Monolithic all-solid-state dye-sensitized solar cells

Yaoguang Rong, Zhiliang Ku, MiXu, Guanghui Liu, Heng Wang, Hongwei Han*
Michael Grtzel Center for Mesoscopic Solar Cells, Wuhan National Laboratory for Optoelectronics,
School of Optical and Electronic Information, Huazhong University of Science and Technology,
Wuhan 430074, Hubei, P. R. China

ABSTRACT

The high cost of electricity produced by solar cells compared with electricity from other energy sources inhibits a more
widespread adoption of solar energy. Here, a low-cost monolithic all-solid-state dye-sensitized solar cell (DSSC) was
developed with a mesoscopic carbon counter electrode (CE). Based on the design of a triple layer structure, the TiO2
working electrode layer, ZrO2 spacer layer and carbon counter electrode (CE) layer are constructed on a single
conducting glass substrate by screen-printing. With a vacuum pore-filling technique, solid-state materials such as
PEO/PVDF polymer composite, poly(3-hexylthiophene) (P3HT) and 2,2,7,7-tetrakis(N,N-di-p-methoxyphenylamine)-
9,9-spirobifluorene (spiro-OMeTAD) hole transport material (HTM) could effectively infiltrate the multilayer thick
films to assemble all-solid-state devices. The high surface area and large pore volume favor the penetration of the solid-
state electrolyte materials and could reduce the resistance of the interface between CE and solid-state electrolyte.
Correspondingly, efficiency up to 3.23% was obtained with polymer composite electrolyte and the dye of N719. With
the dye of D102, efficiencies of 3.11% and 3.45% were obtained for the HTMs of P3HT and spiro-OMeTAD based
electrolytes. In addition, a mesoscopic methylammonium lead iodide (CH3NH3PbI3) perovskite/TiO2 heterojunction solar
cell was developed based on the monolithic structure and showed an efficiency of up to 6.53%. This design for
monolithic DSSC with a carbon CE presents a promising commercial application prospect for this photovoltaic
technology.

Keywords: dye-sensitized solar cells, all-solid-state, monolithic, low-cost, hole transport material, perovskite

1. INTRODUCTION

Photovoltaic (PV) technology has been acknowledged as the most promising renewable power source for the fulfillment
of increasing world energy consumption with the least impact on the environment. In the development of PV technology,
solid-state junction devices, usually based on silicon, dominate the commercial market. However, the dominance of the
PV field by inorganic solid-state junction devices is now being challenged by the emergence of a third generation of
solar cells such as dye-sensitized solar cells (DSSCs) [1]. DSSCs attract such attention because they could be fabricated
from materials that do not need to be highly purified, by low-cost fabrication procedures [2,3]. Moreover, DSSCs are
unique in that the electron transport, light absorption and charge separation are each accomplished by different materials
in the device. Conventional DSSCs are usually based on a sandwich structure comprising two conducting glass
substrates, between which exists a liquid-state electrolyte. The highest power conversion efficiency (PCE) for DSSCs
based on this structure has reached over 12% [4,5]. However, DSSCs using a liquid-state electrolyte containing volatile
solvent always suffer leakage, dye desorption, complicated sealing process and other problems, preventing the further
applications of DSSCs. Replacing the liquid electrolyte with a solid-state medium such as hole conductors and polymer
electrolyte seems to be a solution to these problems [6-9]. Recently, the PCE for all-solid-state DSSCs has also reached
over 12% [10-12]. Furthermore, all-solid-state DSSCs are usually constructed on a single conducting glass substrate.This
feature would decrease the material cost for the fabrication of DSSCs significantly, since the conducting glass substrate
accounts for most of the process material cost [13]. It should be noted that the counter electrodes of conventional solid-
state DSSCs were fabricated by depositing noble metals such as gold or platinum on the solid-state medium. Obviously,
this counter electrode, with its high-cost metals, remains a barrier for the development of DSSC application due to the
highly energy consumptive vacuum deposition.

Organic Photovoltaics XIV, edited by Zakya H. Kafafi, Paul A. Lane, Proc. of SPIE Vol. 8830, 88301W
2013 SPIE CCC code: 0277-786X/13/$18 doi: 10.1117/12.2023774

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 In this report, we mainly focus on monolithic all-solid-state DSSCs, which offer the prospect of being lower cost
and requiring simpler manufacturing processes. Eliminating the second conducting glass substrate and using a carbon
counter electrode (CE) instead of a noble metal CE decrease the material cost of this design greatly compared with
conventional sandwich structure liquid-state DSSCs. With a vacuum pore-filling technique, solid-state materials such as
PEO/PVDF polymer composite, poly(3-hexylthiophene) (P3HT) and 2,2,7,7-tetrakis(N,N-di-p-methoxyphenylamine)-
9,9-spirobifluorene (spiro-OMeTAD) hole transport material (HTM) could effectively infiltrate the multilayer thick
films to assemble all-solid-state devices. The high surface area and large pore volume of the carbon counter electrode
favor the penetration of the solid-state electrolyte materials and could reduce the resistance of the interface between CE
and solid-state electrolyte. Based on this design, a mesoscopic methylammonium lead iodide (CH3NH3PbI3)
perovskite/TiO2 heterojunction solar cell was also developed. Replacing the liquid-state electrolyte with a solid-state
medium solves the problems caused by the corrosiveness of the redox couple (I-/I3-) and that of potential leakage, linked
to the high volatility of the solvent. All these advantages make this design a promising path for the commercialization of
DSSCs.

2. EXPERIMENTAL

2.1 Preparation of solid-state electrolyte

The polymer composite electrolyte was prepared by dissolving 0.944 g poly(ethylene oxide) (PEO) (Mw=600 000)
and 1.418 g poly(vinylidene fluoride) (PVDF) (Mw=150 000) in 30 ml dimethylformamide (DMF)/acetonitrile (ACN)
mixture (7:3; v/v). After stirring for 4 h, 1.623 g I-/I3- redox couple solution was added. The redox couple solution
consisted of 0.115 g I2, 0.117 g LiI and 1.391 g 1,2-dimethyl-3-propylimidazolium iodide (DMPII) dissolved in 10 ml
DMF/CN (7:3; v/v). The P3HT based electrolyte was prepared by dissolving 0.4 g P3HT in 10 ml 1,2-dichlorebenzene.
The Spiro-OMeTAD based electrolyte was prepared by dissolving Spiro-OMeTAD, LiTFSI and TBP in chlorobenzene
with a concentration of 0.15 M, 0.021 M and 0.12 M. Then, a chemical dopant FK102 was dissolved in acetonitrile and
added to the HTM solution with a molar ratio of 1.5%. For the CH3NH3PbI3 precursor, 0.123 g CH3NH3I and 0.3625 g
PbI2 were mixed in 1mL -butyrolactonel.

Structuring
FTO glass
I- Washing
FTO glass
Depositing
dense layer
Printing
working
electrode

Printing Drying Printing Sintering

counter
electrode 100 C spacer layer 500 C

1
Sintering Dye Surface Electrolyte
400 C
11110.
application treatment application

Fig. 1 Overview of the fabrication process steps for monolithic all-solid-state DSSCs.

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 2.2 Fabrication of the monolithic all-solid-state DSSCs

The fabrication process steps for typical monolithic all-solid-state DSSCs are presented in Fig. 1. After the
pretreatment of the glass substrate (TEC-15, Pilkington, USA) including the laser structuring of the FTO layer and the
washing of the glass, a dense TiO2 layer was deposited on the conducting glass substrate by spray pyrolysis deposition
with di-isopropoxytitaniumbis(acetyl acetonate) solution. Then a nanoporous TiO2 layer, a ZrO2 layer, and a carbon layer
were screen-printed on the substrate layer by layer. The TiO2 paste was commercial available (JGC Catalysts and
Chemicals Ltd., Japan) and the ZrO2 paste and carbon paste were prepared according to the published procedures using
commercial ZrO2 nanoparticle, carbon black and graphite [7,8]. The TiO2 layer and ZrO2 layer were sintered for 30 min
at 500 oC, and the carbon layer was sintered at 400 oC for 30 min. After cooling to 60 oC, the substrate was immersed in
the acetonitrile and tert-butyl alcohol mixed solution (volume ratio, 1:1) containing 0.5 mM dye (N719 or D102) at room
temperature for about 24 h. After that, the solid-state electrolyte solution was dropped and spread on the top of the
carbon layer. With a vacuum pore-filling technique, the solid-state electrolytes penetrated all the three porous layers
effectively.

For the mesoscopic methylammonium lead iodide (CH3NH3PbI3) perovskite/TiO2 heterojunction solar cell, without
dye processing, 5 L of CH3NH3PbI3 precursor was dipped on the top of the mesoscopic carbon layer directly. Then the
devices were dried at 50C on a hot plate in dark. During the drying procedure, the color of devices changed from light
yellow to dark brown, indicating the accomplishment of the solar cell. For the test cells, no sealing or insulating process
was applied.

3. Result and discussion

3.1 Structure of monolithic all-solid-state DSSCs

The structure of a typical monolithic DSSC is shown in Fig. 2(a). The FTO conducting layer on the glass substrate
is etched by laser processing to form two insulated areas. Thus, the working electrode (WE) and counter electrode (CE)
could be constructed on the same substrate, between which is the insulating layer (ZrO2 layer). The insulating layer may
also act as a diffuse reflecting layer that reflects light which has not yet been absorbed by the dye-sensitized WE. For the
fabrication of monolithic DSSCs, the largest problem is to prevent the carbon CE from penetrating the other layers. This
may cause direct contact between the carbon layer and the TiO2 layer and, even worse, between the carbon layer and the
FTO layer. Contact between the carbon layer and the TiO2 layer may cause performance losses due to internal losses,
that is, electrons transferring from the TiO2 layer to the carbon layer directly. This problem has been solved through the
use of only one sintering step for ZrO2 layer and carbon layer. Since the porous structure of the ZrO2 layer has not
formed yet when the carbon layer is being printed, almost no carbon penetrates the ZrO2 layer. Even a ZrO2 layer with
the thickness of 1-2 m could function effectively as an insulating layer between the TiO2 layer and carbon layer.

To characterize the morphology of the layers on the conducting glass substrate, scanning electron microscopy
(SEM) test was employed. Fig. 2(b) shows the SEM image of the cross section of a monolithic DSSC. The three layers
that presented in Fig.2 (a) are clearly observed. The surface of the TiO2 layer presents rather flat and the TiO2 seems
quite uniform. The properties of the TiO2 working electrode affect the light harvesting ability and the photovoltaic
performance of the device significantly. Since all the layers are fabricated using screen-printing technology, the
thicknesses of the layers could be controlled precisely, and the distance between the WE and CE could be minimized in
the condition of insulating the WE and CE. Besides, on a single conducting glass substrate, the electrodes of 45 devices
could be fabricated as reported. This design could be used as an efficient tool for testing material components in DSSCs,
the fabricating procedures of which permit excellent reproducibility [14,15].

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 (a)

{,
Carbon layer

Electrolyte Zr02 layer

TiO2 layer

Glass

FTO layer Dense TO

\vo
3 000z 6 .4

Fig. 2 (a) The structure of a typical monolithic all-solid-state DSSC based on mesoscopic CCE. (b) The SEM image of the cross
section of a monolithic DSSC

3.2 Optimization of the carbon counter electrode

For monolithic DSSCs, the carbon counter electrode (CCE) should provide sufficient conductivity for charge
transfer and electrocatalytic activity for the reduction of oxide species such as I3- in the redox couple. Several CCEs have
been developed in our group for all-solid-state DSSCs [15-17].

It is well known that the sheet resistance of the CE influences the fill factor (FF) of DSSCs, which plays a key role
in the performance. For monolithic DSSCs, in order to obtain a high FF, the resistance of CCE should be reduced to that
of the conducting glass substrate. Though the carbon black nanoparticles exhibit high electrocatalytic activity, the carbon
film comprised of only carbon black particles shows a cracked surface resulting in a low lateral conductivity. Among the
carbon materials, the flake graphite is well known for its high lateral conductivity. Thus, we incorporated the flake
graphite with carbon black nanoparticles to prepare the carbon film [16].

Fig. 3 SEM images of the carbon film consisting of carbon black nanoparticles and flake graphite: (a) 50 000; (b) 100 000

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 According to our research, the sheet resistance of the carbon film decreases sharply with an increase in the ratio of
graphite. However, as the amount of the graphite increases, the electrocatalytic activity of the film decreases, since the
high orientated graphite only has a few active sites. Thus, a compromise exists, between these two, on searching for the
optimum ratio for graphite and carbon black. Generally, the ratio was optimized to 3.25:1 for liquid-state electrolyte
based DSSCs [16]. Figure 3 shows the SEM images of the carbon film with a ratio of 3.25:1 for graphite and carbon
black. For the carbon film, graphite flakes and carbon black nanoparticles form an interconnected network with porous
structure. The high surface area with porous nature makes ion diffusion favorable throughout the counter electrode. The
Brunauer-Emmett-Teller (BET) surface area of this layer is 95.42 m2 g1. The Barrett-Joyner-Halenda (BJH) average
pore diameter and pore volume are 10.20 nm and 0.24 cm3 g1, respectively. This means that a carbon layer of 0.36 cm2
geometric area and 1 m thickness has 286.3 cm2 of active surface area and a porosity of 20%.

45

40 -0- Normal
-0- Pt
35 -A- Graphen
30

25

20

15

10

0
10 20 30 40 50 60 70 80

Thickness (pm)

Fig. 4 Dependence of the sheet resistance of the carbon films on the film thickness: normal carbon film (square); platinum
modified carbon film (circle); graphene modified carbon film (triangle).

To further improve the conductivity and electrocatalytic activity of the carbon film, the carbon black/graphite
carbon film was modified with platinum [16] and graphene [15], which were commonly used for both electrode materials
and catalytic materials. Fig. 4 shows the dependence of the sheet resistance of the carbon films on the film thickness.
Generally, modifying with platinum or graphene, the conductivity of the carbon film was significantly improved. For the
normal carbon film containing only graphite/carbon black, the thickness of the film needs to be increased to ~70 m to
decrease the sheet resistance to ~15 square-1. For the platinum modified carbon film, a sheet resistance of ~15
square-1 could be obtained with the thickness of ~45 m, and ~40 m for graphene modified carbon film.

For the electrocatalytic activity against the reduction of the redox couple in the electrolyte, it has been proved that,
for both the traditional I-/I3- redox couple and the iodine-free thiolate/disulfide redox couple, the graphene modified CCE
functions efficiently [15-16].

3.3 Performance of the devices with solid-state electrolyte

For solid-state electrolytes, there are two categories: polymer electrolyte containing redox couple and hole transport
material (HTM). Here for the PEO/PVDF based solid-state polymer electrolyte, alkali salt (LiI) was dissolved in the
polymer matrix, which was acknowledged as an effective method to increase the conductivity of the polymer composite
[18, 19]. With the additives of I2 and ionic liquid of DMPII in the electrolyte and the platinum modified carbon counter
electrode, an efficiency of 3.29% was obtained for the all-solid-state device with a short-circuit current density (Jsc) of
7.15 mA cm-2, an open-circuit voltage (Voc) of 613.75 mV and a fill factor (FF) of 0.77. The high FF indicates fast
charge transfer between the carbon counter electrode (CCE) and the polymer composite electrolyte, which attributes to

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 the high surface area of the platinum modified mesoscopic carbon film. Photocurrent density-voltage (J-V) curves of the
polymer electrolyte and HTM based devices were characterized under 1 sun illumination (AM1.5, 100 mW cm-2) and
shown in Fig. 5. Their performance parameters were summarized in Table. For the P3HT electrolyte based device, an
efficiency of 3.11% was obtained with Jsc of 7.62 mA cm-2, Voc of 620.58 and FF of 0.66. The thicknesses of the three
layers were optimized to 2.0 m for the TiO2 layer, 4.0 m for the ZrO2 layer and 25 m for the carbon layer. For the
Spiro-OMeTAD based devices, an efficiency of 3.45% was obtained with Jsc of 6.23 mA cm-2, Voc of 875.31 and FF of
0.63. The thicknesses of the three layers were optimized to 2.0 m for the TiO2 layer, 1.1 m for the ZrO2 layer and 10
m for the carbon layer.

For the HTMs based electrolyte, there are mainly two factors that limit the all-solid-state DSSCs from obtaining
high efficiency. When the thickness of the TiO2 layer exceeds 2 m, electron-hole recombination and incomplete filling
of the mesoporous TiO2 film with HTMs would affect the performance of the device significantly [20-22]. For
monolithic all-solid-state DSSCs based on mesoscopic CCE, there are the ZrO2 layer and the carbon layer on the top of
mesoscopic TiO2 layer, thus it would be a challenge for the HTM to infiltrate to the bottom of the TiO2 layer. Besides,
the thickness of the ZrO2 also determines the distance between the working electrode and counter electrode, which is also
an issue for obtaining high-efficient all-solid-state DSSCs.

Table 1. Photovoltaic parameters of devices based on different electrolytes and dyes.

Electrolyte Dye Voc / mV Jsc / mA cm-2 FF PCE/%

PEO/PVDF N719 613.75 7.15 0.77 3.38

P3HT D102 620.58 7.62 0.66 3.11

SPIRO D102 875.31 6.23 0.63 3.45

CH3NH3PbI3 883.35 12.38 0.60 6.53

16

PEOPVDF
14 OMeTAD
P3HT
12 CH3NH3Pbl3

10

i i i i i in i i

100 200 300 400 500 600 700 800 900 1000

Voltage (mV)
Fig. 5 J-V curves of monolithic all-solid-state DSSCs based on different solid-state electrolytes.

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 It is well known that a thinner HTM layer between the TiO2 layer and the CE layer corresponds to a smaller series
resistance. Moreover, it also means that more light could be reflected by the CE. As a result, the HTM layer should be as
thin as possible, if that does not lead to a short circuit. According to our research, when the optimized ZrO2 layer
thickness, which determines the distance between the TiO2 layer and the CE layer, is controlled within 1-10 m, the Voc
of the device based on P3HT electrolyte slightly increased from 630 mV to 670 mV and the FF decreased from 0.70 to
0.48. For the Jsc of the device, it increased from 6.1 mA cm-2 to 6.6 mA cm-2 and then decreased sharply to 4.5 mA cm-2
when the thickness of the ZrO2 layer exceeded 6.0 m. This could be attributed to the fact that a ZrO2 layer with a
thickness above 6 m leads to poor pore-filling and a high series resistance. Thus, the optimized ZrO2 film thickness was
in the range 1-6 m for P3HT based monolithic all-solid-state DSSCs [7].

Similar results could be observed for spiro-OMeTAD based devices. When the thickness of ZrO2 layer increases
from 1.1 m to 3.3m, the photovoltaic parameters of the devices show approximate values, where they exhibited Jsc of
6.11-6.25 mA cm-2, Voc of 860-871 mV, FF of 0.53-0.55 and PCE of 2.80-2.98%. When the insulating layer thickness
further increased to 5.1 m, the Voc and FF of the devices decreased sharply to 775 mV and 0.44. ZrO2 layer plays the
key role to break the electrical contact between the electrodes and has significant effect on the electron lifetime. And for
1.1 m ZrO2 layer, the solar cell performance and electron lifetime exhibit better than the other devices [23].

For the counter electrode in HTMs based all-solid-state DSSCs, noble metals such as platinum, gold and silver are
commonly used. Thus, it is a breakthrough for replacing the noble metals with low-cost carbon materials. Actually,
graphite film could be deposited on the substrate by screen printing with a flake graphite paste easily, which consists of a
laminated structure with high conductivity. However, the device assembled with such CCE containing only graphite
shows much lower efficiency compared with that of device based on graphite/carbon black CE. For the P3HT based
devices, the addition of carbon black in the CE decreased the charge recombination between the injected electrons in the
conduction band of TiO2 and the holes in P3HT. Correspondingly, a higher Voc could be obtained. At the same time, the
electron collection efficiency was also enhanced, resulting in an increase in the Jsc. For the Spiro-OMeTAD based
devices, the results were quite different. The Voc of the device decreased when carbon black nanoparticles were added
into the CE, and the Jsc almost stayed the same. However, a dramatic increase in FF of the device was observed. This
phenomenon could be attributed to the improvement of contact between the CE and the solid-state electrolyte, since the
addition of carbon black to the CE increased the surface area and porosity. The interfacial electron transfer resistance
would decrease due to the large active surface area, thus FF increased.

For the CH3NH3PbI3 perovskite/TiO2 heterojunction solar cell, efficiency up to 6.53% has been obtained with Jsc of
12.38 mA cm-2, Voc of 883.35 mV and FF of 0.60. Compared with conventional all-solid-state DSSCs based on HTMs
such as P3HT and spiro-OMeTAD, this perovskite/TiO2 heterojuncion solar cell presents much higher Jsc and PCE.
Actually, there still remains much room for further greatly substantial improvement in the PCE, in particular by
augmentation of the Jsc through control of the CH3NH3PbI3 perovskite crystallinity. The fact that carbon CE can prepared
by screen printing permits the commercial production of this high-efficiency CH3NH3PbI3 perovskite/TiO2
heterojunction solar devices.

4. Conclusions

Monolithic all-solid-state DSSC based on mesoscopic carbon CEs and solid-state electrolytes offer the prospect of much
lower production cost and long-term stability. The high surface area and large pore volume of the mesoscopic carbon
counter electrode favor the penetration of the solid-state electrolyte materials and could reduce the resistance of the
interfaces between CE and solid-state electrolyte. With the polymer composite electrolyte, an efficiency of 3.23% was
obtained. With the hole transport materials of P3HT and spiro-OMeTAD, efficiencies of 3.11% and 3.45% were
achieved, respectively. Based on this design, a mesoscopic CH3NH3PbI3 perovskite/TiO2 heterojunction solar cell was
also developed with an efficiency of 6.53%. All these achievements make monolithic all-solid-state DSSCs a promising
path for the commercialization of DSSCs.

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 Acknowledgements

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 Center for Nanoscaled Characterization and Devices of Wuhan National
Laboratory for Optoelectronics (WNLO) for scanning electron microscopy.

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