Effect of interfacial property on electrochromic response speed of

Ta
2
O
5
/NiO and Ta
2
O
5
/Ni(OH)
2
Kwang-Soon Ahn, Yoon-Chae Nah, Yung-Eun Sung
*
Department of Materials Science and Engineering, Research Center for Energy Conversion and Storage,
Kwangju Institute of Science and Technology (K-JIST), Kwangju 500-712, South Korea
Abstract
Ta
2
O
5
layers were deposited on NiO/indium tin oxide (ITO) and Ni(OH)
2
/ITO, respectively, by means of an RF magnetron
sputtering system, and their electrochromic properties were then compared by means of in situ transmittance measurements
during continuous potential cycling and pulse potential cycling. The electrochromic response speed of the Ta
2
O
5
/Ni(OH)
2
/ITO
was much more rapid than that of the Ta
2
O
5
/NiO/ITO. This can be attributed to the interfacial property between the Ta
2
O
5
and
the electrochromic layer. The NiO layer of Ta
2
O
5
/NiO/ITO was irreversibly transformed into an electrochromic active form,
Ni(OH)
2
, during the first potential cycling, leading to an increase in the interfacial reaction resistance and, as a result, a slow
response speed.
D 2003 Elsevier B.V. All rights reserved.
PACS: 78.40.Ha; 81.40.Tv; 81.15.Cd
Keywords: Electrochromism; Ta
2
O
5
; Ni oxide; Response speed; Interfacial property
1. Introduction
Electrochromism (EC) is defined as a phenomenon
in which a change in color (light transmittance) takes
place in the presence of an applied voltage [1,3].
Because of their low power consumption, high color-
ation efficiency, and memory effects under open
circuit conditions, EC devices have many potential
applications in EC windows such as smart windows,
mirrors, and eyewear as well as in EC displays such as
mobile phones, smart cards, and price labels [1,3].
However, the response time of EC devices may limit
their application to only EC windows. An EC device
generally consists of a transparent electrically con-
ducting layer, electrochromic cathodic and anodic
coloring materials, an ion conducting electrolyte,
and another electrically conducting layer. Tungsten
oxides and Ni oxide/hydroxides are currently in wide-
spread use as cathodic and anodic coloration materi-
als, respectively [1,2,48], and their microstructures
have a strong influence on electrochromic properties
such as the coloration efficiency, optical difference,
and electrochromic response time [4,5,912]. Our
group also previously reported [7,8] that a Ni metal
nano thin layer rather than indium tin oxide (ITO),
which is the most widely used material for the
transparent electrically conducting layer, could be
utilized to prepare an EC device with a faster response
time.
0167-2738/$ - see front matter D 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.ssi.2003.08.027
* Corresponding author. Tel.: +82-62-970-2370; fax: +82-62-
970-2304.
E-mail address: ysung@kjist.ac.kr (Y.-E. Sung).
www.elsevier.com/locate/ssi
Solid State Ionics 165 (2003) 155160
Ta
2
O
5
is promising material for use as the protec-
tive layer [13], because it is stable over a wide range
of potential and pH and is an electrically insulating
material [14]. We previously fabricated all solid-state
EC device composed of WO
3
and Ni(OH)
2
with
Ta
2
O
5
protective layers, in which the Ta
2
O
5
layers
played a role as good protective layers against an
acidic solid polymer electrolyte for the Ni(OH)
2
as
well as WO
3
[15]. However, for fundamental studies
of electrochromism, the use of liquid electrolyte is
more convenient than that of solid electrolyte [16]. In
this paper, Ta
2
O
5
was sputter-deposited on the NiO/
ITO and Ni(OH)
2
/ITO, respectively, and their EC
properties were then investigated using an aqueous 1
M NaOH electrolyte. This study provides some im-
portant insights into the electrochromic response
speed at the interface between the Ta
2
O
5
protective
layer and the electrochromic layer.
2. Experimental
Two types of the electrodes comprised of Ta
2
O
5
/
NiO/ITO and Ta
2
O
5
/Ni(OH)
2
/ITO were prepared, as
shown in Fig. 1. First, NiO films were deposited on the
substrates of ITO-coated glass by RF magnetron
sputtering. NiO was used as target material. The
working pressure was 5 10
3
Torr, and the sputtering
was performed under Ar/O
2
ratio of 1:1. The NiO films
were sputter-deposited at an RF power of 60 W for 60
min at room temperature (RT), the detailed deposition
procedure for which have been reported elsewhere [9
12]. Ni(OH)
2
/ITO was prepared by the continuous
potential cycling (or linear-sweep potential cycling)
of the sputter-deposited NiO/ITO in a 1 M NaOH
electrolyte, which was carried out for up to 20 cycles in
the range of 0.9 to 0.62 V (vs. Ag/AgCl) at a scan
rate of 10 mV/s. Ta
2
O
5
films were then deposited on
NiO/ITO and Ni(OH)
2
/ITO using an RF magnetron
sputtering system. Ta
2
O
5
was used as the target mate-
rial and the distance between the target and the
substrate was 8 cm. The base pressure was below
5 10
6
Torr and the working pressure was 5 10
3
Torr. The RF power was 60 W. Prior to sample
sputtering, a sputter etching of the target was per-
formed for 20 min in order to eliminate contamination
from the target. Sputtering of Ta
2
O
5
was then con-
ducted on NiO/ITO and Ni(OH)
2
/ITO, respectively,
for 5 min at RT. The thicknesses of the Ta
2
O
5
and NiO
were about 30 and 220 nm, respectively, as measured
by cross-sectional scanning electron microscopy
(SEM). The crystallographic microstructure of the
Ta
2
O
5
was amorphous, based on the X-ray diffraction
data.
All electrochemical potential cycling tests were
performed using an Autolab PGSTAT30 (Eco
Chemie) Potentiostat/Galvanostat. Pt wire and Ag/
AgCl were used as the counter and reference elec-
trodes, respectively. Ta
2
O
5
/NiO/ITO and Ta
2
O
5
/
Ni(OH)
2
/ITO were used as the working electrodes
and aqueous 1 M NaOH was used as the electrolyte.
Continuous potential cycling (or linear-sweep poten-
tial cycling) was carried out for up to 20 cycles in
the range of 0.9 to 0.62 V at a scan rate of 10
mV/s. The electrochromic response time was then
tested by applying a pulse potential wave between
0.9 and 0.6 V with a duration time of 30 s,
referred to as pulse potential cycling. The transmit-
tance (633 nm, 10 mW) was simultaneously mea-
sured in situ during all experiments, as described
elsewhere [7,912]. The transmittance of the ITO/
glass with the electrolyte and the cell window was
assumed to be 100%. An ac impedance spectroscopy
(Autolab, Echo Chemie) was then used to investigate
the reaction kinetics at the interfaces between the
Ta
2
O
5
and the electrochromic layer in the frequency
range of 0.1 Hz to 10 kHz. The impedance mea-
surement was equilibrated for 60 s at 0.5 V prior to
the actual collection of data.
3. Results and discussion
Fig. 2 shows in situ transmittance curves during
continuous potential cycling of (a) Ta
2
O
5
/NiO/ITO
and (b) Ta
2
O
5
/Ni(OH)
2
/ITO, respectively. Both the
Fig. 1. Schematic diagrams of Ta
2
O
5
/NiO/ITO (left) and Ta
2
O
5
/
Ni(OH)
2
/ITO (right).
K.-S. Ahn et al. / Solid State Ionics 165 (2003) 155160 156
Ta
2
O
5
/NiO/ITO and Ta
2
O
5
/Ni(OH)
2
/ITO show a sta-
ble bleaching/coloring EC performance. However,
the difference of the transmittance curve between
them was observed during initial bleaching/coloring
processes.
Fig. 3 shows cyclic voltammograms obtained dur-
ing continuous potential cyclings for (a) Ta
2
O
5
/NiO/
ITO and (b) Ta
2
O
5
/Ni(OH)
2
/ITO, respectively. Fig.
3(a) shows a significant irreversible reaction peak
around 0.2 V during the cathodic polarization of
the first potential cycling and an irreversible reaction
peak was not evident during sequent potential
cyclings. Fig. 4 shows an in situ transmittance curve
during the first and second continuous potential
cyclings for the Ta
2
O
5
/NiO/ITO. The transmittance
abruptly increased from 0.1 to 0.7 V during cathod-
ic polarization of the first potential cycling and, then,
changed reversibly during subsequent potential
cyclings. Previous X-ray photoelectron spectroscopy
(XPS) data [17] showed that the sputter-deposited NiO
film was transformed into Ni(OH)
2
during the poten-
tial cycling, in which native Ni hydroxide component
partially existed in the Ni oxide film, but the NiO
component did not exist in the bleached-state film after
the potential cycling and was transformed into the
Ni(OH)
2
component. Therefore, the sputter-deposited
NiO phase was irreversibly transformed into the elec-
trochromic active form, Ni(OH)
2
, during the cathodic
polarization of the first potential cycling, leading to the
abrupt increase in transmittance. The Ni(OH)
2
then
reversibly reacts with the reversible transmittance
Fig. 3. Cyclic voltammograms during the first and second continuous
potential cyclings for (a) Ta
2
O
5
/NiO/ITO and (b) Ta
2
O
5
/Ni(OH)
2
/
ITO, respectively.
Fig. 2. In situ transmittance curves during continuous potential
cycling of (a) Ta
2
O
5
/NiO/ITO and (b) Ta
2
O
5
/Ni(OH)
2
/ITO,
respectively.
K.S. Ahn et al. / Solid State Ionics 165 (2003) 155160 157
change during sequent potential cyclings by the fol-
lowing electrochromic reaction:
NiOH
2
bleached
reduced
$NiOOH H

colored
oxidized
e

Although ionic mechanisms are much debated, the

electrochromic reaction is not simple. Giron and Lamp-
ert [18] reported the detailed electrochromic mecha-
nism involving water and hydroxyl ions. According to
them, during the oxidation process, the above reaction
takes place in the film. The film inserts alkaline cations
and hydroxyl anions from the solution and OH ions
migrate towards the protons, which diffuse in the other
direction and combine to form a water molecule within
the film. During the reduction process, the water
molecules contained in the film dissociate and release
protons, which diffuse towards the oxidized Ni sites,
and hydroxyl anions, which migrate towards the elec-
trolyte. The alkaline cations are simultaneously re-
leased into the solution. The Ta
2
O
5
may be hydrated
in Ta
2
O
5
nH
2
O, because the proton conduction in the
film takes place with the Grotthus-type mechanism of
proton transfer from a H
3
O
+
molecule to an adjacent
H
2
O molecule by the tunneling effect in the hydrogen
bonding, followed by the rotation of molecules for the
next transfer [19], the detailed study of which is
underway.
Fig. 3(a) also shows that a second reaction (near
0.10.2 V) appears during the initial bleaching pro-
cess and then gradually disappears together with
evolution of the first reaction near 0.4 V. The initial
potential cycling performance of the NiO/ITO sample
without the Ta
2
O
5
had similar tendency, indicating that
the second reaction is caused only by Ni oxide/hy-
droxide, but not by Ta
2
O
5
. The existence of the second
reaction during the initial cycling has been reported by
different groups [2023] but remains a controversial
issue. This may be related to the reduction of intrinsi-
cally less active Ni oxides, a change in the electronic
behavior of the Ni hydroxide active material, or a
phase transformation. On the other hand, Fig. 3(b)
showed that the Ta
2
O
5
/Ni(OH)
2
/ITO showed no irre-
versible reaction during the potential cycling, as shown
in Fig. 3(b). This is because the electrochromic active
phase Ni(OH)
2
preexists before the continuous poten-
tial cycling.
The phase transformation during the first potential
cycling may affect the nature of the interface between
the Ta
2
O
5
and the electrochromic layer. Fig. 5 shows
the Nyquist plots of the Ta
2
O
5
/Ni(OH)
2
/ITO (open
circles) and the Ta
2
O
5
/NiO/ITO (close circles) mea-
sured at 0.5 V after the potential cycling tests.
Complex nonlinear least-squares (CNLS) fitting us-
ing an appropriate equivalent circuit model inserted
in Fig. 5 was used to simulate the measured data.
Here, R
sol
is the resistance of the aqueous solution,
R
film
the resistance of the Ta
2
O
5
layer, R
ct
the charge
transfer resistance (interfacial reaction resistance),
and Z
w
the Warburg impedance. The constant phase
Fig. 5. Nyquist plots of Ta
2
O
5
/Ni(OH)
2
/ITO (open circle) and
Ta
2
O
5
/NiO/ITO (closed circle) measured at 0.5 Vafter the potential
cycling tests.
Fig. 4. In situ transmittance curve during continuous potential
cyclings for Ta
2
O
5
/NiO/ITO.
K.-S. Ahn et al. / Solid State Ionics 165 (2003) 155160 158
element (CPE) and limiting capacitance were also
included in this model. The R
sol
was found to be 18
19 V for both samples, due to the similarity of the
electrolyte and cell components. The R
film
and R
ct
values were 2 and 137 V, respectively, for the Ta
2
O
5
/
Ni(OH)
2
/ITO. On the other hand, the Ta
2
O
5
/NiO/ITO
had much larger R
film
and R
ct
values (12 and 366 V,
respectively) than Ta
2
O
5
/Ni(OH)
2
/ITO. This indicates
that the irreversible phase transformation of NiO to
Ni(OH)
2
in Ta
2
O
5
/NiO/ITO during the first potential
cycling causes a degradation in the interfacial prop-
erty between the Ta
2
O
5
and the electrochromic layer
due to the physically severe volume change of phase
during the first cycling, resulting in high R
ct
and R
film
values.
In order to investigate the effect of the interfacial
property on the electrochromic response kinetics,
pulse potential cycling tests were performed after the
continuous potential cycling tests. Fig. 6(a) shows in
situ transmittance curves during the pulse potential
cycling test (0.9 and 0.6 V, duration time of 30 s)
after the continuous potential cycling test of Ta
2
O
5
/
NiO/ITO (dotted line) and Ta
2
O
5
/Ni(OH)
2
/ITO (solid
line). All samples showed a stable pulse potential
cycling performance and had a similar optical differ-
ence (DOD) of 0.43, in which DOD is defined as log
(T
bleached
/T
colored
) where T
bleached
and T
colored
are the
transmittances of the bleached and colored states,
respectively. However, the electrochromic response
kinetics was strongly dependent on the interfacial
property between the Ta
2
O
5
and the electrochromic
layer. The response times during the coloring/bleach-
ing processes were quantitatively calculated from
normalized transmittance data [912] of the first
transmittance curves of the pulse potential cycling
data, as shown in Fig. 6(b). The electrochromic re-
sponse times were calculated on the level of a 90%
transmittance change. The coloring response time was,
on the whole, higher than the bleaching response time,
because the conductivity of Ni(OH)
2
is lower than that
of NiOOH [6,912]. The response times during the
coloring and bleaching processes were about 1 and 5.2
s, respectively, for Ta
2
O
5
/Ni(OH)
2
/ITO and about 2
and 10.1 s, respectively, for Ta
2
O
5
/NiO/ITO. That is,
the electrochromic response speed of the Ta
2
O
5
/
Ni(OH)
2
/ITO was much faster than that of Ta
2
O
5
/
NiO/ITO. This suggests that the electrochromic re-
sponse speed is significantly related to the property of
the interface between the Ta
2
O
5
and the electrochro-
mic layer or the properties of the Ta
2
O
5
itself after the
phase transformation of the NiO into Ni(OH)
2
. The
irreversible phase transformation of NiO into Ni(OH)
2
during the first continuous potential cycling of the
Ta
2
O
5
/NiO/ITO caused an increase in the interfacial
reaction resistance, indicating a disturbance in proton
movement during the coloring/bleaching processes.
On the other hand, the Ta
2
O
5
/Ni(OH)
2
/ITO showed
no irreversible phase transformation, essentially result-
ing in a superior interfacial property between the
Ta
2
O
5
and the electrochromic layer and electrochromic
response speed.
Fig. 6. (a) In situ transmittance curves during the pulse potential
cycling test ( 0.9 and 0.6 V, duration time of 30 s) after the
continuous potential cycling test of Ta
2
O
5
/NiO/ITO (dotted line) and
Ta
2
O
5
/Ni(OH)
2
/ITO (solid line). (b) Normalized transmittance
curves during the first pulse potential cycling of Ta
2
O
5
/Ni(OH)
2
/
ITO (open circle) and Ta
2
O
5
/NiO/ITO (closed circle).
K.S. Ahn et al. / Solid State Ionics 165 (2003) 155160 159
4. Conclusions
Ta
2
O
5
films were deposited on NiO/ITO and
Ni(OH)
2
/ITO, respectively, using an RF magnetron
sputtering system, and the samples were then tested
by continuous potential cycling followed by pulse
potential cycling test. Although both samples had
similar optical differences and stable cycling perfor-
mance, the Ta
2
O
5
/Ni(OH)
2
/ITO clearly showed a su-
perior electrochromic response speed, compared to
Ta
2
O
5
/NiO/ITO. This indicates that the electrochromic
response speed can be considerably influenced by the
interfacial property between the Ta
2
O
5
and the electro-
chromic layer. Unlike Ta
2
O
5
/Ni(OH)
2
/ITO, Ta
2
O
5
/
NiO/ITO showed an irreversible phase transformation
of NiO into Ni(OH)
2
during the first continuous poten-
tial cycling, resulting in a degradation of the interfacial
property between the Ta
2
O
5
and the electrochromic
layer and, as a result, a slow electrochromic response
speed.
Acknowledgements
This work was supported by KOSEF through the
Research Center for Energy Conversion and Storage
and the Ministry of Commerce, Industry and Energy,
and the Brain Korea 21 program of the Ministry of
Education.
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