APPLIED PHYSICS LETTERS VOLUME 76, NUMBER 26 26 JUNE 2000

Alternating current impedance and Raman spectroscopic study

on electrochromic a -WO3 films
Se-Hee Leea)
National Renewable Energy Laboratory, Golden, Colorado 80401
Hyeonsik M. Cheong
National Renewable Energy Laboratory, Golden, Colorado 80401
and Department of Physics, Sogang University, Seoul 121-742, Korea
C. Edwin Tracy, Angelo Mascarenhas, J. Roland Pitts, Gary Jorgensen,
and Satyen K. Deb
National Renewable Energy Laboratory, Golden, Colorado 80401
共Received 13 March 2000; accepted for publication 3 May 2000兲
The chemical diffusion of lithium ions in a-Lix WO3 films is investigated using alternating current
impedance spectroscopy and Raman scattering measurements. The diffusion coefficients increase
with increasing x in a-Lix WO3 up to x⫽0.072 and then decrease. Raman measurements show that
the W6⫹⫽O/O–W6⫹ –O ratio also increases at the early stage of lithium insertion and then decreases
with further lithium insertion. We conclude that the diffusion kinetics of lithium ions in a-Lix WO3
films is very closely related to the W6⫹⫽O/O–W6⫹ –O ratio. © 2000 American Institute of
Physics. 关S0003-6951共00兲04626-X兴

Electrochromism in amorphous tungsten oxide films has
been extensively studied since it was discovered in 1969.1
Transmittance modulation is obtained by electrically control-
ling the oxidation states of an electrochromic 共EC兲 electrode
and a counter electrode by inserting or extracting small alkali
metal ions.2 Understanding the mechanism of ion insertion
into a-WO3 films is one of the key issues that remains to be
resolved to better understand the coloring/bleaching process
in EC devices because this mechanism determines the re-
sponse time and the durability of the device. It has been
reported that the chemical diffusion coefficients of lithium
ions in a-WO3 thin films are influenced by lithium concen-
tration in the films and are closely related to the
microstructure.3–5 However, the exact mechanism that can
explain the relationship between the chemical diffusion co-
efficients of lithium ions and the microstructural changes of
the a-WO3 films with lithium insertion is not clear as yet.
Therefore, finding a correlation between the chemical diffu-
sion of lithium ion and the microstructure of the a-WO3
films, as well as the chemical and physical characteristics of
a-WO3⫺y films, can provide important insight into the
mechanism of ion insertion into a-WO3 films and eventually
result in improved device performance. In this work, we
have studied the effect of the microstructural changes in
amorphous lithiated tungsten oxide (a-Lix WO3) films on the
chemical diffusion of lithium ions as a function of lithium
concentration and have correlated these kinetic properties
with changes in the Raman spectra resulting from electro-
chemical ion insertion or extraction.
The a-WO3 films used in this study were prepared on
polished stainless steel substrates by evaporation of WO3
powder of purity 99.99%. The thickness of the samples was
about 250 nm. In order to prevent water absorption into the
a兲
Electronic mail: slee@nrel.gov
lithiated samples, we deposited 200–300 nm of LiAlF4 solid
electrolyte on top of the a-WO3 films. LiAlF4 is known to
have a high ionic conductivity and stability in ambient
atmosphere.6 The electrochemical insertion and removal of
lithium in the a-WO3 films was carried out in a dry box
using 1 M LiClO4 in propylene carbonate 共PC兲 as an elec-
trolyte with lithium metal as both a reference and a counter
electrode.
The lithium ion diffusion in the a-Lix WO3 films was
studied with alternating current 共ac兲 impedance spectros-
copy, using a Solartron model 1260/1265. An ac impedance
spectrum is obtained by measuring the complex impedance
of the WO3 working electrode as a function of the applied
frequency, f , which we varied between 50 kHz and 0.001
Hz. The electrical behavior of an ion-insertion electrode in a
liquid electrolyte is well known to be equivalent to the so-
called Randles circuit 关Fig. 1共a兲兴. Here, R e is the electronic
resistance of the system, R ct is the charge transfer resistance
共interfacial reaction resistance兲, C dl is the double layer ca-
pacitance of the electrode-electrolyte interface, Z w is the so-
called Warburg diffusion impedance 共ionic diffusion in the
electrode兲, C L is the limiting capacitance, and R L is the lim-
iting resistance. The complex impedance spectrum 共Nyquist
Plot兲 of the circuit in Fig. 1共a兲 shows three regions corre-
sponding to high, low, and intermediate frequencies 关Fig.
1共b兲兴. In particular, the analyses of the response in the low
frequency, limiting capacity regions, allow us to obtain the
value of the diffusion coefficient, D, in the a-Lix WO3 films,
by the use of the equation
l2
D⫽ , 共1兲
3C L R L
where l is the thickness of the a-Lix WO3 film.7–9 The Ra-
man spectra were taken in the quasibackscattering geometry
using 100 mW of the 514.5 nm line of an Ar ion laser. The

0003-6951/2000/76(26)/3908/3/$17.00 3908 © 2000 American Institute of Physics

Appl. Phys. Lett., Vol. 76, No. 26, 26 June 2000 Lee et al. 3909

TABLE I. Results from the ac impedance spectroscopy measurements; elec-

trochemical parameters at nine different levels of ion insertion.

Level of
lithium insertion D
x in Lix WO3 R L 共⍀兲 C L 共mF兲 (⫻10⫺11 cm2/sec兲

0.005 8955 1.2 1.9

0.018 3209 3.2 2.0
0.036 1438 4.7 3.1
0.054 719 5.8 5.0
0.072 546 6.7 5.7
0.090 507 8.9 4.6
0.135 481 12.0 3.6
0.180 464 14.0 3.2
0.225 450 15.4 3.0

770 cm⫺1, due to the O–W6⫹ –O bonds.10 There is also a

relatively sharp peak at 950 cm⫺1, which has been assigned
FIG. 1. 共a兲 Equivalent electrical model of a WO3 thin film electrode on a to the W6⫹⫽O stretching mode of terminal oxygen atoms on
transparent electronic conductor. 共b兲 Typical complex ac impedance spec-
trum 共Nyquist plot兲 of the circuit shown in Fig. 1共a兲.
the surfaces of the cluster and microvoid structures in the
film.11 With lithium insertion, the overall intensity of the two
peaks decreases due to the reduction of the (W6⫹ and oxy-
signal was dispersed by a 0.6 m triple spectrometer and de-
gen兲 bonds to the (W5⫹ and oxygen兲 bonds.12–14 The ratio of
tected with a liquid-nitrogen-cooled charge-coupled-device
the integrated intensity of the W6⫹⫽O bond peak at
detector array.
950 cm⫺1 to that of the O–W6⫹ –O peak at 770 cm⫺1 is plot-
The typical impedance diagram of an a-Li0.09WO3 thin
ted in Fig. 4, along with the diffusion coefficients of the
film electrode in LiClO4 –PC electrolyte is shown in Fig. 2.
lithium ions in a-Lix WO3 film, as function of lithium con-
At very low frequencies the phase angle begins to increase
centration. The data show that with lithium insertion, the
due to the onset of finite length effects. This Nyquist plot of
W6⫹⫽O/O–W6⫹ –O ratio increases at the early stage of
the Li0.09WO3 thin film electrode suggests a low-resistance
lithium insertion up to x⫽0.05 in a-Lix WO3 and then de-
electrode interface process with the spectrum mostly domi-
creases in similar fashion of the change of the diffusion co-
nated by a diffusion-limited process. The diffusion coeffi-
efficient with lithium ion insertion. An initial increase of the
cients of lithium ions were obtained from the limiting resis-
W6⫹⫽O/O–W6⫹ –O ratio with lithium insertion indicates
tance and the limiting capacitance. Table I gives the
that the inserted lithium ions and electrons have converted
electrochemical parameters of the sample at nine different
more W6⫹ into W5⫹ in O–W6⫹ –O sites rather than in
levels of lithium insertion. The limiting resistance and the
W6⫹⫽O sites. In other words, when lithium ions and elec-
limiting capacitance were measured using ac impedance
trons are inserted into a-WO3 films, the inserted lithium ions
spectroscopy. The diffusion coefficients increase with in-
and electrons preferentially go to the O–W6⫹ –O bonds
creasing x in a-Lix WO3 showing a maximum at x⫽0.072 in
rather than to the W6⫹⫽O bonds at the early stage of lithium
a-Lix WO3 and then decrease.
insertion. After a certain amount of lithium insertion, the
Figure 3 shows the Raman spectra for an evaporated
decrease of the W6⫹⫽O/O–W6⫹ –O ratio indicates that the
a-WO3 film with various amounts of lithium insertion. The
spectrum of an as-deposited film 共a兲 shows a broad peak at

FIG. 3. Raman spectra of a-WO3 films as a function of lithium concentra-

FIG. 2. Typical impedance diagram of a-Li0.09WO3 thin film electrode in tion. x in a-Lix WO3 is 共a兲 0.0 共as-deposited兲, 共b兲 0.018, 共c兲 0.054, 共d兲 0.090,
LiClO4 –PC electrolyte. 共e兲 0.180, and 共f兲 0.225.
3910 Appl. Phys. Lett., Vol. 76, No. 26, 26 June 2000
FIG. 4. 共a兲 The diffusion coefficient (D) and 共b兲 the Raman intensity ratio
of W6⫹⫽O/O–W6⫹ –O as a function of lithium concentration x in
a-Lix WO3 thin film.
inserted lithium ions and electrons preferentially go to
W6⫹⫽O bonds than to the O–W6⫹ –O bonds.
To date, many groups have separately reported on Ra-
man spectroscopic results and diffusion kinetic results. How-
ever, all these investigations have been done independently,
resulting in little correlation between the chemical diffusion
of lithium ions and the microstructure of the a-WO3 films. A
survey of the literature indicates that there are no obvious
general trends in the diffusion constant and Raman measure-
ments. Delichere et al.15 and Paul and Lassegues16 observed
that upon H⫹/Li⫹ insertion, an increase of the W6⫹⫽O peak
at ⬃950 cm⫺1 occurs, while Otsuka et al.17 showed that a
depression of the W6⫹⫽O peak occurs with lithium inser-
tion. With respect to diffusion constants, Zhang et al.4 re-
ported a decrease of diffusion coefficients of lithium ions at
low insertion levels, while Pyun and Bae5 reported an in-
crease in diffusion coefficients of lithium ions at low inser-
tion levels.
Our results show that there is a direct correlation be-
tween the diffusion coefficient and the W6⫹⫽O/O–W6⫹ –O
ratio. Hence, we propose a new diffusion mechanism in
a-Lix WO3 films that can also explain the seemingly contra-
Lee et al.
dictory results previously reported by other groups. We sug-
gest that there are two diffusion paths in a-WO3 films: the
surface of the WO3 clusters where the W6⫹⫽O bonds are
located, and the inside of the WO3 clusters where the
O–W6⫹ –O bonds are located. It has been shown12,13 that
when lithium ions and electrons are inserted, the electrons
reduce W6⫹ ions to W5⫹ ions, thus creating O–W5⫹ –O and
W5⫹⫽O bonds. The inserted lithium ions also stay close to
(W5⫹ and oxygen兲 bonds without forming any type of Li
bonding. As a result, the O–W5⫹ –O and W5⫹⫽O bonds are
no longer able to serve as a diffusion path because there are
the lithium ions combined with (W5⫹ and oxygen兲 bonds. It
also has been established that the surfaces of WO3 clusters
show a faster lithium ion diffusion than the inside of the
clusters, and that more porous a-WO3 films show a faster
lithium ion diffusion.4,18 Therefore, films with a higher
W6⫹⫽O/O–W6⫹ –O ratio should have a faster diffusion than
those with a lower W6⫹⫽O/O–W6⫹ –O ratio.
This work was supported by the DOE Office of Building
Technology, State and Local Programs, Sam Taylor, Pro-
gram Manager under Contract No. DE-AC36-99GO10337.
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