxVO
2
thin lm with more addition of cerium.
Acknowledgments This work was nancially supported by the
National Science Foundation of China (Grant Nos. 61271075). We
would also thank the Analytical & Testing center of Sichuan Uni-
versity for their XRD and SEM analysis.
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