Comparison of Plastic Based Counter Electrodes for Dye

Sensitized Solar Cells

Ghufran Hashmi, Kati Miettunen, Janne Halme, Imran Asghar, Henri Vahlman, Tapio
Saukkonen, Zhu Huaijin and Peter Lund
J. Electrochem. Soc. 2012, Volume 159, Issue 7, Pages H656-H661.
doi: 10.1149/2.059207jes
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2012 The Electrochemical Society

H656

Journal of The Electrochemical Society, 159 (7) H656-H661 (2012)

0013-4651/2012/159(7)/H656/6/$28.00 The Electrochemical Society

Comparison of Plastic Based Counter Electrodes

for Dye Sensitized Solar Cells
Ghufran Hashmi,a,z Kati Miettunen,a,z Janne Halme,a Imran Asghar,a Henri Vahlman,a
Tapio Saukkonen,b Zhu Huaijin,c and Peter Lunda
a New Energy Technologies Group, Department of Applied Physics, Aalto University, FIN-00076 Aalto,
b Engineering Materials Group, Department of Engineering Design and Production, Aalto University,

Finland

FIN-00076 Aalto, Finland

of Materials Science and Engineering, Chongqing University, Chongqing 400045, China

c College

The characteristics of different types of catalyst layers based on Pt, polymer and carbon for flexible dye sensitized solar cells
(DSSC) are investigated. These counter electrodes prepared at low temperature on indium doped tin oxide polyethyleneterephtalate
(ITO-PET) plastic are compared with high temperature treated platinum and carbon catalyst layers on fluorine doped tin oxide
(FTO) coated glass substrates. Here the electrical characteristics of the counter electrode and their optical performance are evaluated
in order to compare their suitability for direct and reverse illumination. The morphology of the catalyst layers to the substrate is
also investigated. Among the studied materials, the chemically platinized and carbon gel based counter electrodes demonstrated the
highest potential for flexible DSSC.
2012 The Electrochemical Society. [DOI: 10.1149/2.059207jes] All rights reserved.
Manuscript submitted March 9, 2012; revised manuscript received April 12, 2012. Published July 17, 2012.

Dye sensitized solar cells (DSSC) prepared using low cost materials and easy manufacturing methods are an interesting alternative to
current pn-junction solar cells. It has been proposed that further cost
reductions could be achieved by using flexible substrates which enable roll-to-roll mass production.13 The flexible DSSCs can be made
by using plastic substrates47 or combination of a metal and a plastic
substrate.811 As the preparation of high performance photoelectrodes
at low temperature has proven to be challenging, the use of metal at
the photoelectrode has become a common approach.811 In that case
the cell is illuminated from the counter electrode side which causes
additional optical losses.12 In fact, the highest flexible DSSC efficiency (8.6%) has been reached by using a metal as a photoelectrode
substrate.13 Recently, good stability results have also been reported
with Inconel alloy and titanium based photoelectrodes.14
In the literature several methods have been introduced for the
preparation of counter electrodes at low temperature.9,11,13,15,16 Quite
often the characteristics of the counter electrode have not, however,
been studied separately and their performance shows only in the current voltage (I-V) curve of the complete DSSC. As the photoelectrode
of the cells is different in the different studies and as the photoelectrodes have a significant effect on solar cell efficiency it does not
suffice to judge the counter electrodes merely on the best overall
efficiency.
The overall goal is to find best plastic based counter electrodes to be
used with plastic photoelectrode (direct illumination) and metal photoelectrode (indirect illumination). For this purpose different plastic
CEs were tested in this work under similar preparation and measurement conditions. Many of the tested methods to prepare a catalyst
layer on plastics such as chemical platinization,13 electrochemical
platinization11 and spin-coated PEDOT-TsO9 have been demonstrated
in the studies of DSSCs with metal photoelectrodes. Additionally
completely opaque carbon gel catalyst layers16 were also examined.
The plastic electrodes are compared to FTO-glass based counter electrodes with thermal platinization and with high temperature sintered
carbon prepared using commercial paste. In addition to electrical performance, also the optical characteristics were investigated.
Experimental Methods
Counter electrodes. The counter electrode catalyst layers were
deposited on ITO-PET substrates (sheet resistance 60 /sq., Bekaert).
The reference glass counter electrode and samples for scanning electron microscopy (SEM) imaging were prepared on FTO glass substrates (15 /sq.).
z

E-mail: ghufran.hashmi@aalto.fi; kati.miettunen@aalto.fi

Chemical platinization.ITO-PET plastics cannot endure chemical

treatment as well as FTO-glass; some chemical treatments that have
given very good results with FTO-glass such as.17 In our test, the acids
used in the treatment, however, dissolved the conducting ITO layer
when it was applied for ITO-PET substrates. Hence other acid free
methods were examined. A chemical platinization method that had
previously been employed for plastic counter electrodes which were
used with metal based photoelectrodes was tested:13 40 mM H2 PtCl6 in
2-propanol was spread on the substrate. A previously noted issue with
this type of method has been the uneven distribution of the catalyst.9
Here it was found that this problem could be alleviated with UV-O3
treatment of the substrates (10 min) before applying the Pt solution.
After the spreading of the solution, counter electrodes were dried at
130 C as instructed in the literature.13 It was noted that the heating
time could be reduced from 2 h to 30 min without any changes to the
performance of the catalyst layer. The electrodes were then dipped to
50 mM NaBH4 in H2 O and ethanol mixture with 8:2 ratio followed
by rinsing and drying at 130 C.13 The heating time was again reduced
to 30 min.
Electrochemical platinization.In the electrochemical platinization
the substrate to be coated is placed in 5 mM H2 PtCl6 in H2 O solution
with a ready Pt catalyst layer (here a FTO glass with thick sputtered
Pt layer).11 The two substrates were placed 4 mm apart and voltage
of 1.8 V was applied for 30 s. The deposition time used here was
doubled compared to11 in order to improve charge transfer resistance
to sufficient level. After treatment the electrodes were placed on the
hot plate for 15 min at 150 C.
Spin coating of PEDOT-TsO.For the spin coating we used 0.5 wt%
PEDOT-TsO dispersion in nitromethane (Sigma-Aldrich). The catalyst film consisted of three layers deposited using a PWM32 spinner
(Headway Research Inc.) with speed 700 RPM for 1 min for each
layer.9
Carbon Gel.The carbon gel paste was obtained as in16 by grinding 0.4 g of Sb:SnO2 (Zelec ECP 3010-XC, Milliken chemicals)
1.6 g of graphite powder (synthetic, conducting grade, 325 mesh,
Alfa Aesar), 0.4 g of carbon black (Printex XE2, Degussa), and 3 g
of 3-methoxypropionitrile (3-MePRN) (Alfa Aesar) for 20 minutes
in the mortar. After that 0.2 g of gelator poly(vinylidenefluoride-cohexafluoropropylene) (PVdF-HFP) and 9 g of 3-methoxypropionitrile
(3-MePRN) was added in the mixture. Gelation of the (PVdF-HFP)
was performed by heating the paste at 130 C for 16 h.16 The ready
carbon gel paste was applied to the substrate by doctor blading it
through a tape mask.16 The individual layer was heated in mild temperature and then pressed to adhere it.16 3 layers were prepared on
each substrate giving a thickness of about 10 m for the catalyst
layer.

Journal of The Electrochemical Society, 159 (7) H656-H661 (2012)

High temperature platinization on glass.For the high temperature
Pt counter electrodes that were employed as a reference, we used
5 mM H2 PtCl6 in 2-propanol. 4 L was deposited on each substrate
and then the electrodes were fired at 385 C for 15 min.
High temperature carbon on glass.We additionally tested a commercial carbon paste (Elcocarb C/SP, Solaronix). One layer of the
paste was doctor bladed via a tape mask. The film was then fired at
450 C for 30 min as instructed by the manufacturer. The resulting
thickness was 20 m.
Cell assembly. The photoelectrodes consisted of a screen printed
TiO2 film deposited on fluorine-doped tin oxide (FTO) coated glass
substrates. In the printing, commercial TiO2 paste (Dyesol TiO2
18NR-T Dyesol) was employed. Three layers were deposited and
after that the electrodes were sintered at 450 C for 30 min. The resulting 13 m thick TiO2 films (area 0.4 cm2 ) were sensitized using a
dye solution consisting of 0.32 mM cis-bis (isothiocyanato) bis(2,2 bipyridyl-4,4 -dicarboxylato)-ruthenium(II) bis-tetrabutylammonium
(Dyesol) in ethanol (99.5 wt-%) for 16 h. The counter electrodes
were heated for a couple of hours at 110 C before the cell assembly.
The electrodes were sealed with a 25 m thick Surlyn ionomer resin
film spacer (DuPont) for all the cases except for the high temperature
carbon layers in which case two polymer spacer foils were used to facilitate enough space between the electrodes. Commercial electrolyte
(HSE-EL, DyeSol) was inserted through filling channels drilled in the
photoelectrode substrate. The filling holes were sealed with a Surlyn
polymer foil and a thin cover glass.
Measurements. Current-voltage (I-V) curves were recorded using a Keithley 2420 Source meter with light intensity equivalent to 1
Sun (1000 W/m2 ) at 25 C. Electrochemical impedance spectroscopy
(EIS) was carried out with the Zahner-Elektrik IM6 potentiostat using the same lighting setup as in IV measurements at open circuit.
The studied frequency range was from 100 mHz to 100 KHz and the
amplitude 10 mV. Incident-photon-to-collected-electron (IPCE) measurements were performed from both PE and CE sides of the solar cells
with Spectral Response/QE/IPCE (model QEX7, PV measurements
Inc) measurement system within a wavelength range of 300800 nm.

H657

Spectral transmittance (T) of the counter electrodes was measured

also with the IPCE system over wavelengths range of 3001000 nm.
Results and Discussion
Morphology of the catalyst layers. Figure 1a-1h illustrates SEM
images of the different counter electrodes described in Experimental Methods. For these SEM images all the catalyst layers were deposited on FTO glass as plastic substrates do not suit well to SEM
imaging. Figure 1a represents glass substrate coated with large sized
(50200 nm) crystalline shaped FTO particles. The commonly used
thermal platinization introduces very small sized (<5 nm) Pt particles
rather evenly across the surface of FTO glass (Figure 1b). As the Pt
particles are very small, the FTO layer is dominating the appearance
of the thermally platinized counter electrode (Figure 1b).
The electrochemical platinized catalyst layer (Figure 1c) has significantly larger Pt particle size (up to 50 nm) compared to the thermal
platinization. The Pt layer was very similar all across the electrode. In
contrast, the chemically platinized layer had quite a lot spatial variation across the electrode and Figure 1d represents a medium Pt layer
thickness. The typical Pt particle size for the chemical platinization
ranged between 2040 nm (Figure 1d). There were also some larger
clusters of Pt nanoparticles of about 200 nm.
In the case of PEDOT CE, a non-uniform thin layer of polymer
was seen in the SEM images (Figures 1e and 1f). Figure 1f shows how
certain areas are uncovered by the polymer and the gaps in the polymer
coating are in the range of 14 m. These gaps (i.e. catalytically in
active areas) are still smaller compared to the general dimensions of
the cell e.g. the thickness of the porous TiO2 layer and thus they should
not significantly hinder the performance of the cell.
In the case of carbon layers (Figures 1g and 1h) their features were
in a larger scale compared the Pt and PEDOT samples (Figures 1a-1f).
In the case of the high temperature carbon catalyst layer, the graphite
particles (about 2 m) form a porous multi layer. The plastic carbon
gel catalyst layer has large cluster size (about 3 m) but those are
actually highly porous as they consist of nanoparticles (50 nm) and
graphite crystals. Due to the high porosity of the carbon gel layers, they
appear to have a higher surface area compared to the high temperature
glass carbon catalyst layers.

Figure 1. SEM image of a) Bare FTO Glass substrate and FTO glass substrate with b) thermal platinum, c) electrochemical Pt, d) chemical Pt, e) PEDOT-TsO
(close up), f) PEDOT-TsO, g) HT carbon paste, and h) plastic carbon gel.

H658

Journal of The Electrochemical Society, 159 (7) H656-H661 (2012)

Table I. Average VOC , JSC , FF, efficiency, Rcell , and their standard deviations of all the different cell types with PE and CE illumination.
JSC (mA/cm2 )

VOC (mV)

FF (%)

(%)

Rcell ()

PE illumination
Chemical Platinization
Electrochemical Platinization
PEDOT TsO
Carbon Gel
Glass Platinum
Glass Carbon (Solaronix)

11.7 0.7
12 1
9.4 0.4
11.3 0.1
11.7 0.1
11.4 0.5

675 8
668 12
651 9
669 5
671 13
673 15

54 3
42.6 0.3
55 5
47.3 0.8
65 1
49 3

4.3 1
3.4 0.2
3.35 0.08
3.57 0.07
5.1 0.2
3.7 0.3

18 2
28 7
21 10
24 4
11 2
40 40

CE illumination
Chemical Platinization
Electrochemical Platinization
PEDOT TsO
Carbon Gel
Glass Platinum
Glass Carbon (Solaronix)

81
7.9 0.3
5.6 0.1
0.94 0.01
8.91 0.3
1.0 0.1

649 3
645 12
624 9
554 2
650 4
565 6

60 3
52 2
63 2
71 11
67 1
66.0 0.6

3.1 0.3
2.64 0.08
2.2 0.1
0.37 0.05
3.9 0.4
0.35 0.04

20 2
28 4
23 9
84 10
12 3
76 11

Type of cell

Photovoltaic performance. The photovoltaic parameters of the

cells measured from both the photoelectrode (PE) and counter electrode (CE) side are listed in Table I and typical I-V curves are shown
in Figure S1 (supporting information18 ). The former case (PE illumination) represent the normal cell setup while the latter (CE illumination) relates to the case where the photoelectrode substrate is
non-transparent e.g. metal. The short circuit current density JSC and
open circuit voltage VOC from the PE side are almost 12 mA/cm2 and
670 mV respectively in all the cells except PEDOT-TsO ones. The
PEDOT-TsO based CEs exhibited repeatedly over 20% lower photocurrents (9.4 mA) although the same type of PE were fabricated
for all the cells. Apparently the PEDOT-TsO counter electrode has
affected the performance of the PE in this case and this is investigated
more later on in Optical characteristics. Low photocurrents have been
reported with PEDOT films in comparison with Pt films also earlier.9,19
There are also some studies which showed similar photocurrent from
cells with PEDOT-TsO and Pt.20,21
Among the flexible counter electrodes in the case of CE illumination, the highest JSC values of about 8 mA/cm2 were achieved with
the chemical and electrochemical platinized catalyst layers (Table I).
These CE side JSC values are lower compared to PE illumination. This
is mainly caused by the additional optical losses such as absorption
in the catalyst and the bulk electrolyte layers. The electrolyte used
here had a high tri-iodide concentration and thus JSC measured from
the CE side could probably be enhanced by adjusting the layer thickness of electrolyte and optimizing the tri-iodide concentration, but
that is out of scope of this contribution. In Optical characteristics in
which the optical characteristics of the electrodes are investigated, it
is determined how largely the difference in the transmittance explain
the differences in the JSC values in the case of semi-transparent electrodes. The photocurrents in the case of the opaque carbon catalyst
layers with CE illumination are very small and such catalyst layers
are practically suitable only for the PE side illumination.

The differences in the catalytic performance of the counter electrodes affect mainly series connected resistances (Rcell ), the fill factor
(FF) and the efficiency (). The Rcell is a combination of all series connected resistances in the cell (i.e. the sheet resistance of the
substrates, resistivity of electrical contacts and electrolytes, charge
transfer resistance at the counter electrode and Nernst diffusion of
the electrolyte) and ideality of the photoelectrode. The approximate
value of Rcell can be determined from the slope of the IV curves at
open-circuit condition. Most of the factors affecting Rcell except for
the charge transfer resistance at the counter electrode and the sheet
resistance at the counter electrode should be the similar due to similar
materials and preparation. Thus the changes in Rcell should mainly
reflect changes at the counter electrode. The Rcell values give rough
indication of which counter electrodes work well but for a more detailed and quantitative analysis of the resistances, electrochemical
impedance analysis needed and that it is presented in Resistance at
the counter electrode/electrolyte surface.
The initial photovoltaic data shows that the chemical platinized
electrodes resulted in the highest efficiency among the plastic CEs
with both PE (4.3%) and CE illumination (3.1%). The carbon gel
counter electrodes are a good alternative among alternative catalyst
material when used with PE illumination. We envision that the low
temperature carbon electrodes could have even more potential as with
further development they might become conductive enough to transfer the current effectively also in lateral dimension so to omit the
expensive TCO layer from the CE side. Very thick (60 m) high temperature carbon counter electrodes have already been demonstrated to
be sufficiently conductive to be used even without a TCO layer.22
Optical characteristics. Figure 2a shows the transmittance data
of different semi-transparent counter electrodes. Both electrochemical
platinized and PEDOT-TsO counter electrodes exhibited lower transmittance (70%) in comparison with chemical platinized (75%) plastics

Figure 2. a) Transmittance of different kinds of

semi-transparent CEs. b) Jsc of different CE vs
transmittance at 500 nm. The trend line in b is
a linear fit between origin and glass Pt cell to
show how increased transmittance should affect
JSC .

Journal of The Electrochemical Society, 159 (7) H656-H661 (2012)

and thermal platinized (80%) glass at 550 nm. The optical characteristics are in accordance with the SEM images as those showed higher
coverage and/or particle size of the catalysts (Figure 1) for the counter
electrodes which have lower transmittance (Figure 2a). Additionally
Figure 2 reveals that the plain ITO-PET electrodes have higher transparency (90% at 550 nm) compared to the FTO-glass (85% at 550 nm).
Hence it can be said that from optical perspective the chemical platinized CEs are the best of the studied choices for CE side illumination.
Next we evaluated how the differences in the transmittance
(Figure 2a) explain the differences in the measured JSC values with
CE illumination (Table I). There is a linear relation between TCE and
JSC in the CE side in the wavelength region that DSSCs here use (See
supporting information section S2).18 When plotting the measured
TCE values against JSC (Figure 2b), we find that the differences in JSC
except for the PEDOT-TsO can be interpreted through the optical differences. Thus in the case of PEDOT-TsO some other factors such as
electron injection, regeneration or collection efficiencies are limiting
JSC . The counter electrode catalyst could affect such characteristics
of the photoelectrode for instance if PEDOT-TsO was dissolved in
the electrolyte and via the electrolyte diffused to the photoelectrode.
At the photoelectrode, the catalyst particles would increase current
leakage which would result in losses in electron collection.
Quantum efficiency. Partial quantum efficiencies, i.e. light harvesting (LH ), electron injection (INJ ), charge collection (COL ) and
regeneration (REG ) efficiency, define the total incident photon to collected electron efficiency (IPCE ) as
IPCE () =

JSC ()
= L H () I N J ()C O L () R E G ()
q()

(1)

in which () is the photon flux at a given wavelength and q is the

elementary charge. Figures S3a and S3b in supporting section S318
represent the average IPCE data of the cells with different types of CE
from PE and CE side respectively.
In general large electron collection losses can result in redshift of
the peak of IPCE spectrum measured with CE side illumination.23
The light harvesting efficiency LH() is assumed to be quite similar
since all the cells had similar photoelectrodes (thickness 12 m).
Moreover, no peak shifts in the CE side IPCE measurements were
observed (Figure S3b, supporting information18 ), except perhaps for
the PEDOT-TsO cells for which it is difficult to evaluate the peak position. Thus for all cells except for PEDOT-TsO ones, the recombination
appears to be very similar to Glass-Pt cells.
To further investigate the difference between the PEDOT-TsO and
other cells, the IPCE ratio of the PEDOT-TsO and electrochemically platinized cells was calculated (Figure 3). It was observed
that the IPCE ratio (i.e. IPCE,CE divided by IPCE,PE ) for PEDOT-TsO
cells was significantly smaller than for the other types, for instance
cells for the electrochemical platinized counter electrode. Those two
cells had similar substrates, photoelectrode and electrolyte. Based on

Figure 3. IPCE ratios of CEs.

H659

Table II. Typical RCE,TOT , and RS values of all the different

cell types taken at OC under illumination. RCE total includes the
charge transfer resistance as well as the possible in-pore diffusion
resistances and/or interfacial resistances at the counter electrode.
The relative error for RCE,TOT was estimated to be 15% based
on the average relative error of three chemical platinized samples
(14%) and three glass platinized samples (16%).

CE
Chemical Pt
E. chemical Pt
Plastic C
PEDOT
Glass-C
Glass Pt

RS
(cm2 )

RCE,TOT
(cm2 )

(TPT )
at 550 nm

-RCE ln
(TPT )

11
13
10
16
4.1
4.6

3.7
12
11
5.8
17
2.6

0.86
0.77

0.55
3.13

0.98

0.05

Figure 2a, electrochemical Pt had the same TCE above 600 nm than the
PEDOT-TsO CEs. Hence, we can conclude that the lower IPCE-ratio
(above 600 nm) with the PEDOT-TsO than with the electrochemical platinization CE is solely due to lower COL , meaning a shorter
electron diffusion length in the PEDOT-TsO cells than in the electrochemical Pt cells. Note that the electrochemical Pt cells are good
representatives of the normal PE performance, since they are giving
similar performance (IPCE) as the glass Pt cells (Figure S3, supporting information).18 The most likely reason for the shorter diffusion
length in the PEDOT-TsO cells is, as already mentioned in the paper,
faster electron recombination due to residues of PEDOT-TsO dissolving/detaching from the CE and depositing on the PE.
Resistance at the counter electrode/electrolyte interface.
Figure 4 represents the typical electrochemical impedance spectra
of complete DSSCs with each type CEs. The measurements were
carried out under illumination (1 Sun) at VOC conditions. As the
current through cells is zero, the voltage over the counter electrodes
is also zero (i.e. the same in all the cells) and thus their performance
can be directly compared. (Note that there is some variation in VOC
meaning that the photoelectrodes are not similarly polarized and thus
their performance cannot be quantitatively compared based on this
data). Typical equivalent circuit24 was used for fitting the EIS data
which describes the different impedances of DSSC.25
The cells with ITO-PET based counter electrode have 23 times
larger RS values (10 cm2 ) than the FTO-glass based cells
(4.6 cm2 ) which are apparently due to the 4-times higher sheet resistance (Table II). The series resistance of the carbon based counter electrodes is slightly smaller compared to the other counter electrodes on
the same substrate: the plastic carbon CE has smaller series resistance
(10 cm2 ) with respect to the chemical (11 cm2 ) and electrochemical platinized CEs (13 cm2 ). Evidently the carbon gel catalyst layer
has a relatively high conductivity so that it can act as a significant additional current pathway (c.f. parallel connected sheet resistor) with
ITO layer and thus results in decrease in the overall sheet resistance
of the electrode. The series resistance of glass-carbon electrode based
DSSC (4.1 cm2 ) is, however, only fractionally smaller compared to
the reference glass-Pt DSSC (4.6 cm2 ). This may be either because
the lateral conductivity of the high temperature carbon is really not
that good or alternatively as the sheet resistance of FTO is much better
compared to ITO, the effect of the additional current pathway does
not simply show that well.
The width of the high frequency semicircles (the one left in
Figure 4a) for instance in the case of chemical platinized CE or glass
platinized CE is associated with the charge transfer resistance RCE
at the counter electrode. Both chemical platinized and PEDOT-TsO
counter electrodes exhibit relatively low RCE (3.7 cm2 and 2.8 cm2
respectively) and their catalytic performance is not far from that of
the platinized glass (2.6 cm2 ). This suggests that in these three cases
the variation in FF and Rcell in Table I was apparently mostly due to

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Journal of The Electrochemical Society, 159 (7) H656-H661 (2012)

Figure 4. Typical EIS response of the DSSCs measured at VOC under illumination represented as a) Nyquist plot, as b) imaginary impedance Z and c) real
impedance Z as a function of frequency f. All solid lines correspond to the fitted data where as the points represent the measured data.

variation in the RS as suggested earlier. The glass-Pt CE and chemical

platinized having low charge transfer resistances exhibit the highest
efficiencies (5.1% and 4.3% respectively). However the lowest efficiency was recorded with the PEDOT based CE.
The analysis of the porous carbon electrodes is not as straight
forward as in that case the response is at the same frequencies with
the photoelectrode response i.e. they overlap. Therefore the low frequency semicircle (the one on left in Figure 4a) is a combination of the
charge transfer resistance RCE at the carbon gel counter electrode and
the recombination resistance at the photoelectrode RPE (7.3 cm2 ).16
We estimated RCE (3.8 cm2 ) since the PEs of each type of cell is assumed to be identical and having similar VOC : we can subtract the RPE
(3.5 cm2 ) of reference glass-Pt based DSSC from combined resistance of the glass carbon based 7 cm2 .16 In the case of both carbon
electrode there is also semi-circle at high frequencies. This may be
related to interfacial resistances e.g. the substrate/catalyst interface.
Another interpretation for the high frequency resistances is that they
are related to in-pore diffusion at the porous carbon electrode.19 These
resistances increase the resistance at the counter electrode even further
and are therefore added to the total charge transfer resistance values of
the counter electrode RCE,TOT values. Thus RCE,TOT in case of carbon
plastic and carbon glass are 10.8 cm2 and 17 cm2 respectively.
The better performance of the carbon gel layer compared to the high
temperature one is likely related to the apparent larger surface area
of the latter one as seen in the SEM analysis (see Morphology of the
catalyst layers).
Another key question is that among chemical, electrochemical and
thermal platinization methods there might be different amount of Pt
deposited on the substrate which would have an effect on the RCE
but also on the transmittance of the film. The idea in the following
is to determine basically how effectively the catalyst is used, using
transmittance of the film as a measure of the effective thickness of
the Pt film and normalizing RCE data with respect to this thickness,

assuming that the Pt layer behaves electrochemically like a thin porous

electrode.
We can express these relations with the following equations:
RC E = rC E d P1T

(2)

TPt = e Pt d Pt

(3)

rC E Pt = RC E ln(TPt )

(4)

where rC E is the charge transfer resistance per unit thickness, dPt is the
thickness of the platinum layer, TPt is the transmittance of platinum
layer and Pt is the absorbance of Pt (which is assumed to be constant
for all layers). Note that equation (4) is independent of the thickness
and reveals that the charge transfer resistance of the different Pt layers normalized for their amount (rC E ) can be compared in terms of a
figure of merit determined by the measured RCE and TPt : -RCE ln(TPt ).
These figure of merit values of the Pt utilization for different platinized
deposition methods are presented in Table II and reveals that the electrochemical platinization method may consume large amount of Pt
and still exhibit high charge transfer resistance (i.e. is not very economic) in the comparison with chemical and reference glass platinum
counter electrodes. These results are in good correspondence with the
morphology analysis: The reference glass counter electrode has small
Pt particles that absorb very little light (Figures 1 and 2). In contrast,
the electrochemical Pt layer is formed of larger particles, which do
not increase the surface area of the catalyst (i.e. the catalytic activity) much but do increase the optical losses (Figures 1 and 2). These
results thus represent a good agreement between morphological, optical and electrochemical properties of the plastic based Pt counter
electrodes and demonstrate the importance of small catalyst particle

Journal of The Electrochemical Society, 159 (7) H656-H661 (2012)

size, which is a well known design criterion for electrocatalyst in
general.
Conclusions
The purpose of these experiments was to perform a systematic
comparison of different counter electrode catalyst materials prepared
at low-temperature and deposition methods in order to find the most
suitable alternative for a semitransparent CE. The results were analyzed and discussed from the point of view of two alternative configurations: reverse illuminated metal based flexible DSSCs and front
illuminated ITO-plastic based flexible DSSCs. The best performance
was reached with chemical platinization in the case of both front and
reverse illumination.
The adhesion of catalyst in the case of PEDOT-TsO appeared to
be a problem: based on the increased collection losses at the photoelectrode in the case of cells with PEDOT-TsO, it seems apparent
that some of the PEDOT-TsO catalyst had indeed detached from the
counter electrode and diffused to the photoelectrode. There were no
such problems in the case of other tested counter electrodes. Based
on these results getting good adhesion with PEDOT-TsO is not trivial
and this needs to be focused on when working with these kinds of
films.
The carbon gel catalyst layer showed relatively good catalytic
activity, and interestingly, they worked much better than the commercial paste on FTO glass that required high temperature treatment
giving 20% higher overall cell efficiency. The carbon gel may be an
interesting low cost roll to roll applicable options to be used with
plastic based photoelectrodes but its charge transfer resistance needs
to be improved (lowered) by a factor of 3 to be compatible to the
chemical platinization method and by a factor of 4 to match thermal Pt on FTO-glass substrates compared at the same preparation
conditions.
Acknowledgments
This study was funded by the Academy of Finland and the National
Nature Science Foundation of China (Grant no. 50711130638). G.H
and K.M are thankful to Academy of Finland for the grant.

H661

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Supporting information [Ref 18]

Section S1. Typical IV data of Different CEs

Figure S1. Typical I-V of the cells measured with PE illumination.

Section S2. Relation between JSC and TCE

When illuminating from the CE, the JSC is directly proportional to the transmittance. This
can be derived mathematically starting from the partial efficiencies in the incident photon
to collected electron equation:
(1)
Where qC is the electron charge, INJ is the electron injection efficiency, REG is the dye
regeneration efficiency, COL is the electron collection efficiency, LH() is the light
harvesting efficiency and () is the light intensity at given wavelength. The light
harvesting efficiency from the CE side can be written as
(2)
Where TCE is the transmittance of counter electrode, TEL is the transmittance of the
electrolyte, (1-e-()d) is the absorption by the dye at the photoelectrode (PE) and (1RPE()) is the reflectance of the PE. Therefore the JSC can be further transformed
(3)

As Figure 2a shows, the transmittance of the counter electrodes does not vary much in the
wavelengths above 400 nm. Thus in the spectral region that DSCs use, the transmittance
at the CE can be assumed independent of wavelength giving the linear relation between
JSC and TCE
(4)

Section S3.

Figure S3. Typical IPCE data of the cells (a) measured with PE and (b) measured with CE illumination.