Solar Energy Materials & Solar Cells 105 (2012) 148–152

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Solar Energy Materials & Solar Cells

journal homepage: www.elsevier.com/locate/solmat

Monolithic all-solid-state dye-sensitized solar module based on mesoscopic

carbon counter electrodes
Yaoguang Rong, Xiong Li, Zhiliang Ku, Guanghui Liu, Heng Wang, Mi Xu, Linfeng Liu,
Min Hu, Peng Xiang, Ziming Zhou, Ting Shu, Hongwei Han n
Michael Grätzel Center for Mesoscopic Solar Cells, Wuhan National Laboratory for Optoelectronics, Huazhong University of Science and Technology, Wuhan, Hubei 430074, PR China

a r t i c l e i n f o a b s t r a c t

Article history: A monolithic all-solid-state dye-sensitized solar cell (DSSC) module based on mesoscopic carbon
Received 21 February 2012 counter electrodes with high stability has been developed, which offers a promising prospect for
Received in revised form commercial applications. Based on the design of a triple layer structure, all the layers are constructed
21 April 2012
on a single conducting glass substrate by screen-printing. A typical monolithic all-solid-state DSSC
Accepted 3 June 2012
Available online 27 June 2012
module, which consists of five series-interconnected unit cells, shows an overall energy conversion
efficiency of 2.57% and a maximum output of 156.9 mW. In the case of applying a solid-state polymer
Keywords: electrolyte, we have developed a novel sealing method for all-solid-state DSSCs. Endurance tests were
Dye-sensitized solar cell carried out to investigate the stability of the module under a hot and high humidity environment
All-solid-state
(60 1C, 85% RH) and heat and cool cycle stress ( 10 and 60 1C), which indicated that the sealing method
Monolithic
improved the stability of the module effectively.
Module
Sealing Crown Copyright & 2012 Published by Elsevier B.V. All rights reserved.
Stability

1. Introduction over 2500 h, which corresponds to around 3 years of outdoor

Growing attention has been concentrated on the utilization of
renewable energies such as photovoltaics in order to deal with
the problems of energy crisis and global warming. Since Professor
M. Grätzel made a breakthrough in 1991 [1], dye-sensitized solar
cells (DSSCs) have been expected to be a potential candidate of
the next-generation solar cells with multiple advantages in
production cost, energy consumption, color choices and transpar-
ency [2,3]. In the past decade, many researchers have focused on
the commercial upscaling of DSSCs, and various approaches in
enlarging the cell size have been attempted.
In 2005, Dai et al. designed and tested DSSC modules with an
overall efficiency of over 6% [4]. In 2009, an efficiency of 8.2% on a
submodule of DSSC with series connected configuration was
achieved by Han et al. [5]. During the same period, Kato et al.
reported a DSSC module for 2.5 years of outdoor tests [6]. Despite
the rather low efficiency, the work of Kato et al. is of major
importance for the technology since it shows its outdoor feasi-
bility. Subsequently, Pettersson et al. presented a parallel-con-
nected monolithic DSSC module with an efficiency of 3.9% and
performed a light-soaking test of the module at 1000 W m  2 for
n
Corresponding author. Tel./fax: þ 86 27 87793027.
E-mail address: hongwei.han@mail.hust.edu.cn (H. Han).
exposure [7].
Unfortunately, all these DSSC modules are based on liquid
electrolytes. It is well known that liquid electrolyte based DSSCs
always couple with leakage, dye desorption, complicated sealing
process and other problems, which block the further applications
of DSSCs. Replacing the liquid electrolyte by a solid-state medium
such as hole conductors and polymer electrolyte seems to be a
solution to these problems [8–10]. However, the counter electro-
des of conventional all-solid-state DSSCs were fabricated by
depositing noble metals such as gold or platinum on the solid-
state medium. Obviously, this counter electrode using high-cost
metals is still an issue for its wide application since the vacuum
deposition process is also highly energy consumptive.
Recently, we reported a novel design for monolithic all-solid-
state DSSCs with a carbon counter electrode [11]. This design
escapes from second conducting glass and noble metals used for
counter electrodes and has a simple fabrication process. However,
the characterization of large-sized monolithic all-solid-state
DSSCs with a carbon counter electrode is still unknown. The
manufacturing, reliability, performance and stability of a module
are complex due to its large size and thus increased risk of
defects. Herein we successfully fabricated a carbon counter
electrode based monolithic all-solid-state DSSC module with the
size 10 cm  10 cm, with simple and low-cost procedures entirely
based on screen-printing. Since there is no risk of leakage of the
electrolyte, the module becomes suitable for indoor applications,

0927-0248/$ - see front matter Crown Copyright & 2012 Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.solmat.2012.06.004
 Y. Rong et al. / Solar Energy Materials & Solar Cells 105 (2012) 148–152
Fig. 1. Structure of a monolithic all-solid-state DSSC module with five cells
connected in series, and an enlargement of the center of two adjacent cells
including the TiO2 working electrode (1), the spacer layer (2), the carbon counter
electrode (3), the silver current collectors (4), the solid-state polymer electrolyte
(5), the glass substrate (6), the EVA film (7), and the PET film (8).
and is even portable. Besides, we have developed a novel sealing
method for solid-state DSSCs. The stability of the module was
investigated, and the sealing method was proven to be reliable in
a highly humid environment. The solid-state polymer electrolyte
presents stability during an endurance test under the heat and
cool cycle stress ( 10 and 60 1C) for more than 200 cycles. It is
worth mentioning that, to the best of our knowledge, although
many works have focused on the optimization of solid-state
polymer electrolytes and their application to solar cells [12,13],
this is the first time a stable large-sized DSSC module with a solid-
state polymer electrolyte and carbon counter electrode has been
achieved.
2. Experiment
2.1. Fabrication of the module
Fig. 1 shows the structure of a typical monolithic all-solid-
state DSSC module. Five rectangular unit cells (12.22 cm2 active
TiO2 area/cell, i.e. 61.1 cm2 active TiO2 area/module) were fabri-
cated on a FTO glass (10 cm  10 cm, TEC-15, Pilkington, USA),
which were monolithically interconnected in series. Each cell
comprised a TiO2 layer, ZrO2 layer and carbon layer deposited on
the glass substrate, and thicknesses of the layers were approxi-
mately 8 mm (TiO2), 12 mm (ZrO2) and 60 mm (carbon). After pre-
treatment of the glass substrate, including the laser structuring of
the FTO layer and the washing of the glass, two silver grids were
screen-printed on the substrate to collect current, and the silver
paste was sintered at 50 1C for 30 min. Then the layers of TiO2,
ZrO2 and carbon counter electrode were subsequently screen-
printed on the glass substrate. The TiO2 paste was commercially
available from JGC Catalysts and Chemicals Ltd., Japan (PASOL
HPW-18NR). The ZrO2 paste and the platinized carbon paste were
prepared according to the procedures of Han et al. [11]. These
three layers were sintered separately; the TiO2 layer at 450 1C for
30 min, the ZrO2 layer at 500 1C for 30 min and the carbon layer at
149
400 1C for 30 min. After that the substrate was sensitized with N719
solution. Finally, a polymer electrolyte of the PEO/PVDF/LiI/I2
system was filled into the cells from the carbon layers by a vacuum
method as reported previously [14]. And then it was stored at 80 1C
for more than 24 h to remove all the remaining solvent. Generally, a
monolithic all-solid-state DSSC module based on five series-inter-
connected unit cells was fabricated.
2.2. Sealing and packaging
In order to prevent the module from moisture and oxygen, a
novel sealing process was developed. As primary sealing, a hot
melt film of 40 mm thickness made of ethylene vinyl acetate
copolymer (EVA) and a plastic film of 200 mm thickness made of
polyethylene terephthalate (PET) were applied on the back of the
module. The EVA serves as an adhesive and PET acts as a back
plate to cover the whole module. Then the module with EVA film
and PET film was processed for sealing by application of vacuum,
heating and compressing. Finally, the module was secondarily
packaged with a metallic frame and specific solar sealant. Fig. 2
shows images of the module with the front site (a), back site
(b) and a panel consisting of 20 present modules (c).
2.3. Endurance tests of the modules
Fabricated modules were subjected to two endurance tests.
To investigate the stability under a hot and high humidity
environment, modules were kept in a climatic and environmental
test chamber (Vötsch C4-180) at 60 1C and 85% RH static condition.
In order to clarify the influence of different temperatures on the
modules’ performance, modules were kept in the chamber with the
temperature alternating between  10 and 60 1C for a thermal
cycling test, and one cycle was completed in 3 h. The endurance
tests were conducted with the modules operating under open-
circuit condition. Photovoltaic property was measured at room
temperature.
2.4. Characterization and measurements
The surface appearance of mesoscopic carbon layer was studied
using a Sirion 200 field emission scanning electron microscope
(FE-SEM, Holland). Veeco Dektak 150 was used to detect the thick-
ness of each layer. The conductivity of the carbon layer was measured
by a four-point probe sheet resistance measurement (RTS-8,
Mydream Electronic, PR China). All presented module efficiencies
were calculated from the current–voltage (I–V) characteristics of the
Fig. 2. Images of the monolithic all-solid-state DSSC module with the front site
(a), back site (b) and a panel consisting of 20 modules (c).
150 Y. Rong et al. / Solar Energy Materials & Solar Cells 105 (2012) 148–152

modules. The I–V characteristic of the module was characterized by a

Keithley digital source meter (Model 2400) and a Newport Oriel
300 W Solar Simulator, giving light with simulated AM1.5 solar
illumination of 1000 W m  2.

3. Result and discussion

3.1. Microstructural characterization

Fig. 3 shows a scanning electron microscopy (SEM) image of

the carbon layer. Graphite flakes and carbon black particles
(particle size 30 nm) form an interconnected network with
porous structure. According to the Brunauer–Emmett–Teller
(BET) test, the surface area of this porous layer is 91.08 m2 g  1,
and the Barrett–Joyner–Halenda (BJH) average pore diameter and
pore volume are 14.7 nm and 0.33 cm3 g  1, respectively. The high
surface area with porous nature makes ion diffusion favorable Fig. 4. Sheet resistance of mesoscopic carbon film and the corresponding fill factor
throughout the counter electrode. In order to enhance the of the monolithic all-solid-state DSSC change with the thickness of mesoscopic
catalytic activity of the counter electrode towards triiodide carbon layer.
reduction, we coated the graphite and carbon black with platinum
particles. As shown in Fig. 3, the white nanoparticles on the
surface of flake graphite and carbon black are platinum and ZrO2.
The ZrO2 nanoparticles, acting as binders for the sintering of the
carbon layer, were homogeneously distributed in the carbon layer
and are not expected to prevent the uniform infiltration of the
carbon electrode by the polymer electrolyte.

3.2. Optimization of the carbon layer

The properties of the carbon counter electrode affect the internal

resistance of the cell [15]. To reduce the charge-transfer resistance
of the carbon counter electrode, the approach of increasing layer
thickness may be applied. However, this approach will result in
incomplete filling of the solid-state polymer electrolyte. Therefore,
the optimized thickness of the carbon layer is a compromise
between conductivity and electrolyte infiltration. Pronounced
changes in the fill factor (FF) and the sheet resistance of the carbon
layer were observed while changing the thickness of the carbon
layer. Generally, FF indicates the internal resistance of cells and the Fig. 5. Current–voltage curve of a monolithic all-solid-state DSSC module with
situation of electrolyte infiltration. Fig. 4 shows the dependence of size 10 cm  10 cm.
FF on the sheet resistance of the carbon layer. The results show that
the smaller resistance of the carbon layer, the greater the FF, when
improvement in conductivity of the carbon layer, which decreases
the layer thickness is under 60 mm. This effect is linked to the
the electron transfer resistance of the counter electrode. For the
layer thicker than 60 mm such as 75 mm, the FF decreases sharply to
0.28. This can be attributed to incomplete electrolyte infiltration.
As a vacuum method was used to fill the polymer electrolyte, the
solvent in the electrolyte volatilized very quickly during the filling
process. For the layer thicker than 70 mm, the electrolyte may turn
into a solid state before it infiltrates into the TiO2 layer. Therefore,
the carbon layer was optimized to about 60 mm for the highest
efficiency.

3.3. Performance of the module

The module efficiency is calculated from the aperture defined

Fig. 3. SEM image of the carbon layer on FTO glass substrate.
by the exterior edges of the TiO2 layers of the module. Fig. 5
shows the performance of a typical monolithic all-solid-state
DSSC module. The overall energy conversion efficiency has been
2.57% with 61.1 cm2 active area. Correspondingly, the module
offers a power of 156.9 mW for maximum, and shows a short-
circuit photocurrent (Isc) of 73.3 mA, open-circuit voltage (Voc) of
3.68 V and FF of 58.2%. When connecting cells in series, it will be
important to overcome the differences in cell performances to
avoid significant energy losses. This issue seems to be solved by
 Y. Rong et al. / Solar Energy Materials & Solar Cells 105 (2012) 148–152
employing screen-printing technology to fabricate all the layers.
In solid-state DSSCs, incomplete filling of the electrolyte is a
major limitation on the efficiency and performance of the cells.
The relatively high FF of 58.2%, which is comparable to the FF of
liquid-state DSSC module, indicates an effective filling of the
electrolyte. It can be concluded that the introducing of the
vacuum pore-filling technique in large-sized DSSC is feasible
and it is anticipated that the technique shall be applicable to a
wide range of solid-state materials. Besides, it should be noted
that the present module is not optimized for high performance,
and there is scope for improvement through adjusting the
dimensions of the active layer [16,17]. Also the non-active area
can be reduced by more stringent control over the material
components and process parameters.
3.4. Stability of the module
Moisture intrusion was an intrinsic problem for the stability of
DSSCs [18], so that a novel sealing process was employed. The
metallic frame and sealant ensured that no moisture intruded
into the module and affected the components of the cells. Fig. 6
shows the changes of Isc, Voc, FF and the energy conversion
efficiency (Z) of the module with and without sealing process
under the hot and high humidity conditions (60 1C, 85% RH)
during a period of over 1000 h. Each parameter was normalized
using the initial value before the test. As seen in Fig. 6, the
performance of the module without sealing process diminished
completely after the first 200 h. Since the solid-state polymer
electrolyte was exposed to a highly humid atmosphere, this great
degradation of the module performance could be caused by the
loss of redox function in the electrolyte. It was observed that the
polymer electrolyte lost the color attributed to existence of I3
Fig. 6. Stability of the module under the heat and high humidity environment
(60 1C, 85% RH). The solid line and dashed line indicate the performance of the
module with and without sealing process, respectively.
151
after 200 h under highly humid condition. We suppose that this is
caused by the reaction between electrolyte and the components
from the high humidity atmosphere or by the loss of iodine.
Besides, obvious decolorization of the dye-sensitized working
electrode was also observed. A possibility for this is desorption
or degradation of the dye. As shown by Agrell et al. [19],
degradation of the dye in air is probably due to the oxygen and
water contents in air. The thiocyanate ion ligands of the dye may
exchange with H2O and/or OH  ligands, reducing the stability of
the solar cell.
In contrast, the module with sealing process presented much
better stability against the highly humid environment, though a
slight degradation of the efficiency of the module was observed
(deterioration factor 1.049  10  4/h). The gradual degradation
of the efficiency was due to the slight decrease of the Voc and the
FF, which were similar to those of modules using liquid-state
electrolytes [18]. In general, the decrease of the Voc and FF could
mainly be attributed to the increase of the internal series
resistance of the module. As reported by Haque et al. [20], the
charge recombination kinetics in DSSCs is strongly dependent
upon the electrolyte composition. Besides, the influence from
outside has been prevented by employing a sealing process. Thus,
we suspect that the increase of the internal series resistance may
be caused by the change of components in unit cells, especially in
the electrolyte. It is possible that some components of the
electrolyte degraded or decomposed in the long-term endurance
test, and caused an incorrect chemical balancing of the electrolyte
components.
Since no initial decay in the performance was observed, the
existence of residual solvent in the solid-state polymer electrolyte
could be eliminated [21]. Moreover, no visible change of the
components in the module was found. These results indicated an
effective prevention of moisture intrusion. It should also be noted
that the sealing material seems be mechanically and thermally
stable and chemically inert against the electrolyte components,
especially the I  /I3 . Though the stability of the module improved
after the sealing process was employed, further investigations are
necessary to study the dynamic behavior of module performance
in the long-term stability test.
In order to study the stability of the components of the module
in a more practical environment, an endurance test under a heat
and cool cycle stress in the range of  10 and 60 1C was performed.
Fig. 7 shows the changes of Isc, Voc, FF and Z of the module during
the test. The Voc and FF were almost stable, while the Isc gradually
decreased in the first 100 cycles and then stayed constant. After 200
cycles, the module retained over 92% of the initial conversion
efficiency. Even though the reason for the change of Isc was unclear
so far, a stable all-solid-state DSSC module was successfully
produced. Although the efficiency is low in comparison to those
of modules assembled with liquid-state electrolytes, the present
module is the first successful attempt with solid-state polymer
electrolyte and carbon counter electrode. This design is suitable for
indoor applications and is even portable due to the advantages of
no risk of electrolyte leakage and less weight because of elimination
of the second glass substrate.
4. Conclusions
A low-cost monolithic all-solid-state DSSC module of size
10 cm  10 cm was developed, with a simple manufacturing
process, low material cost and high stability. Efficiency about
2.57% has been achieved on the active area (61.1% of total area)
under full sunlight condition, capable of offering a power of
156.9 mW for maximum and even higher with further optimiza-
tion. Moreover a novel sealing method was developed to avoid
152 Y. Rong et al. / Solar Energy Materials & Solar Cells 105 (2012) 148–152
Fig. 7. Stability of the module under the heat and cool cycle stress ( 10 and 60 1C).
the degradation of the module attributed to moisture intrusion.
All these values make the design a promising path for the
commercialization of DSSCs.
Acknowledgments
The authors acknowledge the financial support by the National
Natural Science Foundation of China (Grant no. 61106056), the
Nature Science Foundation of Hubei Province (2008CDA042),
Scientific Research Foundation for Returned Scholars, Ministry
of Education of China and the Fundamental Research Funds for
the Central Universities (Hust, 2011TS020). We also thank the
Analytical and Testing Center of Huazhong University of Science
and Technology [HUST] for field emission scanning electron
microscopy [FE-SEM] testing.
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