Journal of The Electrochemical Society, 161 (14) E191-E201 (2014) E191

Electrochromic Enhancement of WO3 -TiO2 Composite Films

Produced by Electrochemical Anodization
Y. Gui and D. J. Blackwoodz
Department of Materials Science and Engineering, National University of Singapore, Singapore 117574

An enhancement of the electrochromic properties of WO3 thin films by the incorporation of TiO2 is presented. The composite films
are obtained by anodizing co-sputtered tungsten / titanium on conductive glass substrates in 1 M H2 SO4 solution containing 0.3
wt% NaF. As the titanium content is increased from 0 to 15 at.% a morphology evolution occurs, from nano-porous to nano-flakes
and finally to nano-blocks interweaved with nano-pores. The nano-flakes, obtained at 10 at% Ti, proved to be the most conducive
structure for the insertion and removal of Li+ ions such that this composition exhibits transmittance regulation abilities of 58.5%,
72% and 77.7% at 550 nm, 632.8 nm and 800 nm respectively, which are more than a 25% improvement at all wavelengths over a
pure WO3 film formed in the same way. The WO3 /TiO2 film with addition of 10 at.% Ti also has faster coloration/bleaching times,
especially in the critical near infrared region with values of 10 s / 64 s at 800 nm compared with 32 s / 90 s of a pure WO3 thin film,
as well as improved stability losing less than 5% of its capacity after 1000 switching cycles.
© The Author(s) 2014. Published by ECS. This is an open access article distributed under the terms of the Creative Commons
Attribution 4.0 License (CC BY, http://creativecommons.org/licenses/by/4.0/), which permits unrestricted reuse of the work in any
medium, provided the original work is properly cited. [DOI: 10.1149/2.0631414jes] All rights reserved.

Manuscript submitted August 18, 2014; revised manuscript received October 3, 2014. Published October 11, 2014.

Tungsten trioxide displays an electrochromic effect the inten- Experimental

sity of which is closely correlated with its morphology, poros-
ity and composition, that in turn are influenced by its fabrication
process.1–4 Thus, various methods used to fabricate WO3 are reported,
such as evaporation,5–7 spray pyrolysis,8 pulsed layer deposition9,10
and electrodeposition.11,12 However, the electrochemical anodization
method adopted in this work provides a simple and economic way of
synthesizing targeted morphologies such as nanoporous or nanotube
structures. Unfortunately there are still drawbacks when compared to
vacuum deposited films, for instance the electrochemically prepared
WO3 has poorer reversibility and stability as well as a shorter opti-
cal modulation range. This has led to interest in mixed metal oxide
composite systems to compensate for these eficiencies.13–19
To date, there are many reports on the doping or mixing other ox-
ides with WO3 to improve its electrochromic properties, with oxides
of barium,20 cobalt, 21 nickel,22 molybdenum23 and most successfully
titanium.24 Even a small quantity of the guest oxide has a profound
effect on the host’s optical properties. Hashimoto and Matsuoka first
reported in 1991 that an amorphous WO3 -TiO2 film, produced by elec-
tron beam deposition method, exhibits a longer life-time than a pure
tungsten oxide film.24 Subsequently, in 1993, Gottsche et al.25 com-
pared the electrochromic properties of mixed WO3 -TiO2 thin films
fabricated by sputtering and sol-gel techniques. These authors point
out that the addition of TiO2 with molar percentages ranging from
10% to 15% reduced the crystallinity of WO3 host and led to signifi-
cant structural changes. Later, Wang and Hu successfully composed a
TiO2 -doped WO3 film by spin coating and found that the Ti-addition
stabilized the peroxotungstic acid in the spin coating solutions.26 In
2005, Patil et al.27 prepared WO3 -TiO2 films via a spray pyrolysis
method and discussed the improved electrochromic reversibility and
coloration efficiency.
However, in these earlier works the coloration efficiency has not
improved significantly to the level where it can be used in a practical
smart window. Indeed, in some cases certain levels of TiO2 addi-
tions were detrimental to the coloration efficiency.13,25 Therefore, this
work reports a study on the influence of titanium content in WO3 -
TiO2 films produced by anodization of co-sputtered W/Ti films, a
technique, apparently, not previously adopted. It will be shown that
the titanium addition of up to 10 at.% greatly improves both the
electrochromic reversibility and coloration efficiency, however high
loadings are detrimental. The mechanisms by which these improve-
ments are achieved are also proposed based on the findings from
electrochemical impedance spectroscopy and various materials char-
acterization techniques.
z
E-mail: msedjb@nus.edu.sg
Fluorine coated tin oxide (FTO) glass substrates of sheet resistance
15 •sq−1 were cut to 24 mm × 50 mm rectangles and cleaned by
sequential ultrasonication in 5% Deconex@90, Milli-Q water (Re-
sistivity ∼10 M•cm), isopropanol, acetone and absolute ethanol,
each for 15 minutes. The cleaned FTO glasses were kept in clean
isopropanol solutions to avoid contaminations and ready for use.
For the film deposition, the clean substrates, with 20% covered
by aluminum foil in order to expose parts of conductive surface for
electrical connecting with wires, were placed into the chamber of a DC
Magnetron Sputter. The targets (AJA International, Inc.) were 99.99%
W and 99.99% Ti. The distance between each target and the substrate
was 8 cm. Before deposition, the sputtering chamber was evacuated
to 6.0 × 10−7 Torr for almost 12 hours at room temperature, then
sputtering of tantalum and titanium was conducted simultaneously in
an inert argon atmosphere (2.0 × 10−6 Torr) on to the cleaned FTO
substrates at a temperature of 400◦ C. During sputtering, the flow rate
of argon was kept at 27×10−3 torr min−1 .28,29
The 0% and approximately 7%, 13% and 17% atomic ratios of
titanium over tungsten in W/Ti films were obtained by adjusting the
RF power the titanium target to 0, 10, 15 and 20 W respectively,
keeping that to the tungsten target at 90 W. The titanium sputtering
rate was about 1 nm min−1 with RF power of 10 W and the tungsten
was 6 nm min−1 at 90 W. During the sputtering process, not all the
atoms can be collected by the substrates, hence there is a loss of atoms
so the atomic ratio should not be estimated according to the sputtering
rate related RF power. Therefore atomic ratios quoted shown above
were determined by EDS after co-sputtering. All the thickness of the
films was controlled at around 450 nm.
After magnetron sputtering deposition, the pure tungsten and W/Ti
thin films were anodized in 1 M H2 SO4 solution containing 0.3 wt.%
NaF using a two electrode system with a platinum cathode, initially
at a sweep rate of 1 V s−1 was imposed to 40 V with the positive limit
being maintained for 40 min (Keithley 236 Source Measuring Unit).
Then, the samples were carefully washed with Milli-Q water and dried
in a stream of nitrogen gas. Finally, to ensure complete oxidation, the
samples were annealed in air at a temperature of 450◦ C for 3 hours,
using a ramp rate of 2◦ C min−1 .
The morphologies and elemental distributions of the WO3 /TiO2
thin films were investigated by using a Zeiss Field Emission Scanning
Electron Microscopes (FESEM). The crystal structures of the thin
films were probed using a Bragg-Brentato theta-two theta diffrac-
tometer (Brucker D8 Advance) scanning from 20◦ to 80◦ with Cu K-α
X-ray source (1.54 Å). The oxidation states and surface composition
of the as-prepared samples were confirmed by high-resolution X-
ray photoelectron spectroscopy with a Kratos Axis UltraDLD X-ray

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 E192 Journal of The Electrochemical Society, 161 (14) E191-E201 (2014)
461.5nm
Figure 1. SEM images (a) top view and (b) cross section of as-sputtered pure
tungsten thin film; the addition of titanium did not change the morphology of
the films.
photoelectron spectrometer equipped with an Al Kα X-ray source
(1486.6 eV), with the high resolution HRXPS spectra being analyzed
with the aid of Casa-XPS software. The peak of carbon at 284.5 eV
was used as an internal standard for calibration of the binding ener-
gies and originated from surface adsorbed carbon moieties. Except for
this, there were no other discernable impurities in the samples. Raman
measurements were performed with a Renishaw Raman microscope
with an Ar ion laser at 532 nm excitation wavelength.
The electrochemical and optical properties were investigated in
1 M LiClO4 (anhydrous) dissolved in propylene carbonate using a
conventional three electrode cell, with a Pt counter electrode and a
non-aqueous Ag/Ag+ reference electrode system consisting of a sil-
ver wire placed in 0.01 M AgNO3 plus 0.1 M tetrabutylammonium
perchlorate dissolved in acetonitrile and all potentials in this work are
versus this reference system (0.30 V vs SHE). Cyclic voltammetry
(CV), electrochemical impedance spectroscopy (EIS) and chronoam-
perometry (CA) measurements were conducted at room temperature
and controlled by an Autolab PGSTAT302N potentiostat with Gpes
software. The CV tests were carried out at a scan rate of 50 mV/s from
−2.0 V to +1.0 V vs. Ag/Ag+ . EIS tests were carried out with a su-
perimposed 5 mV sinusoidal (RMS) perturbation over the frequency
range from 100 kHz to 0.01 Hz and analyzed by fitting to an equiva-
lent circuit with the aid of Z-View software (Scribner Associates Inc.).
The fit errors were calculated as in the following example: if the best
value for a particular resistor is 200 , the value is increased until the
goodness of fit starts to decrease. If 196  and 204  produce a very
similar goodness of fit, but 195  and 205  produces a poorer fit,
the error is reported as 4  and the percentage fitting error is 2%. In
addition, chi-square goodness of fit tests were performed between the
experimental data.
Chronoamperometry tests were performed by applying repetitive
potential cycles that consisted of holding the films at −1.0 V vs.
Ag/Ag+ for 50 s and then stepping to +1.0 V vs. Ag/Ag+ for 150
s. The electrochromic properties of the target films were recorded by
conducting in-situ electrochemical experiments in a quartz cuvette
located in a Shimadzu UV-Vis 1800 spectrometer, i.e. the changes in
the transmittance of the films were followed simultaneously with the
CA tests. The reference side of the UV-Vis spectrometer contained
a quartz cuvette filled with 1 M LiClO4 dissolved in propylene car-
bonate. All solvents and chemicals were of analytical grade and used
without further purification.
Results and Discussion
Typical SEM images of the as-sputtered pure tungsten thin film
on FTO are shown in Figure 1; the morphology of the co-sputtered
thin film was the same as the pure tungsten one. From the top view it
can be seen that the as-sputtered films consist of octahedral particles,
while the cross section image shows arrow-head shaped particles that
stack layer by layer to form column structures. These columns appear
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Anodization Current density (mA cm )
-2
WT0
WT7
4 WT10
WT15
I
3
2
II
0
0 5 10 15 20 25 30 35 40
Anodization time (min)
Figure 2. Anodic current density transients for W/Ti films in 0.3 wt% NaF
dissolved in 1 M H2 SO4 under a sweep rate of 1 V s−1 for 40 s to a fixed
potential of 40 V for 40 min.
strongly adhered to the FTO, as no cracks are found at the interface
between the bottom of film and substrate. Besides, these columns also
appear closely packed, implying a compact structure which is impor-
tant for obtaining an oxide film with good qualities during anodization.
From the cross section SEM the thickness of the as-sputtered films is
estimated to be 450 nm.
The amounts of titanium mixed into the tungsten matrix through
co-sputtering as analyzed by SEM-EDS were 10 at.%, 13 at.% and 17
at.%, with only a small variation of 0.6 at% found at different locations
across a single surface. By adjusting the electron beam density of
SEM-EDS from 10 keV to 20 keV it is found that the titanium was
distributed uniformly throughout the depth of the samples.
Figure 2 shows that once the positive voltage limit of the an-
odization process was obtained the current density initially declined
rapidly declined (Region I) as the anodic oxide thickened and high
field conditions were lost. However, after about 5 min the current
density settled to a near constant value (Region II) indicating that a
steady-state had been achieved between the oxide’s electrochemical
formation and chemical dissolution rates, as shown in Equations from
(1) to (4).30,31 It is in this second region that pores develop in the oxide
films.
T i + 2H2 O ↔ T i O2 + 4H + + 4e− [1]
T i O2 + 6H F ↔ T i F62− + 2H2 O + 2H + [2]
W + 3H2 O ↔ W O3 + 6H + + 6e− [3]
W O3 + H F ↔ f luoride complex + H2 O + H + [4]
Elemental analysis by EDS revealed that the atomic percentage of
titanium (only considering the metal components W and Ti) of the
anodized and annealed films decreased by approximately 3 at.%, to
7 at.%, 10 at.% and 15 at.% respectively, which likely reflects the
faster dissolution rate of the titanium over tungsten as also indicated
in Figure 2 where the current density increases with titanium content.
At this point the anodized films were named as WT0, WT7, WT10
and WT15, which represent WO3 /TiO2 films with 0 at.%, 7 at.%, 10
at.% and 15 at.% of titanium respectively.
Figure 3 shows SEM images of the films after anodization and
heat-treatment at 450◦ C for 3 hours, which has been reported to yield
a fully crystallinity film.32 It can be seen that as the amount of titanium
is increased the morphology changes from nano-porous for WT0 and
WT7 to nano-flakes for WT10 and finally to nano-block inter-weaved
 Journal of The Electrochemical Society, 161 (14) E191-E201 (2014) E193

Figure 4. SEM cross section images after anodization in 0.3 wt% NaF dis-
solved in 1 M H2 SO4 at 40 V for 40 mins and annealed at 450◦ C for 3 h:
(a) WT0, (b) WT7, (c) WT10 and (d) WT15.
Figure 3. SEM top images of films after anodization in 0.3 wt% NaF dissolved
in 1 M H2 SO4 at40 V for 40 mins and annealing at 450◦ C for 3 h: (a) WT0,
(b) WT7, (c) WT10 and (d) WT15. However, W O2+ is believed to act as the primary particle nuclei
2
instigating precipitation, so if its accumulation at the surface reaches
super-saturation conditions thickening of the formed nanostructures
porous structures for WT15. The formation of the nano-porous struc-
will occur and increase the possibility of forming flakes or blocks.35
ture of pure WO3 films anodized in fluoride ion (F− ) aqueous solutions
Figure 5 shows XRD patterns for WT0, WT7, WT10 and WT15
is the morphology commonly reported by many other groups.33 It can
thin films, along with indicated positions of the peaks belonging to
also be seen that the WT0 has good integrity without the appearance
the FTO substrate. All the remaining peaks in the diffraction patterns
any of the cracks and an average pore size of 80 nm. The similarity
can be indexed to the ICDD data file for WO3 with monoclinic struc-
in the porous structure of WT7 to that of WT0 indicates that 7 at.%
ture. The easily identified peak alignments along [001], [020] and
Ti has only a very limited effect on film morphology. However, rather
[200] directions separately in the diffraction patterns of pure WO3
than being nanoporous WT10 consisted of nano-flakes that were per-
pendicular to the substrate and disorderly arranged, forming spacious thin film corresponded to the characteristic lattice reflection planes of
channels and a large wall surface. On increasing the atomic percent- (001), (020) and (200) in typical monoclinic structures.36 From the
magnification of the 20◦ -30◦ region in Figure 5b, it can be seen that
age of titanium to 15% the pores collapse and become blocked with
the addition of titanium caused the peak at [020] direction to become
scattered nano-blocks as observed in WT15.
a preferential orientation and decreased the relative intensity of the
The cross section SEM images in Figure 4 reveal that anodizing
[001] and [200] direction peaks to the extent that the former is no
has reduced the thickness of all the films from their as-sputtered
longer resolved as a separate peak and the latter is too low to be de-
450 nm to 330 nm, 300 nm, 285 nm and 275 nm for WT0, WT7, WT10
tected for both of WT7 and WT10 films, but is just about identifiable
and WT15 respectively. The decreasing thickness with increasing
in WT15. The details of peak positions are listed in Table I.
titanium content is consistent with the earlier hypothesis that titanium
There was no obvious peak shift in the XRD patterns as the amount
oxides are more soluble in acidic fluorinated solutions than tungsten
of titanium was increased from 0 to 15 at%, except the [200] peak
oxides. Furthermore, from the view at their cross sections, it can also
of WT7 and WT10 moved slightly by −0.2◦ and −0.4◦ respectively
be seen that in: WT0 and WT7 the pores are orderly arranged, but no
compared with pure WO3 thin film. In addition, along this orientation
pores are observed close to the oxide/substrate interface; WT10 has
the peak intensity is decreased dramatically. Both these phenomenon
vertically aligned plates, which is in agreement with the nano-flake
reflect firstly that the titanium is likely to prefer occupying (200) planes
structure of the top-view image; WT15 has a less porous structure
inducing lattice variations and secondly the titanium interrupts orderly
due to coverage by interweaved nano-blocks, which is also consistent
arranged atoms on this plane resulting in a decrease in crystallinity.
with its top-view image.
For the WT15 thin film, it can be seen from Figure 5 that intensity
From a comparison of the respective anodic current density tran-
of all the XRD peaks dropped greatly; despite the same detectable
sient curves shown in Figure 2, it can be seen that the anodic current
surface area as the other films. This indicates a lower crystallinity in
density increases with increasing content in the as-sputtered film.
the WO3 /TiO2 thin films than the pure WO3 and that the degree of
Since the anodic current density predominantly arises from Reactions
the disorder is enhanced with the increasing percentage of titanium in
1 and 3, any increase in its rate will lead to an increase in the local
pure WO3 matrix. This conclusion is consistent with the SEM images
acidity at the electrodes surface, i.e. increased titanium content leads
to a drop in the localized pH. In turn, as the solubility of WO3 increases in which the pure WO3 thin film shows self-ordered porous structures,
with decreasing pH, the presence of titanium increases the rate of its WT10 exhibits randomly arranged nano-flakes vertically stacking on
dissolution as this can now precede via both Reactions 4 and 5.34 the FTO substrate and WT15 totally disorder structures with scattered
nano-blocks within the formed network of the nano-pores (Figures 3
W O3 + 2H+ = W O2+
2 + H2 O [5] & 4). The same phenomena were also observed by Lethy et al. who

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 E194 Journal of The Electrochemical Society, 161 (14) E191-E201 (2014)

(a) WT15
WT15

WT10
WT10
WT7 983
WT7
807.2
001 020 200
WT0
WT0
718.7
FTO 275.9
20 30 40 50 60 70 80 329.1
2 Theta
200 400 600 800 1000 1200
-1
Raman Shift (cm )
(b)
WT15
Figure 6. Raman spectra of WT0, WT7, WT10 and WT15.

WT10
WT7
001
020
200
WT0
FTO
20 22 24 26 28
2 Theta
Figure 5. (a) XRD patterns for WT0, WT7, WT10 and WT15 and (b) mag-
nification of the region between 20o and 30o .
used a pulsed laser deposition technique to produce WO3 /TiO2 films
on quartz substrates.37
Finally, no traces of TiO2 can be found in any of the XRD patterns
suggesting that the titanium was incorporated into the WO3 lattice
rather than forming a separate phase, although the lack of TiO2 peaks
could also be due to the low content of titanium or this could have
remained amorphous even after annealing.
Figure 6 shows the room temperature Raman spectra of the elec-
trochromic films after anodization and annealing, in which the previ-
ously reported O–W6+ –O stretching and bending modes expected
for monoclinic WO3 can be found.38,39 It can also be seen that
incorporation of titanium causes the O-W6+ -O stretching band at
719 cm−1 in pure WO3 (WT0) to red-shifts by about 20 wavenum-
bers and broaden considerably. Lethy et al.37 and Shigesato et al.40
explained the broaden of stretching mode in terms of neighboring ge-
ometric disorientation based on the molecular theory of vibration.41
This is consistent with the present XRD observations since the broad-
ening of the main diffraction peaks with increasing titanium content
implies an interruption on the atoms alignment, especially on (200)
planes. Alternatively, the red-shift of the Raman peaks at 719 cm−1
could be attributed to increased tensile strain as proposed by Liao et
al.42 and Portinha et al.43 when studying on ZrO2 and IrO2 thin films.
Figure 6 also reveals that the frequencies of the two low fre-
quency bending modes are broadened and their intensities weakened
by increasing titanium content, to the extent that they were almost
undetectable at the highest titanium loadings (WT15). In the light of
the molecular theory of vibration, it is likely that the substitution of
W6+ by Ti4+ ions caused local geometric disorientation in WO3 thin
film.43 Besides, the addition of titanium also led to the appearance of
a new Raman band near 983 cm−1 , which likely the same feature as
reported by Dikit et al.45 at 996 cm−1 for WO3 /transition metal oxide
catalysts, including WO3 /TiO2 , and assigned to a W = O symmetrical
stretching mode characteristic of the WO3 monolayer dispersion. Thus
this additional band proves a change of structure due to the titanium
additions.
30
As with the XRD the Raman spectra show no evidence of any
separate TiO2 phases, for which the A1g mode at 612 cm−1 / 512 cm−1
is the strongest followed closely by the Eg mode at 447 cm−1 / 634
cm−1 for rutile / anatase TiO2 .46,47
In order to ascertain the surface composition and chemical states,
XPS scans of WT0, WT7, WT10 and WT15 thin films after annealing
were obtained and shown are in Figure 7. As expected all the films
contain tungsten and oxygen elements, with titanium element also
detected in WT7, WT10 and WT15 with atom ratio of Ti/W 7 at.%,
12 at.% and 18 at.% separately which is an average difference of 2
at.% from the SEM-EDS data. The variation between the values de-
termined by the two techniques is likely due to the differences in their
probe depths, being several micrometers for SEM-EDS and only about
5–15 nm for XPS, which in turn suggests that the surface concentration
of titanium is about 2 at.% higher than its bulk value.
The W4f7/2 and W4f5/2 peaks were found to be well resolved in all
the spectra, being located at 35.2 eV∼35.8 eV and 37.3 eV∼38.9 eV
belonging to W6+ without other oxidation states being present.48–51
Likewise, the binding energies of Ti 2p3/2 and Ti 2p1/2 located at
458.4 eV ∼ 459.0 eV and 464.2 eV ∼ 464.8 eV are attributed to
Ti4+ ,52,53 whereas the O1s binding energy of 529.9 eV∼ 530.5 eV
are identified and classified to the oxygen in the WO3 structure.54
However, it can be seen from Figure 7 that all the XPS peaks exhibits
a trend toward higher binding energies with increasing of titanium
content. This upward shift is possibly ascribed to the formation of W-
O-Ti linkage.55 Meanwhile, the O1s binding energy in Figure 7b also
shows a positive shift, besides it is broader with increasing titanium
contents, which indicates that the O1s is shared by W-O and Ti-
O to form W-O-Ti linkage. The substitution of Ti4+ instead of W6+ ,
proposed from XPS result, is agreement with the discussion of Raman
Spectrum.56,58
Figure 8 shows cyclic voltammograms for each of the four thin
films at their first, 500th and 1000th cycles in 1 M LiClO4 dissolved

Table I. XRD peak positions for WT0, WT7, WT10 and WT15 along with the standard positions for monoclinic WO3 .

Monoclinic [001] [020] [200] [−111] [−221] [022] [041] [−401] [−222]
23.1 23.6 24.4 28.7 41.5 53.6 54.3 55.8 59.4
WT0 23.2 23.6 24.3 28.7 41.4 53.6 54.5 55.9 –
WT7 23.2 23.6 24.1 28.9 41.4 – 54.5 – –
WT10 23.2 23.6 23.9 28.6 41.6 – 54.2 – –
WT15 23.3 23.6 24.1 – – – 54.6 – –

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 Journal of The Electrochemical Society, 161 (14) E191-E201 (2014) E195

(a) (W4f) WT15 (b) (O1s) 530.5eV WT15

35.8eV 37.9eV 532.0eV
530.5eV WT10
35.7eV 37.7eV WT10 532.0eV
35.4eV 37.5eV 530.1eV WT7
WT7 531.6eV
35.2eV 529.9eV
37.3eV WT0
WT0
531.3eV

34 36 38 40 528 530 532 534

Binding Energy (eV) Binding Energy (eV)

Figure 7. Comparison of XPS spectrum of WT0, WT7, WT10 and

WT15 thin films: (a) W4f, (b) O1s and (c) Ti2p orbits.

(c) (Ti2p)
459.0eV
464.8eV WT15

458.7eV
464.3eV WT10

458.4eV WT7
464.2eV

455 460 465 470

Binding Energy (eV)

0.0010 0.0010
(a) WT0 (b) th WT7
1000
th
500
th st 500
1 0.0005 st
1
Current density (A cm )

0.0005
Current density (A cm )

th
-2

-2

1000
0.0000
0.0000
-0.0005
st
1
-0.0005
-0.0010 th
1000
th
500
-0.0010 -0.0015
-2.0 -1.5 -1.0 -0.5 0.0 0.5 1.0 -2.0 -1.5 -1.0 -0.5 0.0 0.5 1.0
Figure 8. Cyclic voltammograms collected on their 1st ,
500th and 1000th cycle in 1 M LiClO4 dissolved in propy-
+ +
potential (V vs Ag/Ag ) Potential (V vs Ag/Ag )
lene carbonate at a sweep rate of 50 mV s−1 from −2.0 V
to 1.0 V vs. Ag/Ag+ for (a) WTO, (b) WT7, (c) WT10,
0.0010 0.0015 (d) WT15.
(c) st WT10 (d) st WT15
1 0.0010
1
0.0005
Current density (A cm )

Current density (A cm )

0.0005
-2

-2

0.0000
0.0000

-0.0005 -0.0005

-0.0010
-0.0010 st
1 -0.0015
-0.0015 th
500 -0.0020
th
1000
-0.0020 -0.0025
-2.0 -1.5 -1.0 -0.5 0.0 0.5 1.0 -2.0 -1.5 -1.0 -0.5 0.0 0.5 1.0
+ +
Potential (V vs Ag/Ag ) Potential (V vs Ag/Ag )

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 E196 Journal of The Electrochemical Society, 161 (14) E191-E201 (2014)

st 0.005
0.04 1 cycle
Inserted charge density (C cm -2)
th WT0
500 cycle
0.004 WT7
th
1000 cycle

Current Density (A.cm )

WT10

-2
0.03 WT15
0.003

0.002
0.02
0.001

0.01 0.000

-2 0 2 4 6 8 10 12 14 16 -0.001
0 30 60 90 120 150
Atomic Ratio of Ti/W Time (s)
Figure 9. Charge accommodation capacities of WT0, WT7, WT10 and WT15 Figure 10. Chronoamperometric measurements performed by applying alter-
at their 1st , 500th and 1000th cycle respectively calculated from the CV curves native potentials of −1 V for 50 s followed by 1 V for 150 s, i.e. coloration
of Figure.8. and bleaching respectively, in 1 M LiClO4 dissolved in propylene carbonate.

in propylene carbonate at a sweep rate of 50 mV/s. The capacity of

the electrochromic process can be ascertained from the total charge
inserted into the films during each scan (i.e. the area enclosed by the
CV curves). Therefore, through comparison of Figures 2a to 2e, it
can be judged that the pure WO3 thin film has the worst charge ac-
commodation capacity. This was confirmed when the actual capacity
values were calculated, as displayed in Figure 9 and Table II. Note
that non-faradaic capacitance charging was neglected; analysis of the
later EIS data suggests that these would contribute much less than
10% of the total charge passed.
From Figure 9 and Table II, it can be seen that at the amount of
charge (in the form of Li+ ions) inserted into the films increases with
increasing titanium content, being about a factor of three higher for
WT10 and WT15 compared to WT0. Likewise, the average charge
insertion rate (rin ), defined as the total amount of charge intercalated
into the thin film divided by the charging time, which from the CV’s in
Figure 8 averages 40 seconds, also increases with increasing titanium
content. This increasing trend for rin is believed to be due to the
evolution of the morphology the films to more disordered structures as
their titanium content increases (Figures 3 & 4).58,59 Moreover, after
1000 cycles the capacitance loss of WT0, WT7, WT10 and WT15
reaches 39%, 15%, 5% and 32% respectively, caused by a reduction
in the number of effective places for ion intercalation. Again it seems
that up to 10 at.% titanium is beneficial to the performance of the film
but a further addition to 15 at.% is detrimental, since the capacity of
WT15 falls below that of its WT10 counterpart after 500 cycles. A
possible reason is ascribed to the morphology of the WT15 film, in
which the randomly distributed nano-blocks may impede the transport
of charges. The morphology of WT10 is more conducive for ions
insertion/extraction to avoid retention of ions during de-intercalation
process which will prevent the intercalation of ions in the following
cycles.
Figure 10 shows chronoamperometric curves in 1 M LiClO4 dis-
solved in propylene carbonate, obtained by applying repeated potential
pulses of −1V for 50 s followed by 1V for 150 s. Based on their re-
spective first cycle, the reversibility of the electrochromic process in
the WT0, WT7, WT10 and WT15 films is calculated to be 94%, 88%,
100% and 86% respectively. For WT10 film, it seems that virtually
all inserted Li+ can be extracted during the reversed electrochem-
ical process. In the work reported by Patil et al,15 they found that
the reversibility of films produced by spray deposition was increased
dramatically from 69% to 96% with an increase of titanium content
from 13% to 38% (volume ratio of titanium precursor over tungsten
precursor). In the present case, an optimum reversibility is found in
the WT10 film. Figure 11 displays optical images of the various thin
films in their colored and bleached states, from which the superior
electrochromic performance of the WT10 film can be clearly seen.
Figure 12 shows kinetic transmittance changes at 550 nm, 632.8
nm and 800 nm that were collected during the pulse experiments.
Through comparison, it can be seen that the addition of titanium is
advantageous in producing a deeper blue color compared with the pure
WO3 thin film. This agrees with the CV tests in which the capacity of
the thin film increased with increasing of titanium content. In addition,
at 800nm the transmittances of WT7 and WT10 are close to zero after
coloration, indicating an improvement in light absorption near the NIR
range, which is vital for efficient cooling of buildings. This could be
caused by a defect energy level formed within the forbidden bandgap
of the TiO2 mixed WO3 thin film resulting in a decrease of the bandgap
during the calcination process.60,61
For all three wavelengths investigated WT10 exhibits the best light
modulation ability, defined as the transmittance differences between
the lowest value at color state and highest value after bleaching of
58.5%, 72% and 77.7% at the wavelength of 550 nm, 632.8 nm and
800 nm respectively, which are 1.8, 1.7 and 2.1 times higher than the
pure WO3 thin film at the same corresponding wavelength.
The light modulation range of each thin film at selected wave-
lengths and the respective dynamic electrochromic process parame-

Table II. Charge densities and charge/discharge rates of all films obtained from the cyclic voltammograms in Figure 8. Where qin denotes the
intercalated charge density (i.e. capacitance), qin % denotes the relative loss in capacitance compared to the first cycle and rin denotes the average
rate of charge insertion during the 40 s charging cycle.

1st 500th 1000th

qin mC rin mC qin mC rin mC qin mC rin mC

cm−2 cm−2 s−1 cm−2 cm−2 s−1 qin % cm−2 cm−2 s−1 qin %
WT0 13 0.33 11.5 0.29 −13 8 0.20 −39
WT7 25 0.63 20 0.50 −21 22 0.54 −15
WT10 33 0.83 33 0.83 −2 32 0.80 −5
WT15 40 1.00 27 0.68 −33 27 0.69 −32

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 Journal of The Electrochemical Society, 161 (14) E191-E201 (2014) E197

Figure 11. Optical images of the films at their colored (left, deep blue with suffix C) and bleached (right, transparent with suffix B) states.

100 100
(a) WT0 WT7 (b) WT0 WT7
WT10 WT15 WT10 WT15
80 80
Transmittance %
Transmittance %

60 60

40 40

20 20

550nm 632.8nm
0 0
0 200 400 600 0 200 400 600
Time (s) Time (s) Figure 12. In situ transmittance corresponding to Figure 10
recorded at wavelengths of (a) 550 nm, (b) 632.8 nm and
(c) 800 nm.
100
(c) WT0 WT7
WT10 WT15
80
Transmittance %

60

40

20

800nm
0
0 200 400 600
Time (s)

Table III. Optical and kinetic parameters for WT0, WT7, WT10 and WT15 obtained from Figure 12 at wavelengths of 550, 632.8 and 800 nm.

Transmittance Change (%) CE cm2 C−1 Coloration/Bleaching Time (s)

Wavelength nm 550 632.8 800 550 632.8 800 550 632.8 800
WT0 31.9 41.9 37.0 18.8 31.1 49.1 39/52 39/50 32/90
WT7 41.1 59.3 49.7 19.2 36.5 75.4 35/32 28/85 21/90
WT10 58.5 72.0 77.7 43.2 46.8 105.8 38/34 33/60 10/64
WT15 25.0 36.4 64.5 23.5 33.4 62.8 35/38 32/48 32/72

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 E198 Journal of The Electrochemical Society, 161 (14) E191-E201 (2014)

WT0 (b) WT0

0.6 (a)
WT7 WT7
WT10 0.8 WT10
WT15 WT15
Change in optital density

Change in optital density

0.4

0.4
0.2

0.0 0.0
0.000 0.008 0.016 0.024 0.000 0.008 0.016 0.024
Charge Density (C cm )
-2
Charge Density (C cm )
-2 Figure 13. Variation of the in situ optical density vs. the
charge density corresponding to the in situ transmittance
in Figure 12 at wavelengths of (a) 550 nm, (b) 632.8 nm
1.6 and (c) 800 nm.
(c) WT0
WT7
WT10
1.2 WT15
Change in optital density

0.8

0.4

0.0
0.000 0.008 0.016 0.024
-2
Charge Density (C cm )

ters have been calculated and are listed in Table III. It can be seen that
the average coloration time (defined as the time required for 90% of
the full transmittance to be achieved) for the pure WO3 is about 35 s
regardless of the wavelength. The addition of titanium has less impact
at 550 nm, but at longer wavelengths the coloration time of WT10
was reduced being only 10 s 800 nm. However, if too much titanium
is added this advantage is lost, with the coloration rate of WT15 being
the same as WT0 at 800 nm.
The improvement in the coloration rate of WT7 and WT10 films
over that of WT0 is thought to mainly arise from their morphol-
ogy differences. Firstly, the morphology of WT10 provided larger
channels for charge transport which is an important determinant of
coloration rate.62–64 Secondly, the nano-flake structures of WT10, pro-
vide advantages in both larger intercalation capacitances (as discussed
with the CVs) and convenient channels due to its larger pore diameter
(Figure 3). Moreover, the same conclusion can be made for the bleach-
ing rate, defined as the time required for a 90% change respect to the
lowest transmittance within the full transmittance modulation at the
selected wavelength.
Continuing the discussion of the electrochromic properties of the
films, the coloration efficiency (CE), defined in Equations 6 and 7, for
the various thin films are depicted in Figure 13.
O D
[6]
q of −0.4 V vs. Ag/Ag+ ; this potential was chosen as according to
Tb
O D(λ) = log [7]
Tc
Where OD is the change in optical density, which is proportional to
the amount of created color centers of the film, Tb and Tc are the
transmittances before and after coloration at a given wavelength (λ)
and q is the corresponding injected (or ejected) charge density per
unit area, obtained by measuring the corresponding current density
transient curve (Figure 10).
Figure 13 shows plots of the change in the optical density against
the charge density inserted into the film, the slope of which yields the
coloration efficiency (Equ. 6). It can be seen that for all the films the
calculated value of CE increases at longer wavelengths. Furthermore,
the extent of the increase in CE was larger for all WO3 /TiO2 thin
films relative to the pure WO3 at all wavelengths, with again WT10
showing the largest values. This was ascribed to it having the largest
light modulation range. In addition, within the visible light range,
the CE of WT7, WT10 and WT15 are 19.2/36.5 cm2 C−1 , 43.2/46.8
cm2 C−1 and 23.5/33.4 cm2 C−1 respectively at the wavelengths of
550 nm/632.8 nm, which are 0.4/5.4 cm2 C−1 , 24.4/15.7 cm2 C−1
and 4.7/2.3 cm2 C−1 higher than that of 18.8/31.1 cm2 C−1 for WT0
independently. While, at 800 nm as compared to WT0 the CE of the
titanium containing films improved by factors of 1.5, 2 and 1.3 for
WT7, WT10 and WT15. Therefore, it can be seen that the value of CE
is very sensitive to the light modulation range and that the WT10 film
has the best electrochromic coloration efficiency across the whole of
the spectrum range investigated.
To explore the charge transport mechanisms in the electrochromic
films electrochemical impedance measurements were conducted in
C E(λ) = 1 M LiClO4 dissolved in propylene carbonate solution at a potential
the cyclic voltammetry tests it corresponds to the onset of reduction.
Figure 15 depicts the EIS data for the four different thin films in the
Nyquist format.
It is found that the EIS data could be fit to the equivalent cir-
cuit shown in Figure 15, which is often used to describe lithium ion

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 Journal of The Electrochemical Society, 161 (14) E191-E201 (2014) E199

-18000
WT0 WT7
-25000 (a) (b)
fitting result fitting result
-15000
-20000
-12000
-2

-2
Z" ohm cm

Z" ohm cm
-15000
-9000

-10000
-6000

-5000 -3000

0 0
0 4000 8000 12000 16000 0 3000 6000 9000 12000 15000
Z' ohm cm
-2
Z' ohm cm
-2 Figure 14. Impedance spectrums of WT0, WT7,
WT10 and WT15. The squares are the raw data col-
-600 lected and the solid lines are the fitting results.
WT10 (d) WT15
(c) fitting result
fitting result -800
-500

-400 -600
-2
Z" ohm cm
-2
Z" ohm cm

-300
-400

-200

-200
-100

0 0
0 200 400 600 800 0 150 300 450 600 750
-2 -2
Z' ohm cm Z' ohm cm

(CPE) that represents the modified double layer capacitance due to

Figure 15. Equivalent circuit used to fit the impedance data.
batteries that are mechanistically very similar to electrochromic
windows,65 where: Rs is the series resistance, including the sheet
resistance of FTO, contact resistance and uncompensated solution re-
sistance; Rf is the film resistance; Qdl is a constant phase element
accumulation of ions onto the inhomogeneous surface of the film (the
ideality of the CPE as a capacitor is described by Qn , with pure ca-
pacitive behavior at n = 1);66 Rin denotes a resistance assigned to the
insertion of Li+ into the porous surface of the film; Qin is a constant
phase element formed by intercalation of Li+ in the near-surface re-
gion of the film; Ws1 is a finite length Warburg impedance that gives
information on diffusion of ions within the film and is described by a
time constant τw and at low frequencies converges to a resistor RW .67
In all cases high quality fits were obtained with chi-square values less
than 0.05%, with the fitted parameters displayed in Table IV.
On the basis of the fitting results from Figure 14 and the recorded
data in Table IV, it can be seen that the variations in the fitting

Table IV. Impedance fitting parameters of film WT0, WT7, WT10 and WT15 corresponding to the equivalent circuit in Figure 15.

Film WT0 Er% WT7 Er% WT10 Er% WT15 Er%

Rs /  cm−2 58.9 0.2 116 0.1 71.3 0.2 38.7 6.8
R f /  cm−2 212 16.4 203 15.1 163 1.0 16.5 15.9
Rin /  cm−2 1.6 E+4 6.5 5.3 E+3 3.0 1.8 E+2 4.3 1.1 E+3 0.4
Q dl / (F cm−2 )1/n 1.2 E-4 1.0 1.9 E-4 0.8 9.6 E-4 0.9 8.7 E-7 31.7
n dl 0.9 0.2 0.8 0.2 0.8 0.3 0.8 30.7
Q in / (F cm−2 )1/n 5.7 E-6 11.8 6.0 E-6 16.1 1.4 E-3 3.7 3.2 E-4 1.9
n in 1 0.9 1 0.8 0.9 1.0 0.8 0.2
Rw /  cm−2 2.5 E+5 1.4 1.1 E+5 0.4 1.3 E+3 3.5 2.0 E+4 0.8
τw / s 447 2.0 289 0.7 52.2 5.8 302 0.4

The method of Er % calculation is stated the experimental section.

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 E200 Journal of The Electrochemical Society, 161 (14) E191-E201 (2014)
parameters between nominally the same films along with the per-
centage fit errors that report the quality of the fit to an individual film,
are in most cases very good especially for the best performing film
WT10. From the analysis of the fitting results it can be concluded
that the inclusion of up to 10 at.% titanium content can reduce the
charge transfer resistance of WO3 thin film effectively. A similar phe-
nomenon was also observed by Park el al who studied TiO2 mixed
WO3 film electrodes formed by a doctor-blade method.68 This is also
consistent with the CV test in which a larger current density is ob-
served with an increase in titanium content. Meanwhile, the double
layer capacity (Qdl ) of the samples exhibit a slightly increasing trend
for the sequence of WT0, WT7 and WT10, but WT15 shows a very
low value with a relatively large error 31.7%; this larger fitting error
is largely due to the small magnitude of Qdl as compared to Qin . Oth-
erwise, the larger fitting error of ndl for WT15 also indicates its far
deviation from the ideal capacitor behavior arising from its small Qdl.
The small value of Qdl can be attributed to the morphology of W15
that gives a smaller specific area (Figures 3 and 4).
Table IV also reveals that WT10 has the lowest Li+ insertion and
diffusion resistances, represented by Rin and RW respectively, as well
as the highest capacitance symbolized by Q in , indicating that this
sample has the optimized quantity of titanium in the film and the
best morphology. The low time constant, τw , of the WT10 implies
that either the diffusion path length is shorter (e.g. less tortuous) or
the diffusion coefficient is higher for this film. These lower Rin , RW
and τw , values help to explain why WT10 has the fastest Li+ ion
intercalation rate and its high Qin explains why it has the largest light
modulation range.
Conclusions
In this work mixed WO3 /TiO2 thin films containing 0–15 at.% tita-
nium have been produced by anodization of co-sputtered W/Ti films in
a fluorinated aqueous acidic electrolyte, followed by annealing in air.
SEM images revealed that as the titanium content increased the films
exhibited a morphology evolution from nano-porous structure, un-
dergoing nano-flake, to nano-block decorated porous structure. Both
XRD and Raman spectroscopy results revealed that the crystallinity of
the WO3 /TiO2 thin films decreased with increasing titanium content.
By comparing the electrochromic properties of these films it was
found that WT10 with a porous nano-flake structure displayed both the
best durability, with a loss of only 5% in its ion accommodation ability
after 1000 cycles, and superior capacity in adjusting the light trans-
mittance being 58.5%, 72% and 77.7% at 550 nm, 632.8 nm and 800
nm respectively. Besides, WT10 had the fastest coloration/bleaching
rates being at 10 s / 64 s at 800 nm compared with 32 s / 90 s of a pure
WO3 thin film, and the highest coloration efficiency of 46.8 cm2 C−1
at 632.8 nm.
It was also found that further additions of titanium resulted in a
deterioration of the electrochromic properties as this resulted in the
formation of a nano-block morphology that is less conductive for the
insertion and removal of Li+ ions. Finally, analysis by electrochemi-
cal impedance spectroscopy implied that the mixed titanium content
reduced the ion insertion and diffusion resistances with minimal val-
ues found for WO3 films with 10 at% Ti, as explained by the faster
dynamic responses of the WT10 sample.
Acknowledgment
Financial support was provided by the NUS-MOE Academic Grant
R-284-000-090-112. Y.G. acknowledges the support of an NUS schol-
arship.
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