d 93549007 A | Titanium Dioxide | Physical Chemistry

EIS Analysis on Low Temperature Fabrication of TiO

2
Porous
Films for Dye-Sensitized Solar Cells
Chao-Po Hsu
a
, Kun-Mu Lee
b
, Chia-Yu Lin
a
and Kuo-Chuan Ho
a,b*
a
Department of Chemical Engineering, National Taiwan University, Taipei 10617,
Taiwan
b
Institute of Polymer Science and Engineering, National Taiwan University, Taipei
10617, Taiwan
*
Corresponding author: E-mail: kcho@ntu.edu.tw
Manuscript prepared for the oral presentation at the 7
th
International Symposium
on Electrochemical Impedance Spectroscopy, France, June 3-8, 2007, and
submitted for the publication in Electrochimica Acta.
2
EIS Analysis on Low Temperature Fabrication of TiO
2
Porous Films for
Dye-Sensitized Solar Cells
Chao-Po Hsu
a
, Kun-Mu Lee
b
, Chia-Yu Lin
a
and Kuo-Chuan Ho
a,b*
a
Department of Chemical Engineering, National Taiwan University, Taipei
10617, Taiwan
b
Institute of Polymer Science and Engineering, National Taiwan University, Taipei
10617, Taiwan
*
Corresponding author: E-mail: kcho@ntu.edu.tw
Abstract
A low temperature (<150°C) fabrication method for preparation of TiO
2
porous
films with high efficiency in dye-sensitized solar cells (DSSCs) has been developed.
The Ti(IV) tetraisopropoxide (TTIP) was added to the paste of TiO
2
nanoparticles to
interconnect the TiO
2
particles. The effects of TTIP/TiO
2
molar ratio, TiO
2
film
thickness, TiO
2
morphology and sintering time of TiO
2
film on the cell performance
were investigated. It was found that as the TTIP/TiO
2
molar ratio increased from 0.02
to 0.08, the interconnections became better and the best result was obtained at a molar
ratio of 0.08. However, higher molar ratios led to the formation of amorphous TiO
2
in
large quantity around the P25 titanium particles. The electrochemical impedance
3
spectroscopy (EIS) technique was employed to quantify the charge transport
resistance at the TiO
2
/dye/electrolyte interface (R
ct2
) and electron lifetime in the TiO
2
film (t
e
) under different molar ratios of TTIP/TiO
2
and TiO
2
thicknesses. It was found
that the R
ct2
decreased as the molar ratio increased from 0.02 to 0.08, however, it
increased at a molar ratio of 0.2 due to the reduction in surface area and less adsorbed
dye. In addition, the characteristic frequency peak shifted to lower frequency at a
molar ratio of 0.08, indicating the longer electron lifetime. As for the thickness effect,
TiO
2
film with a thickness around 17 µm achieved the best cell efficiency. This is
because larger film thickness tends to increase the amount of dye adsorption, but it
also causes larger electron transport resistance and reduces the open-circuit voltage
and conversion efficiency. EIS study also confirms that, under illumination, the
smallest R
ct2
is associated with a TiO
2
thickness of 17 µm, with the R
ct2
increase as
the thickness of TiO
2
film increase. In the Bode plots, the characteristic frequency
peaks shifted to higher frequency when the thickness of TiO
2
increased from 17.2 to
48.2 µm. This indicates that the electron recombination increases as the thickness of
the TiO
2
electrode increases.
To make better use of longer wavelength light, 30 wt% of larger TiO
2
particle
(300 nm) was mixed with P25 TiO
2
as light scattering particles. It effectively
increased the short-circuit current density and cell conversion efficiency from 7.44
4
mA/cm
2
and 3.75 % to 8.80 mA/cm
2
and 4.20 %, respectively.
Keywords: Low temperature fabrication of TiO
2
film, dye-sensitized solar cell, EIS
5
1. Introduction
The dye-sensitized solar cell (DSSC) has attracted much attention as the
next-generation solar cell. Remarkably, the low production costs and good efficiency
for energy conversion, reaching 11 % and module efficiency for 7 % in some cases
[1]. Their energy conversion working principle is based upon the injection of
electrons from a photoexcited state of the sensitizer into the conduction band of the
semiconductor. A charge mediator, i.e., a suitable redox couple, must be added to the
electrolyte for reducing the oxidized dye. The mediator also needs to be renewed in
the counter-electrode, making the photoelectrochemical cell regenerative.
At the present time, research pursues the development of the inexpensive solar
cell based on flexible plastic substrate as the nanocrystalline TiO
2
electrode and
counter electrode [2]. However, the conventional method for the preparation of TiO
2
electrodes for DSSCs using colloidal suspensions of TiO
2
nanopaticles includes
high-temperature sintering at 450~500
o
C which is necessary to establish a good
interconnection between the TiO
2
particles and to remove organic additives such as
precursor or polymer for cement the connection between TiO
2
particles and the
substrate. But this method cannot be applied to prepare films on plastic substrates
because plastic substrates structure would crack at such high temperature.
The development of low-temperature fabrication methods should overcome two
6
main problems such as incomplete necking of the particles and presence of residual
organics in the film [3]. These problems cause lower diffusion coefficient and the
lifetime of the electrons. The film revealed a larger inherent resistance than the
conventional ones. Recently, some efforts have been made to develop methods
compatible with plastic substrate such as electrophoretical deposition [4], gas phase
hydrothermal preparation [5], chemical sintering [6], mechanical compression of
crystalline particles [7], and UV/O zone treatment [8]. At present, the efficiency level
could achieve 4.5% under irradiation of 100 mW/cm
2
.
In this study, we prepared porous TiO
2
film based on sintering of colloids and
precursor at a low temperature (150
o
C). TTIP mixed with nanocrystalline TiO
2
powder is hydrolyzed and crystallizes into TiO
2
when they are treated by low
temperature sintering in the oven. The newly formed TiO
2
acts as “glue” interconnects
of the TiO
2
particles as well as that between the film and the substrate [9]. It would
improve the connection between TiO
2
particles resulted from the low sintering
temperature which caused a poor electric contact between particles in the film.
In addition, electrochemical impedance spectroscopy (EIS) is a useful method
for analysis of charge transport process. EIS is a steady state method measuring the
current response to the application of an ac voltage as function of the frequency [10].
EIS has been widely employed to study the kinetics of electrochemical and
7
photoelectrochemical processes including the elucidation of salient electronic and
ionic process occurring in the DSSCs [11-14]. In this study, we utilize the EIS not
only analyze the each charge transport resistances in DSSCs but also fit the curves in
Nyquist plots. After calculating the exact resistance, capacitance and time constant in
DSSCs, the effects of low temperature fabrication parameter of TiO
2
electrodes on
DSSCs were studied.
2. Experimental
2.1. Materials
Anhydrous I
2
, ethanol (99.5%), tertiary butanol and 4-tertiary butyl pyridine
(TBP) were obtained from Merck and Titanium (IV) isopropoxide (+98 %) was
purchased from Acros and all were used as such. The N3 dye was the commercial
product obtained from Solaronix S.A., Aubonne, Switzerland.
2.2. Preparation of TiO
2
electrodes
The preparation of TiO
2
precursor and the electrode fabrication were carried out
according to the procedures mentioned in literatures [15]. Degussa P25-TiO
2
, titanium
(IV) isopropoxide (TTIP), and ethanol were mixed at different molar ratios and
dispersed using an ultrasonic horn for 30 min, After stirring for 1 hour, the paste was
coated on fluorine doped SnO
2
-coated conductive glass (FTO/glass ) by a glass rod.
8
The ethanol evaporated in the air at room temperature after a few minutes. Then the
films formed were sintering at 150
o
C for at different times.
2.3. The cell assembly of DSSCs
An active area of 0.25 cm
2
was selected from sintered electrode and the
electrodes were immersed in 3 × 10
-4
M solution of
cis-di(thiocyanato)bis(2,2'-bipyridyl-4,4'-dicarboxylate)ruthenium (II) (N3 dye)
containing acetonitrile and tertiary butanol (in the volume ratio of 1:1) overnight. Pt
(100 nm thick) sputtered on FTO was used here as the counter electrode.
The cell was fabricated by applying an ionomer resin (Surlyn 1702, Dupont,
thickness of 50 µm) between the two electrodes and then two holes were made on the
resin. The whole set-up was heated at 100
o
C on a hot plate till all the resin had been
melted and the electrolyte was injected into the space between the electrodes through
these two holes. Finally, these two holes were sealed completely by the Torr Seal
®
cement (Varian, MA, USA). The electrolyte was composed of 0.8 M
1-methyl-3-propylimidazolium iodide (MPII) /0.1 M LiI /0.05 M I
2
/0.5 M TBP in
CH
3
CN.
2.4. Instrumenst and measurements
The photoelectrochemical characterizations of the DSSCs were carried out by
using an AM 1.5 simulated light radiation (1 sun). The light source was a 450 W Xe
9
lamp (Oriel, #6266) equipped with a water-based IR filter and AM 1.5 filter (Oriel,
#81075). UV–visible absorption data were measured by UV-visible spectra (Jasco,
V-570). Photoelectrochemical characteristics and the electrochemical impedance
spectroscopy (EIS) measurements of the DSSCs were recorded with a
potentiostat/galvanostat (PGSTAT 30, Autolab, Eco-Chemie, Netherland) under
100mW/cm
2
. The frequency range was explored from 10 mHz to 65 kHz. The applied
bias voltage and ac amplitude were set at open-circuit voltage of the DSSCs at 10 mV
between the FTO-Pt counter electrode and the FTO-TiO
2
-dye working electrode,
respectively, starting from the short-circuit condition [16]. The impedance spectra
were analyzed by an equivalent circuit model interpreting the characteristics of the
DSSCs [17].
10
3. Results and discussion
3.1 The effects of different TTIP/TiO
2
molar ratios on DSSCs
First of all, to optimize the molar ratio of TTIP with respect to TiO
2
powder for
film preparation, the films made up of pastes with different TTIP concentrations were
investigated. The TiO
2
films with different molar ratios of TTIP/TiO
2
between 0.02
and 0.20 were measured. The change of their surface parameters and cell
performances were shown in Table 1. With the increase of TTIP/TiO
2
molar ratio
from 0.02 to 0.20, it was found that the interconnections were poor between TiO
2
particles at molar ratio of 0.02 and the best result was obtained at a molar ratio of 0.08.
At this condition, the surface area and the pore size were 46.7 m
2
/g and 11.0 nm,
respectively. Higher molar ratios led to the formation of amorphous TiO
2
in large
quantity around the P25 titanium particles and thus, the pore diameter decreased from
11.0 to 6.9 nm and the I
-
/I
3
-
ions were difficult to penetrate into the inner pore of TiO
2
electrode to reduce the oxided (oxidized) dyes, resulting in poor conversion efficiency.
This observation could be explained by the fact that the pores with a diameter of
about 7 nm and 3 nm are occupied by the N3 dye molecules and leaves an aperture of
only 3-4 nm for the diffusion of the electrolyte. This distance is only little larger than
the size of the I
3
-
ion, if one considers the solvation shell and Fick’s law of diffusion
that maybe not valid [18].
11
From ASAP data, when the molar ratios increase from 0.02 to 0.08, surface area
did not vary significantly, which around 47–49 m
2
/g, and the pore diameter have
slightly decreased from 11.8 to 11.0 nm. However, when the TTIP/TiO
2
ratio was
increased to 0.20, the TiO
2
particles became “flack form” and thus reducing the
surface area as well as the pore diameter to 36.8 m
2
/g and 6.9 nm, respectively. The
morphology of TiO
2
film prepared at optimized molar ratio of 0.08 was studied by
using SEM images and its corresponding pictures are shown in Fig. 1. The results
depict similarity to that film prepared by the conventional method i.e prepared by
annealing under 500
o
C. Its high porosity and high surface area caused the higher
amount of adsorbed dyes and the photocurrent. However, the film obtained at molar
ratio of 0.20 had larger amount of amorphous TiO
2
due to ambient hydrolysis of TTIP,
which ultimately decreased the surface area and pore diameter of the film.
Consequently, the addition of optimum TTIP in TiO
2
powder is in order to cover the
surface of TiO
2
particles to increase the good interconnection. It was expected that the
TTIP is completely converted into anatase TiO
2
after annealing to transport electrons
which obtained from excited dyes rapidly so as to have longer electron lifetime [ ].
Furthermore, using electrochemical impedance spectroscopy (EIS) the internal
resistances and the electron transport kinetic of the TiO
2
films in DSSCs are also
studied. Fig. 2 (a) and (b) showed the Nyquist plots of the electrochemical impedance
12
spectra of the DSSCs for different TTIP/TiO
2
ratios measured under 100 mW/cm
2
,
and the equivalent circuit showed in the inset of Fig. 2 (a). All the spectra exhibit
three semicircles, which are assigned to electrochemical reaction at Pt counter
electrode, charge transfer at the TiO
2
/dye/electrode and Warburg diffusion process of
I
-
/I
3
-
[16, 17]. It was found that the charge transport resistance at the
TiO
2
/dye/electrolyte interface (R
ct2
) decreased as a function of the molar ratio of
TTIP/TiO
2
from 0.02 to 0.08 (Fig. 2 (b)), and increased at a molar ratio of 0.20 due to
the decrease in surface area thus adsorbed less dyes and the difficult of redox couples
penetrated into TiO
2
pores (Fig. 2 (a)). Correspondingly, the characteristic frequency
peaks (1-10
3
Hz) in Bode phase plots were shown in Fig. 2 (c). The characteristic
frequency peak shifted to lower frequency when the molar ratio increased to 0.08 and
then shifted back again to higher frequency when the ratio was 0.20. The
characteristic frequency was expressed as the inverse of recombination lifetime (t
r
),
or electron lifetime in TiO
2
[19-21]. It also indicated that the 0.08 molar ratio has the
longer electron lifetime. From the results, it is found that the TiO
2
film prepared at the
ratio of 0.20 is not only has high transport resistance but also has lower electron
lifetime in TiO
2
electrode.
Electrochemical impedance was also measured in the dark to elucidate the
correlation of electron transport with different molar ratios. In these cells, the
13
electrons were transported through the mesoscopic TiO
2
network and react with I
3
-
. At
the same time, I
-
was oxidized to I
3
-
at the counter electrode. Hence, the net current
was largely dependent on the applied bias. The fitted data between electron transport
resistances vs capacitance obtained from the Nyquist plots for various molar ratios
under different forward biases were plotted. The time constant can be calculated by
equation (1):

n
= R
ct2
×C

(1)
where R
ct2
and C

are the charge transport resistance and the capacitance at
TiO
2
/dye/electrolyte interface, respectively.
We can see at the ratios of 0.04 and 0.08 have higher resistances ?? than the
others measured in the dark were showed in Fig. 3 (a). This indicates that DSSCs
based on TTIP/TiO
2
ratios of 0.04 or 0.08 have less recombination and higher
open-circuit voltage (V
OC
). The cell capacitances for all TTIP/TiO
2
ratios increased
with increase of the bias (Fig. 3 (b)). The time constants increased with the forward
increase of bias and it was also found higher at ratio of 0.08 than the other ratios as
shown in Fig. 5 (c), which revealed that devices containing TiO
2
with ratio of 0.08
had larger time constant due to slower recapture of conduction band electrons by I
3
-
.
This outcome is consistent with our previous argument.
3.2 The effects of thickness of TiO
2
electrode on DSSCs
14
As for the thickness effect, from Table 2, it was noted that TiO
2
film with a
thickness around 17 µm achieved the best cell efficiency of 4.28 %, and on further
increasing of it caused the lowering of the short circuited current density (J
SC
), the
open-circuit voltage (V
OC
) and conversion efficiency. That is, although larger film
thickness tends to increase the amount of dye adsorption, it causes higher electron
transport resistance and increase the recombination of electron with I
3
-
on TiO
2
surface with film thickness increase, resulting in reduce the V
OC
and conversion
efficiency. It is noticeably that when the thickness of TiO
2
film is larger than 48 µm,
the film stare to peel off and is therefore unstable in that condition, resulting in the
current density decreases obviously to only of 2.22 mA/cm
2
. The variation of dye
loading and photovoltaic characteristics such as J
SC
, V
OC
,FF and q are summarized
in Table 2.
EIS study also confirms above outlooks, under illumination, the smallest R
ct2
is
associated with a TiO
2
thickness of 17.2 µm, with the R
ct2
increased as the thickness
of TiO
2
film increased. In the Bode phase plot, the characteristic frequency peaks
shifted to higher frequency when the thickness of TiO
2
increased from 17.2 to 48.2
µm. This behavior indicates that the electron recombination increases with the
increase of the thickness of TiO
2
electrode. In addition, the electron transport
resistance (R
ct2
) and capacitance (C
µ
) were obtained by fitting the middle frequency
15
semicircles in the Nyquist plot were shown in Fig. 4. It was found that the
capacitances had a liner relationship with the film thickness and there was a lower R
ct2
for the TiO
2
with a thickness of 17.2 µm, further, the R
ct2
increases as the thickness of
TiO
2
increases from 17.2 to 48.2 µm. This observation is rationalized in terms of an
increase in the number of traps encountered by the conduction band electrons with
increasing film thickness. This slows down the electron motion lowering the electron
collection efficiency [22].
3.3 The effect of light intensity on DSSCs
In addition, we also have investigated the effect of light intensity on DSSCs by
using EIS. Figure.5 shows the impedance spectra of DSSCs with TiO
2
electrode
prepared at molar ratio of 0.08 and thickness of 17.2 µm at different light intensities.
The results indicated that R
ct2
decreased and the characteristic frequency peaks were
also shifted to higher frequency as the light intensity increased. Those results
suggested that more electrons are injected in TiO
2
electrode, but the injected electrons
are lost more rapidly with the light intensity increase. Meanwhile, under illumination,
V
OC
can be expressed as [11,23]:
|
|
.
|

\
|
+
=
+ ÷
] [ ] [
ln
2 0 3 1 0
D k n I k n
AI
F
RT
V
OC

(2)
where k
1
and k
2
being the kinetic constant of back reaction of injected electrons with
triiodide and recombination of these electrons with oxidized dye , respectively, and n
0
16
being the concentration of accessible electronic states in the conduction band. (What
about the other symbols) Neglecting the loss term due to recombination with the
oxidized dye molecules, V
OC
depends logarithmically on the inverse concentration of
I
3
-
and increases with incident photo flux I. The V
OC
of DSSCs measured at the molar
ratio of 0.08 and 17.2 µm of TiO
2
electrode under 100, 60 and 10 mW/cm
2
illumination were found to be 0.760, 0.735 and 0.695 V, respectively, . Any variations
of the local triiodide concentration due to light illumination appear to have a small
effect [11].
3.4 Optimization of the preparation of TiO
2
electrode to get better performance of
DSSCs
Understanding about the effects of annealing time on performances of DSSCs is
necessary. Hence, the TiO
2
film fabricated at low temperature was annealed at 150°C
under various times. The current density and conversion efficiency increased gently
with the increase in the annealing time as shown in Fig. 6(a). Further, the crystallanity
of the P25 TiO
2
with and without annealing at 500
o
C were measured by XRD and
shown in Fig. 6(b). To increase the interconnection between TiO
2
particles, it was
annealed in the presence of TTIP solution at 150
o
C for 8 hr and 500
o
C for 30 min (Fig.
6(b)). It was found that there were no change XRD patterns of P25 TiO
2
before and
after annealing. This behavior suggests that the enhancement of the cell performance
17
is due to neither annealing nor addition of the TTIP precursor with P25 TiO
2
particles.
It may be due to the decomposition of organics originating from the TTIP on the TiO
2
surface after thermal treatment like the treatment of UV/O zone [8].
Finally, in order to develop high efficiency DSSC, the tuning of TiO
2
photo
electrode morphology towards optimization has been taken into account [24, 25]. To
reduce the light loss ascribed to the back scattering, double layer film with light
scattering particle has better performance. TiO
2
films were fabricated by mixing up of
nano-particles and large particles (300 nm) at a ratio of 7:3.Finally , the cell
performances were compared for different type of TiO
2
films such as : film contains
(1) only nano-particles, (2) first layer nano particles and second layer course particles
and (3) first layer nano particle and second layer mixture of both. The chart is as
showed in Fig. 7 (a). Since visible light can completely penetrate first on the
transparent film, it is wise to deposit the nanoparticles first on the conducting glass
followed by a second layer for light scattering. The back scattering is expected to be
suppressed in this structure. The cell fabricated using this double layer film as
working electrode achieved high efficiency of 4.20% and evidently improved the cell
performance which fabricated without using light scattering particles (Fig. 7 (b)).
18
4. Conclusions
A low temperature fabrication method for preparation of TiO
2
porous films on
conducting glass substrate with high current efficiency in the DSSC has been
developed. TiO
2
film with a molar ratio of 0.08 and a thickness around 17 µm
achieved the best cell efficiency. The EIS technique was employed to quantify the
charge transport resistance and electron lifetime. The charge transport resistance at the
TiO
2
/dye/electrolyte interface (R
ct2
) decreased as a function of the molar ratio of
TTIP/TiO
2
from 0.02 to 0.08, and the TiO
2
film prepared with molar ratio of 0.08 also
shows the longer electron lifetime. As the further increase of molar ratio, the surface
area and dye loading were decreased, resulting in the decrease of conversion
efficiency. As for the thickness effect, the smallest R
ct2
was associated with a TiO
2
thickness of 17 µm. In the Bode plot, when the thickness of TiO
2
increased from 17.2
to 48.2 µm, the characteristic frequency peaks were shifted to higher frequency and
the electron recombination was also increased.
Due to the decomposition of organics originating from the TTIP on the TiO
2
surface, the conversion efficiency increases gently with the annealing. Finally, adding
30% of larger TiO
2
particle into P25 TiO
2
as light scattering particles could obtain the
best J
SC
and cell conversion efficiency of 8.81 mA/cm
2
and 4.2 %, respectively.
19
Acknowledgement
This work was financially supported by the Academia Sinica, Taipei, Taiwan, the
Republic of China, under Grant AS-94-TP-A02. This work was also pratially
supported by the National Research Council of the Republic of China.
20
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[25] Z.S Wang, H. Kawauchi, T. Kashima, H. Arakawa. Co. Chem. Rev. 248 (2004)
1381.
23
List of Tables
Table 1 The BET data and cell performances of different TTIP/TiO
2
molar ratios in
the paste used for TiO
2
electrode preparation measured under 100 mW/cm
2
.
Table 2 Dye loading and cell performances of DSSCs based on different thickness of
TiO
2
electrodes.
24
Figure Captions
Figure 1. SEM images of TiO
2
electrodes prepared by different TTIP/TiO
2
molar
ratios (a) 0.08; (b) 0.20.
Figure 2. Electrochemical impedance spectra of DSSCs based on different TTIP/TiO
2
molar ratios measured at OCV, 100mW/cm
2
. (a) and (b) are Nyquist plots; (c) Bode
phase plots. The equivalent circuit used in the study was showed in the inset of (a).
Figure 3. (a) electron transport resistance; (b) capacitance and (c) time constant of
DSSCs based on different TTIP/TiO
2
molar ratios obtained from impedance measured
in the dark applied various forward biases.
Figure 4. Electrochemical impedance spectra of DSSCs based on various thickness of
TiO
2
electrodes measured at OCV, 100mW/cm
2
. (a) Nyquist plot; (b) Bode phase plot
and (c) the fitting data of capacitance and electron transport resistance.
Figure 5. Electrochemical impedance spectra of DSSC based on TTIP/TiO
2
molar
ratio of 0.08 and the TiO
2
thickness of 17.2 µm measured under 10, 60 and 100
mW/cm
2
, respectively. (a) Nyquist plot and (b) Bold phase plot.
25
Figure 6. (a) The variation of current density and cell conversion efficiency of DSSCs
based on the TiO
2
electrode treatment at 150
o
C for various hours. (b) The XRD
patterns of P25 TiO
2
with and without sintering at 500
o
C for 30 min and the TTIP
precursor sintering at 150
o
C for 12 hr and 150
o
C for 30 min, respectively.
Figure 7. (a) The sketch plots of different collocations TiO
2
films. (b) I-V curves of
DSSCs for various collocation of TiO
2
electrodes.
26
Table 1
TTIP/TiO
2
(molar ratio)
Surface area
a
( m
2
/g)
Pore size
a
(nm)
J
SC
(mA/cm
2
)
b
V
OC
(V)
b
FF
b q
b
(%)
0.02 48.4 11.8 3.58 0.746 0.67 1.80
0.04 47.8 11.2 5.73 0.792 0.72 3.25
0.08 46.7 11.0 6.08 0.770 0.70 3.28
0.20 36.8 6.9 1.33 0.622 0.63 0.52
a
: measured by ASAP;
b
: The thickness of TiO
2
films were about 9 µm.
Table 2
Thickness of
TiO
2
(µm)
Dye loading
(10
-7
mole/cm
2
)
J
SC
(mA/cm
2
)
V
OC
(V)
FF
q
(%)
6.3 0.81 4.82 0.780 0.73 2.74
17.2 1.20 7.44 0.760 0.67 3.69
23.7 1.52 7.01 0.719 0.63 3.17
48.2 2.13 2.22 0.662 0.76 1.12
27
Fig. 1.
TTIP/TiO
2
= 0.20
(b)
TTIP/TiO
2
= 0.08
(a)
28
Fig. 2.
0 200 400 600
0
50
100
150
200
250
300
(a)
-
Z
'
'
(
o
h
m
)
Z' (ohm)
TTIP/TiO
2
0.02
0.04
0.08
0.20
50 100 150
0
25
50
75
(b)
-
Z
'
'
(
o
h
m
)
Z' (ohm)
TTIP/TiO
2
0.02
0.04
0.08
0.20
Z
w
CPE CPE
R
ct2
R
ct1
R
s
29
Fig. 2.
0.01 0.1 1 10 100 1000 10000
0
-20
-40
-60
(c)
TTIP/TiO
2
0.02
0.04
0.08
0.20
T
h
e
t
a
(
d
e
g
)
Frequency (Hz)
30
Fig. 3.
-0.60 -0.65 -0.70 -0.75 -0.80 -0.85
1E-5
1E-4
1E-3
0.01
(b)
TTIP/TiO
2
0.02
0.04
0.08
0.20
C

(
F
)
Bias (V)
-0.60 -0.65 -0.70 -0.75 -0.80 -0.85
10
100
1000
(a)
TTIP/TiO
2
0.02
0.04
0.08
0.20
R
e
s
i
s
t
a
n
c
e
(
o
h
m
)
Bias (V)
31
Fig. 3.
-0.60 -0.65 -0.70 -0.75 -0.80 -0.85
0.1
(c)
TTIP/TiO
2
0.02
0.04
0.08
0.20

n
(
s
)
Bias (V)
32
Fig. 4.
20 40 60 80 100
0
10
20
30
40
50
(a)
-
Z
"
(
o
h
m
)
Z'(ohm)
6.3 µm
17.2 µm
23.7 µm
48.2 µm
0.01 0.1 1 10 100 1000 10000 100000
0
-10
-20
-30
(b)
6.3 µm
17.2 µm
23.7 µm
48.2 µm
T
h
e
t
a
(
d
e
g
)
Frequency (Hz)
33
Fig. 4.
0 10 20 30 40 50
0
200
400
600
800
(c)
Capacitance
C
a
p
a
c
i
t
a
n
c
e
(

F
)
Thickness of TiO
2
film (m)
0
50
100
150
200
250
Resistance
R
e
s
i
s
t
a
n
c
e
(
o
h
m
)
34
Fig. 5.
0.01 0.1 1 10 100 1000 10000
0
-10
-20
-30
-40
-50
-60
(b)
10 mW/cm
2
60 mW/cm
2
100 mW/cm
2
T
h
e
t
a
(
d
e
g
)
Frequency (Hz)
0 50 100 150 200 250
0
40
80
120
(a)
-
Z
"
(
o
h
m
)
Z' (ohm)
10 mW/cm
2
60 mW/cm
2
100 mW/cm
2
35
(a)
(b)
Fig. 6.
0 2 4 6 8 10 12
2
3
4
5
6
7
8
9
10
q
J
SC
C
u
r
r
e
n
t
d
e
n
s
i
t
y
(
m
A
/
c
m
2
)
,

(
%
)
Annealing time (hour)
20 30 40 50 60
0
200
400
600
800
1000
1200
P25 - No sintering
P25 - 500
o
C
TTIP - 150
o
C for 12 hr
TTIP - 150
o
C for 30 min
I
n
t
e
n
s
i
t
y
(
a
.
u
.
)
2 Theta degree
36
(a)
(b)
Fig. 7.
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
0
2
4
6
8
10
12
14
C
u
r
r
e
n
t
d
e
n
s
i
t
y
(
m
A
/
c
m
2
)
Voltage (V)
A
AA
AB
A
A
A
FTO glass FTO glass FTO glass
A AA AB
A
B

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