E68 Journal of The Electrochemical Society, 152 共2兲 E68-E73 共2005兲

0013-4651/2005/152共2兲/E68/6/$7.00 © The Electrochemical Society, Inc.

Impedance Analysis of Internal Resistance Affecting the

Photoelectrochemical Performance of Dye-Sensitized Solar Cells
T. Hoshikawa, M. Yamada, R. Kikuchi, and K. Eguchi*,z
Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University,
Kyoto 615-8510, Japan

To clarify the relationships between the performance of dye-sensitized solar cells and their internal resistances, we applied ac
impedance spectroscopy to the analysis of the cells. Impedance and I-V measurements of solar cells were carried out for various
cell compositions and measurement conditions such as different kinds of conductive glass substrates, two kinds of counter
electrodes, calcination temperature, applied bias, and distance between electrodes; in order to separate internal resistances which
occur at different interfaces. Impedance spectra of dye-sensitized solar cells showed that their internal resistance consisted of at
least five components. It was found that the resistance of a conductive glass substrate appeared as ohmic resistance, and that
electron transfer at F-doped SnO2 共FTO兲/TiO2 , TiO2 /TiO2 , Pt/electrolyte, and TiO2 /electrolyte interfaces was identified as the
internal resistances determinative to the performance of dye-sensitized solar cells. Internal resistances at FTO/TiO2 , Pt/electrolyte
and the resistance of conductive glass affected the fill factor. Internal resistances at TiO2 /TiO2 and TiO2 /electrolyte mainly
affected the photocurrent. Particularly, the TiO2 /electrolyte was significant as the interface controlling photocurrent of the dye-
sensitized solar cell. The impedance stemming from the diffusion of the electrolyte had little effect on the performance of the cells.
© 2005 The Electrochemical Society. 关DOI: 10.1149/1.1849776兴 All rights reserved.

Manuscript submitted October 21, 2003; revised manuscript received March 28, 2004. Available electronically January 20, 2005.

The first report on a new type of dye-sensitized solar cell was
published by Grätzel and co-workers, and the overall light-to-
electric energy conversion efficiency was 7.1-7.9% in simulated
solar light.1 After that, they attained 10% of overall energy con-
version efficiency by improving TiO2 electrodes.2 This device has a
future as a low-cost solar cell because of its low-cost preparation
process and its potential for high-energy conversion efficiency.
In the last decade, after their first report on the dye-sensitized
solar cell, a number of investigations on this type solar cells
have been carried out. However, the energy conversion efficiency of
dye-sensitized solar cells has not been improved enough. Because
many electron-transfer processes take part in energy conversion
in a cell and they interact with each other in a complicated
manner, optimization of dye-sensitized solar cells for improving
their conversion efficiencies has not been completed yet. It is
generally agreed that the high efficiency and stability of the
dye-sensitized solar cell is caused by fast electron injection pro-
cesses and a slow back reaction.3 Electron injection from
Ru共dcbpy) 2 (NCS) 2 关dcbpy ⫽ 共2,2⬘-bipyridyl-4,4⬘-dicarboxylate兲兴
on TiO2 thin film occurs in femto- and picoseconds,4,5 while the
decay rate of the dye in an exited state is observed on a nanosecond
time scale.5 The back reaction from the injected electrons to holes
occurs on a time scale of hundreds of milliseconds to seconds.6
Electron transport in TiO2 is controlled by trapping and detrapping
processes on the time scale of milliseconds,7,8 and Yanagida et al.
reported that electron transport in TiO2 in electrolyte was explained
as ambipolar diffusion and that this type of diffusion was influenced
by electron densities and ion concentration in an electrolyte.9-11
Various works on impedance spectroscopy for dye-sensitized solar
cells were published. The charge-transfer resistance at the platinum
electrode/electrolyte interface12,13 and the diffusion coefficient12 of
I⫺
3 were measured from the impedance of a thin-layer cell consisting
of two platinized glass substrates and electrolyte. Some researchers
have proposed physical models considering the nanoporous TiO2
electrode7,14,15 or TiO2 /electrolyte interface16,17 and have confirmed
that their models were compatible with experimental impedance
data. Analyses of dye-sensitized solar cells with different prepara-
tion methods were also carried out by impedance measurements.
Kim et al. prepared cells with and without carboxylic acids and
showed from their impedance spectra that the presence of carboxylic
acids reduced charge-transfer resistance at electrolyte/TiO2 inter-
* Electrochemical Society Active Member.
z
E-mail: eguchi@scl.kyoto-u.ac.jp
face.18 Longo et al. assembled rigid 共used glass substrate兲 and flex-
ible 关ITO-poly共ethylene terephthalate兲, PET substrate兴 solid-state
cells and found that the shapes of impedance spectra were similar
for both cells, but the impedance of the flexible cell was higher than
that of the rigid one.19 Kern et al. analyzed impedance spectra of
cells by varying cell parameters such as Pt thickness, TiO2 thick-
ness, thickness of cells, and influence of tert-butylpyridine. For a
detailed analysis of spectra, they developed an electrochemical
model.20 However, they did not relate the electrochemical perfor-
mance of the dye-sensitized solar cell with the cell parameters. In
most of the studies on impedance analysis of dye-sensitized solar
cells, their major objectives were to establish the electrochemical
equivalent circuit model of the dye-sensitized solar cell and they
interpreted the model by using experimental impedance data of
cells. These are significant for understanding electron transfer pro-
cesses of dye-sensitized solar cells. Nevertheless, relations between
these processes and electrochemical performance of dye-sensitized
solar cells are not clear yet. It is important for improving perfor-
mance of cells to understand these relations. In our previous paper,
we applied ac impedance spectroscopy to dye-sensitized solar cells
and reported that this method could separate internal resistances
caused by electron transfer processes in these cells.21 This study
aims to further analyze internal resistances in dye-sensitized solar
cells by ac impedance spectroscopy and to investigate relations be-
tween the internal resistance and the performance of the cells.
Experimental
Cell preparation.—The standard method for the fabrication of
dye-sensitized solar cells was previously reported.22 Commercial
TiO2 powders 共JRC-TIO-4, Japan Reference Catalyst, Catalyst So-
ciety of Japan, commercially called P25, Nippon Aerosil兲 were em-
ployed for preparation of nanoporous TiO2 films. The TiO2 powders
were ground with distilled water, acetylacetone, and Triton X-100 to
form viscous pastes. The F-doped SnO2 glass 共FTO兲 was covered on
two parallel edges with adhesive tape to control the thickness of the
TiO2 film. The paste was applied to one of the free edges of the FTO
and spread with a glass rod sliding over the tape-covered edges.
After the electrode was dried in air, it was calcined for 1 h at 500°C
in air. The thickness of this film was about 10 ␮m. The electrode
area was 5 ⫻ 5 mm.
A dye, Ru共II)(2,2⬘ -bipyridyl-4,4⬘ -dicarboxylate) 2 (NCS) 2 ,
共hereafter RuN3兲, was used as the sensitizer in this study. Dye ad-
sorption on the TiO2 electrode was carried out by immersing the
electrode into an ethanol solution with a dye concentration of
3 ⫻ 10⫺4 M (M ⫽ mol dm⫺3兲.

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 Journal of The Electrochemical Society, 152 共2兲 E68-E73 共2005兲 E69

A sandwich-type cell was assembled to measure the photoelec-

trochemical properties and impedance of the dye-sensitized solar
cells. As a counter electrode, a thin Pt layer was deposited on a
conductive glass substrate by a rf-magnetron sputtering technique.
As the electrolyte solution, a commercial electrolyte solution 共TG50,
Solaronix兲 and 0.6 M 1-propyl-2,3 dymethylimidazolium iodide
共DMPImI兲, 0.1 M LiI, 0.5 M t-butylpyridine 共t-BuPy兲, and 0.05 M
I2 in methoxyacetonitrile 共MeAN兲 were employed. A 50 ␮m thick
thermoplastic resin film 共Mitui-Du Pont Polychemical Co., Ltd.兲
with a 7 ⫻ 7 mm window was sandwiched between the two glass
substrates, and then the assembly was heated on a hot plate to
tighten the seal. The electrolyte solution was filled between the two
glass substrates. The standard construction of the cell is written as
follows Figure 1. An impedance spectrum in Nyquist presentation obtained
from TiO2 -based standard dye-sensitized solar cell. Bias, OCV; light in-
FTO兩TiO2 兩 dye兩electrolyte兩sputtered Pt共FTO) tensity, 100 mW cm⫺2. Electrolyte: 0.6 M DMPImI, 0.1 M LiI, 0.05 M I2 ,
0.5 M t-BuPy in methoxyacetonitrile. Structure of cell: FTO兩 TiO2
Photoelectrochemical measurement.—Performance and imped- 共P25兲兩dye共RuN3兲兩electrolyte兩sputtered Pt 共FTO兲.
ance of the cells were measured by using a potentiostat 共Solartron
1287兲 and a frequency response analyzer 共Solatron 1260兲. Standard
measurements were carried out under 100 mW cm⫺2 illumination discuss the relationship between the performance of the dye-
and applied open circuit voltage 共OCV兲 as bias. A 500 W Xe lamp sensitized solar cell and components of internal resistance (R 0 and
was used for irradiating the cells. The UV 共⬉400 nm兲 and IR 共⭌800 ␻ 1 -␻ 4 ) of it.
nm兲 components of the light were cut off by filters. Light intensity
was calibrated with a photopower meter. Impedance analyses of various dye-sensitized solar cells.—Glass
Most of the impedance measurement in this study were carried substrate.—R 0 in Fig. 1 was recognized as the ohmic resistance of
out by applying bias at OCV, namely, under the condition of no the dye-sensitized solar cells. Electron transport processes of the
electric current flowing, because the spectra at this condition contain very short time constant are included in R 0 . For example, a resis-
only the information related to the electric transports at various in- tance of a conductive glass substrate is this case. Figure 2a shows
terfaces in the cell. Impedance measurement of cells was recorded I-V curves and Fig. 2b shows Nyquist plots for dye-sensitized solar
over a frequency range of 0.01 to 300 kHz with ac amplitude of 10 cells with various glass substrates for TiO2 electrodes. One In-doped
mV. For the dye-sensitized solar cell, this frequency range is appro- SnO2 glass substrate 共ITO兲 and two kinds of F-doped SnO2 glass
priate, since the total resistance of this cell shows good agreement substrates 共FTO1 and FTO2兲 were used in this experiment. The
values between those calculated from the slope of I-V curves at
OCV and evaluated from impedance spectra at OCV. Results of
impedance measurements were represented as a Nyquist plot. An arc
in the Nyquist plot represents the existence of an electrochemical
interfaces so we can easily distinguish electrochemical interfaces
existing in cells.
It seems difficult to compare I-V and impedance characteristics
with data from others because of the difference in light source and
the diversity of materials of the cells from other workers, thus rela-
tive changes of their values are comparable.
Under dark conditions, similar impedance spectra were observed
when the forward bias was applied to the cell. They consisted of
four semicircles with almost the same characteristic frequency as
those measured under the illumination conditions. Therefore, imped-
ance measurements were carried out under illumination conditions
in this study.

Results and Discussion

Impedance spectrum of a standard dye-sensitized solar
cell.—Figure 1 shows an impedance spectrum in Nyquist presenta-
tion of a TiO2 -based dye-sensitized solar cell made by the standard
fabrication process. This impedance spectrum consists of ohmic re-
sistance (R 0 ) and four arcs (␻ 1 -␻ 4 ). An arc in the Nyquist plot
represents the existence of an electrochemical interfaces. The fre-
quency at the top of this arc, that is, the characteristic frequency ␻
has a special value, which was defined as ␻ ⫽ (RC) ⫺1 , where R
and C are resistance and capacitance at an electrochemical interface,
respectively. Therefore, the appearance of plural arcs in the Nyquist
plot indicates that electrochemical interfaces having different time
constants for electron transport existing in the electrochemical sys-
tem. In the case shown in Fig. 1, at least four different electrochemi-
cal interfaces exist, and these have a direct influence shown on the Figure 2. 共a兲 I-V curves and 共b兲 impedance spectra for dye-sensitized
performance of the dye-sensitized solar cell. Characteristic frequen- solar cells. Three kinds of glass substrates were used for TiO2 electrodes.
cies of these four arcs shown in Fig. 1 were around ␻ 1 : 7500, ␻ 2 : Light intensity: 100 mW cm⫺2. Structure of cell: FTO, ITO兩 TiO2
750, ␻ 3 : 9.5, and ␻ 4 : 0.3 Hz, respectively. In the following, we 共P25兲兩dye共RuN3兲兩electrolyte兩sputtered Pt 共FTO兲.

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E70 Journal of The Electrochemical Society, 152 共2兲 E68-E73 共2005兲
Figure 3. 共a兲 I-V curves and 共b,c兲 impedance spectra for dye-sensitized
solar cells. TiO2 electrodes were calcined at different temperatures. Imped-
ance spectra for 500 and 300°C are magnified at 共c兲. Light intensity: 100 mW
cm⫺2. Structure of cell: FTO兩 TiO2 共P25兲兩dye共RuN3兲兩electrolyte兩sputtered Pt
共FTO兲.
sheet resistance of glass substrates was increased in the samples of
ITO and FTO1 after 500°C calcination of these samples. I-V curves
of these three samples show that samples having higher sheet resis-
tances 共ITO, FTO1兲 displayed lower fill factors. This increase in the
resistance appeared to be the difference of R 0 in the Nyquist plot,
and higher resistances of glass substrates lead to larger R 0 . In the
impedance spectra of ITO and FTO1, arcs of ␻ 1 were relatively
bigger than the arc of ␻ 1 of FTO2. This result suggests the arc of ␻ 1
is attributed to the resistance of the electrochemical interface at glass
substrate/TiO2 .
Calcination temperature.—When the TiO2 electrode is fabricated by
using TiO2 paste, a calcination process is needed. This calcination is
generally carried out at 450-500°C and leads to the promotion of
electron transport at the grain boundary of TiO2 particles and
particles/SnO2 interface. Accordingly, we investigated the influence
of calcinations temperature on the performance of TiO2 electrode.
TiO2 electrodes were calcined at 100, 300, and 500°C, respectively.
Figure 3 shows 共a兲 I-V curves and 共b兲 Nyquist plots for the cells
with TiO2 electrodes calcined at different temperatures. A distinct
change in the Nyquist plots appeared depending on the calcinations
temperature. The arcs, except for that of ␻ 4 , were expanded as the
calcination temperature was decreased. In addition to this, the bor-
der between the arcs of high frequency range (␻ 1 -␻ 3 ) became
vague, and these arcs appeared as one semicircle, when the calcina-
tion temperature was lowered. Especially, the arcs of ␻ 2 and ␻ 3
were enlarged as the calcination temperature was decreased; the ␻ 2
arc was shrunk considerably between the calcination temperatures of
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Figure 4. Thermal analysis of the TiO2 paste.
300 and 500°C, while the ␻ 3 slightly changed its characteristic fre-
quency from 30 to 12 Hz. We reported previously that only one
semicircle at a characteristic frequency of several hundreds hertz
was observed in a impedance spectrum for a TiO2 film, and this
characteristic frequency corresponds to that of ␻ 2 in Fig. 3.21 There-
fore, it can be that, in the samples calcined at lower temperatures,
there remained a lot of grain boundaries between TiO2 particles due
to insufficient sintering, which resulted in the expansion of the ␻ 2
arc. This is consistent with the results of thermal analyses of TiO2
paste shown in Fig. 4. The exothermic weight loss of TiO2 paste was
observed up to 400°C. This weight loss can be brought about by
decomposition of organic compounds contained in the TiO2 paste.
This result suggests that at least a calcination temperature of 400°C
is needed for the TiO2 electrode to exhibit a sufficient performance.
These results indicate that TiO2 electrodes calcined at low tempera-
ture do not sinter sufficiently, so that a lot of grain boundaries re-
main between TiO2 particles. The low photocurrent of the sample
calcined at low temperature can explain that a lot of grain bound-
aries prevent injected electrons from flowing smoothly, and then
most of the injected electrons are lost at the grain boundaries and
cannot attain to the outer circuit.
Counter electrode.—At the counter electrode of dye-sensitized solar
cell, reduction of I⫺ 3 takes place. Pt adhered to a conductive glass
substrate was mainly used as the counter electrode. To investigate
the influence of the counter electrode on the impedance of the dye-
sensitized solar cell, Pt plates with and without sputter-deposited Pt
were used as the counter electrode, instead of a conventional sputter-
deposited Pt on FTO glass in this experiment. I-V curves for the
cells with and without the sputter-deposited Pt electrode show that
the fill factor of the cell with sputter-deposited Pt electrode is supe-
rior to that without sputtered Pt. The Nyquist plots of these samples
are shown in Fig. 5. A distinct difference in the spectra appeared in
the arc with a characteristic frequency of about 1 kHz (␻ 2 compo-
nent兲. The arc of this frequency was enlarged when the Pt electrode
without sputter-deposited Pt was used. This is consistent with the
result reported previously by Kern et al.;20 they showed theoreti-
cally and experimentally inferior performance of the counter elec-
trode resulted in the expansion of the ␻ 2 component. It is expected
that Pt sputter deposition on the counter electrode increasess the
surface area of counter electrode and, consequently, promotes the
reaction of I⫺3 reduction at the Pt/electrolyte interface. Therefore, the
arc with a characteristic frequency of 1 kHz is attributed to the
charge-transfer resistance at this interface, and the decrease in this
resistance improves fill factor. However, this resistance is invisible
in the Nyquist plot of the standard dye-sensitized solar cell, because
this resistance is small when it is compared with others.
Applied bias.—The impedance of dye-sensitized solar cells has been
measured at open circuit conditions. It is also important to study the
impedance under the solar cell being operated. Here, we investi-
gated the changes of impedance spectra applying different biases to
the solar cell. Impedance spectra for the dye-sensitized solar cell
measured under different applied bias, and the I-V curve of this cell
 Journal of The Electrochemical Society, 152 共2兲 E68-E73 共2005兲
Figure 5. 共a兲 I-V curves and 共b兲 impedance spectra for dye-sensitized solar
cells. Cathodes of these cells were Pt plate with and without sputter depos-
ited Pt. Light intensity: 100 mW cm⫺2. Structure of cell: FTO兩 TiO2
共P25兲兩dye共RuN3兲兩electrolyte兩with and without sputtered Pt plate.
are shown in Fig. 6. It is found that the arc of ␻ 3 in the impedance
spectra was gradually enlarged as the applied bias to the cell ap-
proached from open circuit to short circuit. In our previous paper,
we reported that the ␻ 3 was reduced by increasing adsorbing-dye on
the TiO2 surface and by intensifying the irradiating light to the solar
cell,21 and that ␻ 3 was attributable to the electron transport process
at the electrolyte/dye/TiO2 interface. The change of ␻ 3 under differ-
ent applied bias can be explained as follows: when the cell is at open
circuit under illumination, injected electrons accumulate in the TiO2
and generate a photovoltage.23 The generation of photovoltage
means the increase in the electrochemical potential of electrons in
the TiO2 . This potential shift can be the driving force for the back
reactions of the electrons with I⫺3 . The rate of this reaction is faster
as the potential difference between electrochemical potential in the
TiO2 and redox potential of I⫺/I⫺ 3 is larger. Therefore, at open cir-
cuit, almost all the injected electrons can return to the electrolyte by
the back reaction. At short circuit, lots of the injected electrons reach
the external circuit by way of the back contact, and thus the number
of electrons going back to the electrolyte is decreased significantly.
Therefore, the change of ␻ 3 under different applied bias can be
explained as the change of the number of electrons going back to
electrolyte at the TiO2 /electrolyte interface. The arc of ␻ 3 is, thus,
related closely to the short circuit current; expansion of ␻ 3 corre-
sponds to a decrease in the short circuit current. These results indi-
cate that internal resistance at the TiO2 /electrolyte interface in the
dye-sensitized solar cell is an essential component for performance
of the cell.
Distance between electrodes.—In the impedance spectra, the ␻ 4
component was almost unchanged when the measurement param-
eters and the cell components were altered as shown above. Since
the resistance characterized by ␻ 4 is relatively large in the imped-
ance spectra, it is important to clarify the relation between the ␻ 4
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E71
Figure 6. 共a兲 The I-V curve and 共b兲 impedance spectra for dye-sensitized
solar cells under different applied bias. Light intensity: 100 mW cm⫺2. Struc-
ture of cell: FTO兩 TiO2 共P25兲兩dye共RuN3兲兩electrolyte兩sputtered Pt 共FTO兲.
component and the cell performance. We investigated the relation-
ship between the performance of the cell and the distance between
two electrodes of the cell. Altering the thickness of sealant regulated
the distance between the electrodes of the cell. Impedance spectra
for dye-sensitized solar cells with various distances between the
anode and cathode are shown in Fig. 7a. The component of ␻ 4
changes obviously when the distance between anode and cathode of
the cell is varied. As the distance between electrodes is increased,
the arc of ␻ 4 in the impedance spectra becomes enlarged. This phe-
nomenon was also observed in the cell where the electrolytes having
different thicknesses were sealed between two Pt electrodes 共Fig. 8兲.
For the cell consisting of two identical platinized substrates, Hauch
and Georg proposed a equivalent circuit for this cell and concluded
that the arc in the low frequency range was the Nernst diffusion
impedance of I⫺ 13
3 in electrolyte. They insisted that the good agree-
ment of the diffusion constants of I⫺3 determined from the diffusion-
limited current and Nernst impedance was the proof for the interpre-
tation of this arc. We calculated the diffusion constant of I⫺ 3
according to their method. 9.1 ⫻ 10⫺6 cm2 s⫺1 was obtained as the
diffusion constant of I⫺3 from Nernst impedance, and 9.9 ⫻ 10
⫺6
cm2 s⫺1 from diffusion-limited current. These values are appropriate
as compared with their results. Therefore the arc of ␻ 4 in the im-
pedance spectra is presumed to be a Nernst impedance because both
the dye-sensitized solar cell and the electrochemical device consist-
ing of two Pt electrodes have the same characteristic frequency of
␻ 4 when the distance between two electrodes are equal. The rela-
tionship between ␻ 4 and performance of the cell is not so serious.
I-V curves for dye-sensitized solar cells with various distances be-
tween anode and cathode is shown in Fig. 7b. I-V curves of these
E72 Journal of The Electrochemical Society, 152 共2兲 E68-E73 共2005兲
Figure 7. 共a兲 Impedance spectra and 共b兲 I-V curves for dye-
sensitized solar cells with various distances between anode and cathode.
Light intensity: 100 mW cm⫺2. Structure of cell: FTO兩 TiO2
共P25兲兩dye共RuN3兲兩electrolyte兩sputtered Pt 共FTO兲.
cells do not change clearly while ␻ 4 in these ones change remark-
ably. Other researchers have already carried out similar work, and
their results agree well with ours with regard to ␻ 4 in experimental
and calculated impedance spectra.20 Thus, Nernst diffusion imped-
ance of I⫺3 in electrolyte seems not to be a dominating component
for the performance of dye-sensitized solar cell.
Concerning the action at ␻ 3 , Kern et al. observed a discrepancy
between the calculated and measured spectra for the increase in the
distance between the electrodes. The arc at ␻ 3 in the measured
spectra expanded as the distance between the electrodes was longer,
though that in the calculated spectra did not change. In order to
explain this disagreement, they assumed an equilibrium of impuri-
ties adsorbed on the TiO2 surface and residing in the electrolyte. The
impurities act as recombination centers, and these impurities might
affect the effective electron lifetime of the injected electrons. Since
Figure 8. Impedance spectra for electrochemical devices which consist
of two Pt-sputtered substrates. The distance between two electrodes
was changed. Structure of cell: sputtered Pt 共FTO兲兩electrolyte兩sputtered
Pt 共FTO兲.
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the model did not take this effect of the impurities into account, the
calculated results could disagree with the experiments. As for our
results on the ␻ 3 arc, we also observed expansion of the arc as the
distance of the electrodes increased from 44 to 180 ␮m. However,
the ␻ 3 arc was invariable in its size for the further increase in the
distance. In addition, the short circuit current decreased only when
the distance of the electrodes increased from 44 to 180 ␮m. This
might be explained by referring to the above-mentioned impurities
as follows: if the distance between the electrodes becomes long,
namely, a large amount of electrolyte exists in the dye-sensitized
solar cell, the amount of the impurities adsorbed on the TiO2 surface
and in the electrolyte close to the TiO2 surface are expected to
decrease relatively. Thus not many of the photoinjected electrons are
consumed by the recombination reaction with impurities, leading to
a longer effective electron lifetime. The longer electron lifetime in
TiO2 anticipated an increase of photocurrent and photovoltage of
cells. As is expected from the discussion above, in our experiments
photovoltage increased and the resistance at the ␻ 3 component was
enlarged for the increase in the distance from 44 to 180 ␮m. The
resistance at the ␻ 3 component is related to the tendency of recom-
bination at the TiO2 /electrolyte interface as mentioned above, and
thus a high recombination tendency can result in a low resistance at
the ␻ 3 component. Nevertheless, a further explanation is a requisite
for high short circuit current of the 44 ␮m thick sample despite the
short electron lifetime. In the thin sample of 44 ␮m, the photon flux
reflected at the counter electrode can be converted effectively in the
case of the cell having a thin electrolyte layer, but it would have no
effect when the electrolyte layer is thick enough for I⫺ 3 to absorb the
incident photon. This effect leads to lower photocurrent when the
distance between the electrodes was longer.
Conclusions
Impedance measurement for dye-sensitized solar cells is an ef-
fective method for investigating the contribution of each internal
resistance of cells. It was found that internal resistances of the dye-
sensitized solar cells consisted of one ohmic resistance R 0 and four
arcs attributed to electron transfer at electrochemical interface. The
characteristic frequency of the arcs in the impedance spectra, which
suggest existence of different kinds of electrochemical steps, ap-
peared about at ␻ 1 : 7.5 kHz, ␻ 2 : 750 Hz, ␻ 3 : 9.5 Hz and ␻ 4 : 0.3
Hz, respectively. Results of the comparison of impedance spectra for
various kinds of dye-sensitized solar cells indicated that ␻ 1 , ␻ 2 ,
␻ 3 , and ␻ 4 were attributable to the electron transfer at the
SnO2 /TiO2 interface, electron transfer between TiO2 particles, back
reaction from injected electrons in TiO2 to I⫺ 3 in the electrolyte, and
the diffusion impedance of I⫺ 3 in the electrolyte, respectively. De-
crease in R 0 and ␻ 1 impedance spectra for dye-sensitized solar cells
results in the increase of fill factor of the cells. Smaller ␻ 2 and ␻ 3
produce higher photocurrent. The effect of the ␻ 4 component was
not remarkable on the performance of dye-sensitized solar cells.
Particularly, the electron transfer at the TiO2 /electrolyte interface
was crucial in controlling the photocurrent of the dye-sensitized so-
lar cell, so that this interface is decisive for conversion efficiency.
This result indicates that optimization of the TiO2 /electrolyte inter-
face is most important for improve the performances of dye-
sensitized solar cells.
Acknowledgments
This work was supported by a Grant-in-Aid for Scientific Re-
search on Priority Areas 共417兲 from the Ministry of Education, Cul-
ture, Sports, Science and Technology 共MEXT兲 of the Japanese Gov-
ernment and by a JSPS Fellows 共15005584, 2003兲 from Japan
Society for the Promotion of Science.
 Journal of The Electrochemical Society, 152 共2兲 E68-E73 共2005兲
Kyoto University assisted in meeting the publication costs of this article.
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