Hindawi Publishing Corporation

Journal of Nanomaterials
Volume 2012, Article ID 674168, 9 pages
doi:10.1155/2012/674168

Research Article
Electrochromic Devices Based on Porous Tungsten Oxide
Thin Films

Y. Djaoued,1 S. Balaji,1 and R. Brüning2

1 Laboratoirede Recherche en Matériaux et Micro-Spectroscopies Raman et FTIR, Université de Moncton—Campus de Shippagan,
218 Boulevard J.-D. Gauthier, Shippagan, NB, Canada E8S 1P6
2 Physics Department, Mount Allison University, 67 York Street, Sackville, NB, Canada E4L 1E6

Correspondence should be addressed to Y. Djaoued, yahia.djaoued@umoncton.ca

Received 29 May 2012; Accepted 22 June 2012

Academic Editor: Vo-Van Truong

Copyright © 2012 Y. Djaoued et al. This is an open access article distributed under the Creative Commons Attribution License,
which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Recent developments in the synthesis of transition metal oxides in the form of porous thin films have opened up opportunities in
the construction of electrochromic devices with enhanced properties. In this paper, synthesis, characterization and electrochromic
applications of porous WO3 thin films with different nanocrystalline phases, such as hexagonal, monoclinic, and orthorhombic, are
presented. Asymmetric electrochromic devices have been constructed based on these porous WO3 thin films. XRD measurements
of the intercalation/deintercalation of Li+ into/from the WO3 layer of the device as a function of applied coloration/bleaching
voltages show systematic changes in the lattice parameters associated with structural phase transitions in Lix WO3 . Micro-
Raman studies show systematic crystalline phase changes in the spectra of WO3 layers during Li+ ion intercalation and
deintercalation, which agree with the XRD data. These devices exhibit interesting optical modulation (up to ∼70%) due to
intercalation/deintercalation of Li ions into/from the WO3 layer of the devices as a function of applied coloration/bleaching
voltages. The obtained optical modulation of the electrochromic devices indicates that, they are suitable for applications in
electrochromic smart windows.

1. Introduction leading to a bleached state. The EC phenomenon, with xe−

and Li+ ions inserted into (ejected out of) the system, can be
Tungsten oxide (WO3 ) has been one of the most widely represented as:
studied materials due to its multifunctional properties
that have wide spectrum of applications in electrochromic WO3 + xLi+ + xe− ←→ Lix WO3
devices, catalysers, gas sensors, optical switching devices, (1)
clear dark blue
and so forth [1–3]. Over the past three decades, intensive
research has been carried out towards improving WO3 -based The performance of an EC device depends on the crys-
electrochromic (EC) devices due to their important energy tallinity, crystallite size, porosity, and thickness of the elec-
saving properties [4–7]. A typical asymmetric EC device trochromically active layer [10–14]. As far as the preparation
consists of an ion conducting (IC) layer, which also acts of individual layers in an EC device is concerned, PVD
as a counter electrode and a WO3 electrochromic layer as techniques (thermal evaporation, sputtering, pulsed laser
the working cathode, sandwiched between two transparent deposition) and mild chemical approaches such as sol-gel
conductive electrodes (TEs) [8, 9]. When a low voltage (1– processes have been used [10–15]. Among these, the sol-gel
3 V) is applied across the TEs, Li+ ions from the counter technique is attractive. The sol-gel process allows a detailed
electrode and electrons (e− ) from the TE move to the EC control of the film texture and structure, leading to tailored
WO3 layer. This double injection results in the formation electrochromic properties. Mesoporous WO3 films prepared
of colored Lix WO3 bronzes, with a controllable degree of by a sol-gel method with block copolymer templates have
coloration as a function of x (Li ion concentration). When been investigated by Cheng et al. and by Djaoued et al.
the applied voltages are reversed, the Li+ ions deintercalate, [11, 14]. Macroporous WO3 films were also synthesized via
2 Journal of Nanomaterials

sol-gel processing using polyethylene-glycol as a templating intercalation/deintercalation of Li ions into the WO3 layers
agent [12]. Mesoporous materials, due to their higher surface of the operating EC device as a function of applied voltages
area, exhibit better kinetics for coloration and bleaching are described. The optical transmittance data obtained in
in comparison with standard sol-gel-derived WO3 thin conjunction with the Raman and the XRD studies are
films. On the other hand, macroporous WO3 , which may presented to demonstrate the applicability of these materials
have a wider range of applications as an ion hosting for energy saving electrochromic smart windows.
material, has displayed coloration efficiency values higher
than those previously reported in the literature [12]. The
motivation for synthesizing such porous materials emerges
2. Experimental Details
from the increased diffusion constant of intercalating ions In order to obtain porous WO3 films with sufficient thick-
by two orders of magnitude in porous EC-layer-based ness, hybrid organically modified silicates (ORMOSIL) was
devices. Templating agents such as polyethyleneglycol (PEG), used as a template precursor. It was prepared by an acylation
pluronic (P123), or organically modified silane (ORMOSIL) reaction between poly(propylene glycol) bis(2-aminopropyl
increase the porosity of the electrochromic layer [8, 9]. In ether) (2-APPG) with isocyanatopropyltriethoxysilane (ICS)
addition to that ORMOSIL has certain other advantages in tetrahydrofuran (THF) in the volume ratio 1 : 0.1 : 1 [6, 8,
upon annealing, as the silane in the ORMOSIL provides 20].
a silica network which helps to prepare crack-free WO3
films. Crystalline phases of WO3 occur primarily in three
2.1. Synthesis of h-WO3 and m-WO3 . The sol-gel coating
forms: distorted cubic ReO3 structures, hexagonal, and
solutions used for the preparation of h-WO3 and m-WO3
pyrochlore. The distorted cubic ReO3 structure manifests
films were synthesized according to the following procedures.
itself, in monoclinic (Pc), triclinic (P1), monoclinic (P21/n),
WO3 sols were prepared by dissolving tungsten powder
orthorhombic (Pmnb), and tetragonal (P4/nmm) phases
(99.9%) in 35% hydrogen peroxide. The mixture was left to
at various temperatures ranging from −263 to 900◦ C, in
stir at room temperature for 8 hours. After the addition of a
increasing order of symmetry. Usually electrochromic studies
small amount of ethanol (EtOH), the sol was refluxed for 4
have been performed on hexagonal (h), pyrochlore, and
hours at a temperature of 80◦ C. Finally, 1.5 g of the hybrid
monoclinic (m) phases as they are naturally stable or
ORMOSIL dissolved in EtOH was added dropwise into the
metastable at room temperature [4, 8, 9, 16, 17]. Another
WO3 sol and stirred for one hour. The final sol was used
factor that influences the performance of the electrochromic
for the WO3 film coating. The WO3 films were deposited by
devices is the nanostructures of WO3 . A detailed study
dip coating onto SiO2 -coated glass or indium tin oxide (ITO)
of electrochromic properties of nanostructured tungsten
coated-glass substrates with a surface resistivity of 5–15 Ω/sq,
oxide with room temperature stable structure of m-WO3 ,
at a controlled speed of 4 mm/s. After drying at 60◦ C, the
metastable structure of h-WO3 , and titania-stabilized o-WO3
films were annealed at 400 and 500◦ C and were held at the
(higher temperature phase) has not been published until
peak temperature for one hour and then cooled to room tem-
recently. Another interesting aspect is the phase changes that
perature which resulted in h-WO3 and m-WO3 , respectively.
are associated with the electrochromic effect in crystalline
WO3 . Intercalation of Li into ReO3 type tungsten oxides
transforms lower symmetry phases to the higher symmetry 2.2. Synthesis of o-WO3 . It has been a challenge to stabilize
phases. This phase change has been studied by Raman the higher symmetric phases of WO3 such as orthorhombic
spectroscopy or by XRD by many researchers [16–19]. (o), tetragonal (t), and cubic (c) at room temperature, since
When both Raman spectroscopy and XRD techniques are ReO3 -type WO3 reverts to m-WO3 , due to a second-order
employed simultaneously, a detailed study of the interme- Jahn-teller distortion, irrespective of thermal treatment [21].
diate structural changes in the Lix WO3 can be performed. A two-stage process was adopted to prepare o-WO3 thin
These methods are practical for the device characterization films on ITO-coated glass substrates. The first stage involves
as they can be performed nondestructively, they can probe the dip coating of a tungsten oxide film using the above
the structural changes occurring in the EC layer and provide described tungstic acid sol in the presence of ORMOSIL
an estimate of the quantity of intercalated ions. as a templating agent, followed by an annealing at 600◦ C
In this paper, we present a sol-gel methodology based on for one hour, resulting in the formation of a porous WO3
tungstic acid in the presence of ORMOSIL as a templating thin film. In the second stage, the porous WO3 film was
agent to prepare films of nanostructured hexagonal-WO3 , dip coated with a titanium-alkoxide-based ethanol solution
nanostructured monoclinic-WO3 , and titania-stabilized or- containing ORMOSIL, followed by another annealing at
thorhombic WO3 with mesomacroporous features. These 600◦ C to prepare TiO2 -stabilized o-WO3 film.
phases have been stabilized as thin films and used as an
active electrochromic layers for the construction of asym- 2.3. Fabrication of EC Devices. We prepared several elec-
metric electrochromic devices. A detailed micro-Raman trochromic devices with the configuration:
spectroscopic structural characterization of Li ions interca-
lation/deintercalation into the WO3 layer of the operating ITO-coated-glass-1/WO3 /ICL/ITO-coated-glass-2, (2)
EC devices as a function of applied coloration/bleaching
voltages has been performed. Results of the XRD charac- where ITO-coated-glass-1 and ITO-coated-glass-2 are the
terization of the structural changes occurring during the two transparent electrodes (TEs) used to apply the electric
Journal of Nanomaterials 3

(a) 400◦ C (b) 500◦ C (c) 600◦ C

Figure 1: Transmission electron micrographs of tungsten oxide films prepared at 400 (grain size ∼10 nm), 500 (grain size ∼19 nm), and
600◦ C (grain size ∼25 nm).

field, WO3 is the electrochromic layer and ICL is the ion states by fitting the diffraction patterns. Each spectrum is
conducting and electronically insulating layer. The ICL is fitted to a series of Gaussian peaks superimposed on an
applied on top of the WO3 layer and the ITO-coated- overall quadratic background. These fits, shown as lines in
glass-2 is gently pressed against this coating to ensure a the figure, match the data points closely. The peak width,
uniform distribution of the ICL. After making the electrical assumed to be the same for all reflections, and the intensities
connections, the EC device is ready for testing. The area of of the individual peaks are treated as fitting parameters.
the EC devices was 5 × 2.5 cm2 . We correct the peak width for the instrument resolution
and use it to estimate the crystallite size using the Scherrer
2.4. Structural and Optical Characterization method, assuming that for example, crystallite-to-crystallite
variations of the lattice parameter do not contribute to the
2.4.1. Transmission Electron Microscopy. A WO3 layer was peak widths.
deposited onto a SiO2 -coated glass substrate and annealed
in air at 400, 500, or 600◦ C for one hour. TEM of the WO3 2.4.4. UV-VIS Spectrophotometery. The optical transmit-
layers was performed on a small amount of film scrapped off tance spectra of the EC devices in their colored/bleached
the SiO2 -coated glass substrate and placed into a glass vial. states were recorded at normal incidence with a Biochrom
The sample was imaged using a 2011 JEOL STEM at 200 keV. Ultrospec 2000 UV-visible spectrophotometer.
Images were captured on a 4 k × 4 k multiscan CCD camera
using Digital Micrograph from Gatan.
3. Results and Discussion
2.4.2. Raman Spectroscopy. Raman spectra were recorded at 3.1. Microstructure of the EC Layer Prepared at Different
room temperature with a Jobin-Yvon Labram HR micro- Temperatures. TEM of the WO3 layers was performed on
analytical spectrometer equipped with a motorized xy stage a small amount of film scraped off the SiO2 -coated glass
and autofocus. The spectra were generated with 17 mW, substrate. Figure 1(a) shows the TEM image of the nanocrys-
632.8 nm He-Ne laser excitation and dispersed with the talline WO3 annealed at 400◦ C. The nanocrystalline nature
1800 grooves/mm grating across the 0.8 m length of the is evident from the dimension of domain which is showing
spectrograph. The laser power was 4 mW at the sample crystalline lattice. The interplanar distances obtained by
surface. The spectral resolution is estimated to be less than inverse Fast Fourier transforms (FFTs) of lattice spacing
0.5 cm−1 for a slit width of 150 μm and a confocal hole of shown in the region indicated by the box were found to
300 μm. be 0.72 and 0.79 nm, respectively. These lattice spacings
correspond to those of hexagonal WO3 (h-WO3 ) which are
2.4.3. X-Ray Diffraction (XRD). XRD measurements were a = 0.7298(2) nm, c = 0.7798(3) nm. Figure 1(b) shows the
carried out in reflection with a custom built theta-theta TEM image for the film annealed at 500◦ C. The average
diffractometer equipped with pyrolytic graphite monochro- crystallite size was found to be 19.3 nm. The lattice spacings
mator and analyzer crystals. Cu K-α radiation (λ = were determined by the FFT of the lattice fringes at two
0.154178 nm) was used for the measurements, and the data different points on the WO3 crystallites (not shown here)
are shown as a function of the modulus of the scattering and are found to be 0.3658 and 0.3625 nm, again matching
vector q = 4πλ−1 sin θ, where 2θ is the scattering angle. m-WO3 . Figure 1(b) also shows the mesoporous structure
Air scattering was avoided by evacuating the sample space. of the walls separating the macropores in the WO3 films.
We determine the lattice constants for different sample Figure 1(c) shows the TEM image of the similarly prepared
4 Journal of Nanomaterials

690.8
400◦ C

251.4

817.2
Hexagonal

642.8
321.2
161
(a) (a)
Raman intensity (a.u.)

X-ray scattering intensity

806.2
500◦ C

711.6
270.7
Monoclinic
83.6

329.5
134
72

(b) (b)
268.5

712.6
(Anatase TiO 2 )

806.2
600◦ C
133.6

635.5
92.5

328.1
151.5

Orthorhombic

(c)

(220)
(021)
(201)
(120)

(111)
∗
(c)

(020)
(200)
(002)
0 200 400 600 800 1000
Wavenumber (cm−1 )
14 16 18 20 22 24
Figure 2: Micro-Raman spectra of tungsten oxide thin films q (nm−1 )
prepared at 400, 500, 600◦ C indicating the formation of h-WO3 ,
m-WO3 , and o-WO3 . Figure 3: XRD patterns of tungsten oxide thin films prepared at
400, 500, 600◦ C indicating the formation of h-WO3 , m-WO3 , and
o-WO3 . The peak at 15.5 nm−1 , indicated by ∗ , is emerging from the
sample. From the TEM image, it can be observed that the ITO layer (c).
film is composed of WO3 nanocrystallites of an average size
∼25 nm. The value of the interplanar distance is 0.3683 nm,
which is the lattice parameter c of m-WO3 . Pecquenard et al. have shown that o-WO3 can be crystallized
at temperatures between 600 and 800◦ C using titanium
oxide as structure stabilizer [22]. They reported the lattice
3.2. Crystalline Phases of the EC Layers Prepared at 400, 500,
vibrational mode of o-WO3 at 91 cm−1 , which is similar to
and 600◦ C. Raman spectra of the WO3 film heat treated
our result for the WO3 -TiO2 composite film annealed at
at 400 and 500◦ C are shown in Figures 2(a) and 2(b). For
600◦ C.
the films heat treated at 400◦ C, the bands below 200 cm−1
can be ascribed to lattice vibrations. The band observed at Figure 3(a) shows the X-ray scattering of the WO3 layer,
251.4 cm−1 is assigned to δ(O-W-O) deformation vibrations, deposited on the ITO glass substrate and annealed at 400◦ C
while the bands at 690.8 and 817.2 cm−1 are due to ν(O- for one hour corresponds to hexagonal WO3 , for which
W-O) stretching vibrations. These bands are characteristic the JCPDS card 85–2460 diffraction pattern is shown by
features of h-WO3 . The Raman peak positions of our h-WO3 the vertical bars [23]. By fitting the diffraction pattern, we
films match those reported for h-WO3 powder by Daniel et find the lattice constants of the hexagonal phase to be a =
al. [21]. The bands at 817.2 and 690.8 cm−1 are broadened 0.7379 ± 0.0008 and c = 0.7756 ± 0.0002 nm.
due to the nanocrystalline nature of the h-WO3 films. Figure 3(b) shows the diffraction pattern of the WO3 film
Figure 2(b) shows the Raman spectrum of the films prepared heat treated at 500◦ C. It matches with the JCPDS card 43–
at 500◦ C. The m-WO3 features are observed from the Raman 1035 diffraction pattern of pure m-WO3 (vertical bars). The
peaks at 134.0 cm−1 (lattice mode), 270.7 cm−1 δ(O-W-O), lattice parameters obtained from the fitting of the diffraction
and ν(O-W-O) modes at 711.6 and 806.2 cm−1 . pattern are a = 0.7351 ± 0.0002, b = 0.75396 ± 0.0005,
The Raman spectrum (Figure 2(c)) of the WO3 -TiO2 c = 0.7712 ± 0.0002 nm, with β = 90.3◦ . Although the peaks
composite film heat treated at 600◦ C shows peaks at 806.2, are similar in Figures 3(b) and 3(c), the lattice parameters
712.6 cm−1 (ν(O-W-O)), 328.1, 268.5 cm−1 (δ(O-W-O)), obtained from the fitting for the sample annealed at 600◦ C
133.6, 92.5 cm−1 (lattice modes) and a low intensity peak are a = 0.7351 ± 0.0019, b = 0.7566 ± 0.0019, and c =
at 151.5 cm−1 . It is well known that the peak positions 0.7724 ± 0.0021 nm, with β = 90◦ indicating that the WO3
corresponding to the stretching vibrations of O-W-O bonds is in the orthorhombic phase.
are the same for the triclinic, monoclinic, and orthorhombic
phases of WO3 , whereas their lattice vibrations in the 3.3. Construction of Asymmetric Electrochromic Devices Based
range 70–100 cm−1 show a difference in the Raman spectra on h-WO3 , m-WO3 , and o-WO3 Layers. In this section we
[17, 22]. This is primarily due to the fact that the lattice describe the construction of asymmetric EC devices by
vibrational bands arise from the (W2 O2 )n chains of WO3 . As using the thus synthesised h-WO3 , m-WO3 , and o-WO3 thin
the low temperature phases of WO3 are less symmetric than films as the active electrochromic layer. The asymmetric EC
the high-temperature phases, the lattice vibrations between device consists of an ion conductor layer, which also acts
70 and 100 cm−1 in Figure 2(b) exhibit more Raman bands as a counter electrode and a WO3 EC layer as the working
for the monoclinic phase (83.6, and 72.0 cm−1 ) and only one cathode. These are sandwiched between two transparent
mode at 92.5 cm−1 for the orthorhombic phase (Figure 2(c)). conductive electrodes. As a low voltage is applied across the
Journal of Nanomaterials 5

B
2V

Raman intensity (a.u.)

817.2
Scattered X-ray intensity (a.u.)

690.8
251.4
2V
A 0V

0V

−2 V
−2 V
B
14 16 18 20 22 24 26 200 400 600 800 1000
q (nm−1 ) Wavenumber (cm−1 )
(a) (b)

Figure 4: Electrochromic structural changes in the EC device constructed using h-WO3 layer.

transparent conductors (1–3 V), ions move from the counter initially the same, indicating that the unit cell volume
electrode and electrons from the transparent electrode to the decreases as the device ages during cycling. With an applied
EC layer to trigger a color change. The EC phenomenon voltage of ±2.0 V, we observe that the lattice constant c
occurring with such double injection can be represented as: is significantly lower for the Li-intercalated state (positive
voltage) and that c increases as the lithium ions are extracted.
WO3 + xLi+ + xe− ←→ Lix WO3 The crystallite size remains generally close to 10 nm, with a
(3) possible slight increase during the measurement sequence.
clear dark blue
Raman spectra show strong changes in the stretching
where x electrons (e− ) and lithium ions (Li+ ) are inserted bands. Figure 4(b)A shows the Raman spectrum of the pure
into or ejected from the system. Reversing the voltage restores h-WO3 layer. The bands located at 251.4 cm−1 , due to δ(O-
the device to its previous clear (bleached) optical state. The W-O), and at 690.8 and 817.2 cm−1 due to the ν(O-W-
ion conducting layer is a gel which is prepared by mixing O), are the characteristic Raman modes of the h-WO3 . By
lithium iodide (LiI) and iodine (I2 ) in an ethanol solution applying a potential of 2.0 V across the device, Li ions are
with ORMOSIL. A network of silanes, present in ORMOSIL, intercalated from ICL into the h-WO3 layer. Figure 4(b)B
acts as the ion storage layer. This ion conducting layer shows the Raman spectrum of the EC device in its colored
supplies Li+ ions to the EC layer under proper biasing. This state after applying a voltage of 2.0 V. It can be seen that
layer is applied on top of the WO3 layer and another ITO- upon Li intercalation at this potential, the modes due to the
coated glass substrate is gently pressed against the ICL gel. ν(O-W-O) stretching vibrations disappear. Correspondingly,
The transparent conductive electrode (ITO layer) is 190 ± by reversing the potential (−2.0 V), the device reverts to its
40 nm thick. The thickness of the WO3 layer used in the previous bleached state by deintercalating Li (Figure 4(b)B ),
EC device was of 842 ± 50 nm. The 12 ± 1 μm thick ICL is clearly demonstrating the structural reversibility of the active
sandwiched between the WO3 layer and a second ITO coated- layer of the EC device.
glass slide. Then the device is connected to the leads, and it is A striking difference in the Raman spectra of h-Lix WO3 is
ready for the testing. the vanishing of bands at the applied coloration potentials of
2.0 V, although XRD pattern showed no structural transition.
3.4. Electrochromic Structural Studies during Intercalation In order to understand the vanishing of the stretching ν(O-
(Deintercalation) of Li+ Ions into (Ejected out of) the h-WO3 W-O) modes in the Raman spectra (Figure 4(b)B), while
Layer of the EC Device. Figure 4 shows the XRD pattern (a) the EC active layer remains (h-Lix WO3 ) we consider the
and the Raman spectrum (b) of the EC device constructed Li+ occupancy for the applied potential of 2.0 V. In this
by using the h-WO3 layer as an active working layer, in scenario, Li ions inside the hexagonal windows (HW) start
its colored and bleached states for applied potentials of moving towards the four coordinated square window (SW)
0.0 and ±2.0 V. Inserting and extracting lithium at ±2.0 V in order to accommodate the additional Li ions [9]. Hibino
shift the diffraction peak positions as seen in the figure. et al. have suggested that the location of Li ion near the
The lattice parameters of the WO3 EC layer at 0 V are a = SW is governed by the Li-Li ionic distances and the distance
0.7379 ± 0.0008 and c = 0.7756 ± 0.0002 nm. We note that between the SW [24]. As there is no shielding for the Li
the lattice parameter c decreases to 0.76152 ± 0.0003 during ions and the Li-Li ionic distance is more than 5.5 Å, Li ions
the sequence of measurements. The observed variations in can only occupy alternate sites close to SW. This leads to
the lattice parameters of h-WO3 EC layer upon lithiation are ordering of Li ions inside the h-WO3 . Hibino et al. have
compared in the Table 1. The lattice parameter a remains mentioned that for Li/W ratios >0.4, the SWs of the h-WO3
6 Journal of Nanomaterials

Table 1: The lattice parameters of WO3 EC layer prepared at 400, 500, and 600◦ C and the lattice parameters after lithiating the sample at
+2.0 V.
Lattice parameter
S. No. Sample name Coloration voltage nm Angle
a b c β
0V 0.7379 ± 0.0008 — 0.7756 ± 0.0002 —
1 400◦ C (Hexagonal)
+2 V 0.74118 ± 0.0012 0.76152 ± 0.0003
0V 0.7351 ± 0.0002 0.7540 ± 0.0005 0.7712 ± 0.00019 90.3 ± 0.6
2 500◦ C (Monoclinic)
+2 V 0.7397 ± 0.0015 0.7418 ± 0.002 0.7717 ± 0.0002 89.6 ± 10.1
0V 0.7351 ± 0.0019 0.7566 ± 0.0019 0.7724 ± 0.0021 90.0
3 600◦ C (Orthorhombic)
+2 V 0.7445 ± 0.0023 0.7469 ± 0.0058 0.7624 ± 0.0055 90.0
Scattered X-ray intensity (a.u.)

B 2V

Raman intensity (a.u.)

B 2V
133.3
270.7 713.7
A 0V
0V
A

−2 V −2 V
B B

14 16 18 20 22 24 26 200 400 600 800 1000

q (nm−1 ) Wavenumber (cm−1 )
(a) (b)

Figure 5: Electrochromic structural changes in the EC device constructed using m-WO3 layer.

structure start to be occupied. In our case this happens when b = 0.75396 ± 0.0005, c = 0.7712 ± 0.0002 nm, with β =
a coloration voltage of 2.0 V is applied to the EC device [24]. 90.3◦ . As the coloration voltages were applied, the XRD
h-WO3 is constituted by WO6 octahedrons. The ab plane in peaks change in the position and in the intensities indicating
WO6 is already nearly symmetric. When Li is inserted into a structural transition associated with intercalation of Li.
the square windows, the axial oxygen is also symmetrized, When a coloration potential of 2.0 V is applied, the a and
which results in isostructural WO6 octahedra as in the cubic- b lattice parameters converge to a value of 0.7412 nm, while
ReO3 structure. For this type of structure vibrations are c parameter is 0.77165 nm. The XRD pattern of the Lix WO3
not Raman active. Hence Raman modes vanish for the Li after Li intercalation resembles that of the tetragonal WO3
ion intercalation at a coloration potential of 2.0. A detailed crystalline phase (JCPDS 89–1287). The phase transition
account on the structural transformation of h-Lix WO3 is from m-WO3 to tetragonal Lix WO3 (t-Lix WO3 ) is obtained.
presented elsewhere [9]. It should be noted that, when the Li ions are deintercalated
by applying reverse potential, the crystalline structure of m-
3.5. Electrochromic Structural Studies during Intercalation WO3 layer reverts back to the initial monoclinic lattice as
(Deintercalation) of Li+ Ions into (Ejected out of) the m-WO3 shown in Figure 5(a)(B ). The observed variations in the
Layer of the EC Device. Figure 5 shows the XRD pattern (a) lattice parameters of m-WO3 EC layer upon lithiation are
and the Raman spectra (b) of the EC device constructed compared in the Table 1.
by using the m-WO3 layer as an active working layer, in its Figure 5(b) A shows the Raman spectrum of the pure
colored and bleached states for applied potentials of 0.0 and m-WO3 layer. The Raman peaks at 713.7 and 806.2 cm−1 ,
±2.0 V. The X-ray scattering of the Lix WO3 layer of the EC attributed to ν(O-W-O) modes of m-WO3 , were followed
device based on the m-WO3 layer is shown in Figure 5(a) during the EC coloration and bleaching at ±2.0 V. Fig-
as a function of the applied voltage. The diffraction pattern ure 5(b)B shows the Raman spectrum of the m-WO3 layer,
of the pure m-WO3 layer, for which the JCPDS card 43– coloured at 2.0 V. The Raman modes due to ν(O-W-O)
1035 diffraction pattern is represented by the vertical bars, is vanish completely. It has been observed from our previous
shown in Figure 5(a)B . We determine the lattice constants work on XRD of Lix WO3 layer that for the applied coloration
a, b, and c and the angle β of the monoclinic phase for potential of 1.0 V, the lattice parameter c decreases from
different sample states by fitting the diffraction patterns 0.77418 ± 0.0002 nm to 0.7717 ± 0.00015 nm. At the same
shown in Figure 5(a). The XRD pattern of the pure m- time, the lattice parameters a (= 0.7397 ± 0.00145 nm) and b
WO3 layer has the lattice parameter a = 0.7351 ± 0.0002, (= 0.7418 ± 0.0021 nm) converge to a same value within the
Journal of Nanomaterials 7

Scattered X-ray intensity (a.u.)

∗ B
2V

Raman intensity (a.u.)

B 2V
806.5
268.5 712.6
∗ 0V A 0V
A
∗

B −1.8 V
∗
−2 V
B
14 16 18 20 22 24 26 200 400 600 800 1000
q (nm−1 ) Wavenumber (cm−1 )
(a) (b)

Figure 6: Electrochromic structural changes in the EC device constructed using o-WO3 layer.

experimental error. This tendency of c to converge towards a o-WO3 EC layer, upon lithiation, are compared in the
and b indicates that the system is moving towards a cubic Table 1. This observed structural change is consistent with
phase as the amount of intercalated Li is increased. The the well-established Li-induced phase transitions of low-
vanishing of the Raman mode is also attributed to this trend to high-symmetric phases in ReO3 -type tungsten oxides
of Lix WO3 system to move towards cubic phase. It has been [16, 17, 19]. Upon lithium intercalation, the low-symmetry
reported that the cubic Lix WO3 phase was obtained for phases of WO3 , such as triclinic and monoclinic, transform
x > 0.5 [5, 16]. In our case, Li intercalation into WO3 at to higher symmetry structures such as tetragonal and cubic
2.0 V is not sufficient to reach cubic phase, whereas a higher [16, 17, 19]. In this work, upon lithium ion intercalation,
symmetric state than that of the tetragonal phase is clearly we have observed the phase transition from o-WO3 to t-
observed. This indicates that for the applied potential of Lix WO3 , the next higher symmetric phase. In this tetragonal
2.0 V the amount of Li that has intercalated into m-WO3 is phase the “ab” plane of the WO6 octahedron is symmetric,
between 0.23 and 0.5. The complete vanishing of ν(O-W-O) a transformation induced by Li ion intercalation at 2.0 V.
Raman modes observed at a coloration potential of +2.0 V At this potential, the Li ion concentration is 0.226 and a
is attributed to a phase transition to a higher symmetric complete phase transformation to the t-Lix WO3 is achieved.
state than that of t-Lix WO3 . Also, it is possible that atomic These values of Li ion concentrations for the observed phases
displacement within the unit cell could take place with the are consistent with the values reported by other authors
same lattice parameters, as Raman spectroscopy is sensitive [16, 19]. The phase transition as a function of the applied
even to a small change in the lattice parameters. Figure 5(b)B potential occurs gradually from o-WO3 to t-Lix WO3 with a
shows the Raman spectrum of the m-WO3 layer of the EC tendency for a phase transition towards a cubic Lix WO3 , as
device after the deintercalation of Li at −2.0 V. The recorded the concentration of the inserted Li ions increases from 0.090
Raman spectra exhibit the spectral features of the initial to 0.226.
pure m-WO3 layer (Figure 5(b)A). This demonstrates the Figure 6(b) shows the Raman spectra of the o-WO3
structural EC reversibility of the system. layer in a working EC device as a function of applied
voltage. When a coloration potential of 2.0 V is applied,
3.6. Electrochromic Structural Studies during Intercalation all the O-W-O stretching modes vanish (Figure 6(b)B), as
(Deintercalation) of Li+ Ions into (out of) the o-WO3 Layer expected for the more symmetric phases. The XRD analysis
of an EC Device. Figure 6(a) shows the X-ray scattering of shows that the phase transition occurs gradually, and it
the Li+ intercalated/deintercalated o-WO3 layer in a working is impossible to clearly identify the phase of the Lix WO3 ;
EC device for applied potentials of ±2.0 V. The differences in since the lattice parameters are changing continuously as
the positions and intensity of the diffraction lines observed a function of applied potential or in other words, as a
in Figure 6(a) show the structural changes associated with function of the amount of intercalated Li ions. The Raman
Li ion intercalation/deintercalation. The XRD pattern of Li spectrum in Figure 6(b)B shows no O-W-O stretching modes
ion deintercalated state is similar to that of the o-WO3 state due to the fact that the structure of the o-WO3 layer is
at 0 V. The lattice parameters of the o-WO3 layer calculated gradually becoming more symmetric. In a previous work,
from the fitting of the XRD patterns are a = 0.7351 ± 0.0019, we have shown that for higher voltages such as 3.0 V, the
b = 0.7566 ± 0.0019, and c = 0.7724 ± 0.0021 nm, with Lix WO3 attains a cubic phase when starting from the m-
β = 90◦ . Upon applying a coloration potential of 2.0 V, WO3 phase and that all the Raman modes vanished [5].
a transition to the t-Lix WO3 phase is obtained. At this Figure 6(b)B show that the o-WO3 crystalline structure is
potential, the lattice parameters a and b attain about the recovered, when the coloring voltage is reversed (−2.0 V),
same value (a = 0.7445 ± 0.0023, b = 0.7469 ± 0.0058 nm), demonstrating the reversibility of the device. The detailed
whereas c is reduced to 0.7624 ± 0.0055 nm. The observed report on the performance of the o-WO3 layer as EC active
variations in the lattice parameters of titania stabilized layer is presented in our previous paper [25].
8 Journal of Nanomaterials

90 90 100
90
80 80 Bleached
80
Transmittance (%)

Transmittance (%)

Transmittance (%)
70 70 70
60 60 1V
60
50 50 50
1.5 V
40 40 40
30 30 30
20 2V
20 20
10
10 10 0 2.5 V
0 0
200 400 600 800 1000 0 200 400 600 800 1000 200 400 600 800 1000
Wavelength (nm) Wavelength (nm) Wavelength (nm)
(a) (b) (c)
Figure 7: Transmission spectra of the EC devices constructed using h-WO3 , m-WO3 , and o-WO3 in the as prepared state, at coloration
potential of 2.5 V and at bleaching potential of −1.0 V. The photos show the visible coloration to the naked eye when the EC devices are
colored at various coloration potential. The photos represent typically the EC device based on m-WO3 .

3.7. Optical Studies of the Electrochromic Devices Based tungstic acid as a precursor and ORMOSIL as a templating
on the h-WO3 , m-WO3 , and o-WO3 Layers. The optical agent. Pure h-WO3 NC films with crystallite size of ∼10 nm
transmittance of the EC device constructed by using the h- were obtained after calcination at 400◦ C. Pure m-WO3
WO3 , layer in its colored and bleached states for an applied films with crystallite size of ∼16 nm were synthesized after
coloration potential of 2.5 V and at bleaching potential of annealing at 500◦ C. o-WO3 thin films, stabilized by NC
−1.0 V is shown in Figure 7(a). The recorded transmission anatase TiO2 , are obtained by a sol-gel-based two-stage
spectra of the device in the bleached state for potentials at dip coating method and subsequent annealing at 600◦ C.
−2.5 V are indistinguishable from the spectrum of the device Thus prepared WO3 films on ITO coated glass substrate
bleached at −1.0 V (hence not shown), clearly demonstrating were used as the active EC layer for the construction of
the reversibility of the device. In the bleached state, the various asymmetric EC devices. Coloration and bleaching
transmittance of the device at a wavelength 1100 nm was of the EC devices were achieved by intercalating and
76.9%. At +2.5 V the transmittance is reduced 0.1%. When deintercalating Li into the WO3 layers at coloration potential
the coloration potentials of +2.5 V are applied, the maximum of 2.5 V and at bleaching potential of −1.0 V. The EC
transmittance is observed at 403.5 nm, and the transmittance devices based on h-WO3 , m-WO3 , and o-WO3 as EC active
FWHM is 147.0 nm. The optical modulation of ∼76% above layers exhibit an exceptionally high optical modulation
800 nm obtained here is exceptionally high for EC devices of 70% and qualify the device for EC smart window
[26]. Figure 7(b) shows the optical transmittance spectra of applications.
a m-WO3 -(prepared at 500◦ C) based EC device in bleached
state (−1.0 V) and coloured at +2.5 V. In the bleached state,
the transmittance of the device at 1100 nm was 76.4%. At Acknowledgment
the coloration potential of +2.5 V the transmittance was The financial support of the National Science and Engi-
reduced to 0.0%. The device exhibits an optical modulation neering Research Council (NSERC) of Canada is gratefully
of 76.1%. Figure 7(c) shows the transmission spectra of the acknowledged.
o-WO3 , based EC device in its colored and bleached states.
In the bleached state the transmittance at a wavelength of
1100 nm was 78.5%. At a coloration potential of +2.5 V the References
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