Organic Electronics 14 (2013) 628–634

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Organic Electronics
journal homepage: www.elsevier.com/locate/orgel

Efficient monolithic solid-state dye-sensitized solar cell with a

low-cost mesoscopic carbon based screen printable counter
electrode
Mi Xu, Guanghui Liu, Xiong Li, Heng Wang, Yaoguang Rong, Zhiliang Ku, Min Hu, Ying Yang,
Linfeng Liu, Tongfa Liu, Jiangzhao Chen, Hongwei Han ⇑
Michael Grätzel 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, PR China

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

Article history: A low-cost mesoscopic carbon counter electrode (CE) with high surface area is applied in
Received 14 November 2012 solid-state dye-sensitized solar cells (ss-DSCs) using spiro-OMeTAD hole transporting
Received in revised form 11 December 2012 material (HTM). The intensity modulated photovoltage spectroscopy (IMVS) measure-
Accepted 14 December 2012
ments are carried out to ascertain the thickness of insulating layer. The influence of mes-
Available online 29 December 2012
oscopic carbon CE on the charge transfer process is characterized by the electrochemical
impedance spectra (EIS) with CE/HTM/CE dummy symmetric cell, which indicates that
Keywords:
the mesoscopic structure of CE is helpful to reduce the resistance of the interface between
Organic semiconductor
Mesoscopic counter electrode
CE and HTM. A high efficiency up to 4.03% is obtained with D102 dye under 1 sun (AM1.5
Electron lifetime global, 100 mW cm2), which is comparable to that of the conventional ss-DSC based on
Screen printable noble CE.
Solid-state solar cell Ó 2012 Elsevier B.V. All rights reserved.

1. Introduction glass transition temperature, high solubility and proper

Dye-sensitized solar cells (DSCs) have been played an
important role in the new energy fields due to their low
cost and simple production process [1,2]. Although a high
efficiency exceeding 11% has been achieved with I 
3 =I re-
dox coupling [3], those liquid electrolyte based solar cells
suffer from leakage, corrosion and long-term stability
problems, which hinder the commercial application of
DSCs. However, these issues may be avoided by replacing
the liquid electrolyte with the solid hole transporting
materials (HTMs), such as triarylamines [4,5], conducting
polymers [6] and inorganic p-type semiconductors [7,8].
Since the amorphous organic hole transfer material spiro-
OMeTAD (2,20 ,7,70 tetrakis-(N,N-di-p-methoxyphenyl-
amine) 9,90 -spirobifluor-ene) is applied in solid-state DSCs
(ss-DSCs) by U. Bach et al. [5], it has been considered as the
most promising hole conductor for ss-DSCs, due to its high
⇑ Corresponding author. Tel./fax: +86 2787793027.
E-mail address: hongwei.han@mail.hust.edu.cn (H. Han).
absorption spectrum. Up to now, the highest efficiency
over 10% has been attained with this ss-DSCs assembling
with a lead iodide perovskite inorganic sensitizers [9,10]
and 7.2% with a new organic D–p–A dye [11]. However,
the counter electrodes (CEs) of spiro-OMeTAD based DSCs
are made by thermally evaporating noble metals (usually
Au or Ag) [12], which leads to high cost and rigorous craft,
becoming another block of the commercial application.
However, few works have been made to replace the metal
CE for ss-DSCs.
In 1996, Kay and Grätzel firstly reported monolithic li-
quid DSCs with a carbon electrode [13]. Since then, carbon
material electrodes have been widely taken attention for
their low-cost and screen printable deposition technique.
However, some obstacles are confronted when applying
the carbon electrode to ss-DSCs based on HTMs. A tradi-
tional spiro-OMeTAD based DSC uses spin coating tech-
nique to infiltrate the HTM after dye soaking, and then a
metal contact is deposited on the HTM film by evaporation
technology. Nevertheless, the dye and spiro-OMeTAD

1566-1199/$ - see front matter Ó 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.orgel.2012.12.015
 M. Xu et al. / Organic Electronics 14 (2013) 628–634
molecule will arise thermal degradation at the sintering
temperature of 400 °C at the sintering process of meso-
scopic carbon film.
Here we introduce the carbon materials as CE of spiro-
OMeTAD based DSCs, where the CE deposits by screen
printing technology before dye soak and HTM filling.
Meanwhile, the drop casting method is employed instead
of spin coating so that HTM solution could penetrates into
the mesoporous photoanode through the thick carbon
films. The intensity modulated photovoltage spectroscopy
(IMVS) measurements are carried out to ascertain the
thickness of insulating layer. The influence of mesoscopic
carbon CE on the charge transfer process is characterized
by the electrochemical impedance spectra (EIS) with CE/
HTM/CE dummy symmetric cell, which indicates that the
mesoscopic structure of CE is helpful to reduce the resis-
tance of the interface between CE and HTM. A high effi-
ciency up to 4.03% is obtained with typical organic dye
D102 [12,14] under 1 sun (AM1.5 global, 100 mW cm2),
which is comparable to that of the conventional ss-DSC
based on noble CE.
2. Experimental
2.1. Preparation of carbon paste
Carbon black and graphite powders were mixing in a
terpineol (Sigma) solution with stirring for 1 h. And then
the 20 nm ZrO2 nanopowders and hydroxypropyl cellulose
(Sigma) were added and stirred vigorously via ball milling
for 2 h. The mass ratio between carbon material, ZrO2 and
cellulose was controlled to 10:1:2.
2.2. Monolithic ss-DSC fabrication
The typical monolithic ss-DSC was fabricated as follow-
ing: fluorine-doped tin-oxide (FTO) glass substrates were
etched with a laser before being cleaned ultrasonically
with detergent, deionized water and ethanol successively.
A compact TiO2 layer was deposited onto the patterned
substrate by spray pyrolysis, following TiO2 particles (PAS-
OLHPW-18NR) were deposited by screen printing. After
sintering at 500 °C, a ZrO2 (Tosoh zirconia powder TZ-3Y)
layer and a 10 lm-thick carbon layer were printed layer
by layer and sintered at 400 °C for 30 min. When the tem-
perature fell to 80 °C, the devices were then immersed into
D102 solution (0.5 mM in CH3CN: t-BuOH(1:1)) overnight.
Spiro-OMeTAD was dissolved in chlorobenzene at a con-
centration of 0.15 M, then 0.021 M LiTFSI and 0.12 M TBP
added. A chemical dopant FK102 was dissolved in acetoni-
trile before adding to the HTM solution at the molar ratio
of 1.5%. The HTM solution was dropped onto the carbon
layer and soaked at room temperature for 2 min, and then
the devices were heated at 60 °C until they dried. All of the
processes were performed under red light conditions.
2.3. Dummy symmetric cells fabrication
The dummy symmetric cells were assembled as follow-
ing: carbon slurry was printed on the cleaned FTO glass
629
and sintered at 400 °C for 30 min. After that HTM solution
was dropped onto the carbon film and heated to gel, and
then two carbon electrodes with HTM gel were sand-
wiched with a 100 lm film of thick tape and fixed by
two clamps. Finally the dummy symmetric cell was heated
at 60 °C until solvent was evaporated out.
2.4. Characterization
The structure of monolithic ss-DSC was observed using
scanning electron microscopes (SEMs FEI Sirion 200). The
photocurrent density–voltage characteristics were taken
with a Keithley 2400 sourcemeter under illumination with
an Oriel solar simulator composed of a 1000 W xenon arc
lamp and AM 1.5 G filters. Light intensity was calibrated
with a normative silicon cell. The IMVS measurements
were carried out using high-intensity green LEDs
(530 nm) driven by a ZAHNER Xpot frequency response
analyzer over a frequency range of 100 mHz to 10 kHz at
a bias intensity of 0.06 sun. The LED supplied the ac (mod-
ulation depth 10%) and dc components of the illumination.
The Brunauer–Emmerr–Teller (BET) was characterized by
ASAP 2020 accelerated surface area and porosimetry sys-
tem. Electrochemical impedance spectroscopy (EIS) of the
symmetric cell was carried on a potentiostat (EG&G,
M2273) in the frequency range 100 mHz to 1 MHz with
10 mV AC amplitude under dark condition at 25 °C. The
parameters were fitted by Z-View software.
3. Results and discussion
3.1. Structure of the typical monolithic device
The monolithic ss-DSCs with the mesoscopic carbon CE
is presented schematically in Fig. 1. A mesoporous TiO2
layer, a ZrO2 insulating layer and a carbon CE layer are
screen-printed onto the FTO glass orderly before dye soak-
ing. The pores in the matrix are formed and combined into
channels after sintering. And the HTMs solution will pene-
trate through the channels and fulfill the pores of the three
layers. All the process can be accomplished in ambient air.
It has been noticed that pore filling is an important fac-
tor for the improvement of ss-DSC performance within the
previous publications [15,16]. Procedures to measure pore
filling fraction (PFF) are developed by some groups [17,18].
Unfortunately, the calculation method could not be applied
to our devices because of the HTMs in the pore of ZrO2 and
carbon layer which are unable to qualitative analysis.
Herein the state of pore filling is observed by cross-section
scanning electron microscopy (SEM) and presented in
Fig. 2. [15,18]. It could be found in Fig. 2a that ZrO2 insulat-
ing layer and carbon electrode layer have much larger par-
ticles and pore diameter than TiO2 layer, which facilitate
the penetration of HTMs solution. Fig. 2b shows the
cross-section image with high magnification, where the
TiO2 matrix (the light spot) is covered by organic materials
(the dark area), which gives evidence of good penetration
of HTMs into the pores of TiO2. Moreover, it can be found
that throughout the TiO2 layer the penetration seems to
be uniform, the pores at the bottom of the film appears
630 M. Xu et al. / Organic Electronics 14 (2013) 628–634
Fig. 1. The schematic structure of a monolithic ss-DSC with mesoscopic carbon CE.
Fig. 2. (a) Scanning electron micrograph showing the cross sections of the
monolithic ss-DSC with mesoscopic carbon CE and spiro-OMeTAD and (b)
the high magnification images of ZrO2 layer and TiO2 layer.
to be filled the same as those close to the top. Therefore,
the HTM material could penetrate smoothly into the pores
of TiO2 layer and efficient pore filling could be obtained
within this structure.
3.2. Effect of the insulating layer
The wet layer on top of the TiO2 film, which acts as a
reservoir in the traditional ss-DSCs, is considered as an
important parameter for the photovoltaic property and
normally controlled by the spiro-OMeTAD solution con-
centration, deposition temperature or speed of spin coat-
ing [17]. The interaction of the three factors makes the
process more complex and out of control, which leads to
poor repeatability of solar cell performance. An under-
sized reservoir may lead to a poor pore filling resulting in
low hole injection efficiency from dye cations to spiro-
OMeTAD, while an over-sized reservoir will bring about
high series resistance owing to low charge conductivity
of the HTMs [19]. However, the thickness of the HTM layer
between the TiO2 film and the CE layer in this carbon based
monolithic ss-DSCs is determined by the thickness of the
ZrO2 insulating layer, which has much less affection on
pore filling. Therefore, the ZrO2 layer plays the roles of both
insulator to isolate the carbon electrode from the TiO2
working electrode and reflector to enhance the light har-
vesting efficiency.
In order to understand the effect of ZrO2 layer thickness,
a series of photovoltaic devices have been made. The pho-
tocurrent density–voltage (J–V) characteristics of solar de-
vices with different ZrO2 thickness were taken under
simulated one-sun illumination. The active area of
0.13 cm2 was obtained with a mask on a 0.5 cm  0.5 cm
large size cell. Table 1 summarized the characteristic
parameters. It could be found that the maximal perfor-
mance is obtained when the insulating layer equates to
1.1 lm thick, which is much thicker than distance between
TiO2 film and noble metal CE in the traditional ss-DSC.
Compared with 1.1 lm-thickness insulating layer device,
0.6 lm-thick device has a lower open-circuit voltage (Voc)
and short-circuit current density (Jsc), the reduction may
be caused by direct contact between the photoelectrode
and CE. Herein, we noticed that a small amount of carbon
particle would penetrate into ZrO2 layer, result in the ac-
tual distance between CE and photoanode is lower than
the thickness of ZrO2 film. When the thickness of
 M. Xu et al. / Organic Electronics 14 (2013) 628–634 631

Table 1 less, the similar Jsc indicates that the expected enhance-
Photovoltaic performance datum of the ss-DSCs with different thickness of ment in light harvesting is not observed, which is
ZrO2 spacer layer. The thickness of TiO2 layer and carbon CE are 1.5 lm and
10 lm, respectively.
probably ascribed to the poor refractive index of the small
particle size ZrO2.
Thickness/lm Jsc/mA cm2 Voc/mV FF g/% IMVS measurements are taken to obtain the informa-
0.6 4.19 826 0.53 1.84 tion about the charge transport and electron–hole recom-
1.1 6.22 871 0.55 2.98 bination of ss-DSCs using different thick insulating layer
2.5 6.19 862 0.53 2.82
3.3 6.25 860 0.54 2.90
[20,21]. Fig. 3a shows the typical Nyquist plots of IMVS
5.1 6.31 775 0.44 2.15 characterization. The electron lifetimes (sn) are measured
as a function of photovoltage, calculated using the equa-
tion sn = 1/(2pfn,min), where fn,min is the frequency of the
ZrO2 layer increases from 1.1 lm to 3.3 lm, the parame- minimum of the semicircle in the IMVS plots. It can be seen
ters of these devices show approximate values, where they that the device using 1.1 lm insulating layer provides the
exhibited Jsc of 6.11–6.25 mA cm2, Voc of 860–871 mV, fill smallest semicircle and the longest electron lifetime. In
factor (FF) of 0.53–0.55 and power conversion efficiency general, the longer lifetime of excited electron indicates
(g) of 2.80–2.98%. However, when the insulating layer slower recombination rate and the higher conduction band
thickness is further increased to 5.1 lm, the Voc and FF of electron density, related to the higher value of Voc. The re-
ss-DSC decrease to 775 mV and 0.44 mV rapidly. Neverthe- sults of electron lifetime are presented in Fig. 3b, an

Fig. 3. (a) Typical IMVS response of monolithic devices with 0.6, 1.1, 2.5, 3.3, 5.1 lm thick ZrO2 insulating layer, with (b) corresponding electron lifetime of
1.3, 2.3, 1.8, 1.5, 1.0 ms. The frequency range is from 100 mHz to 10 kHz at a bias intensity of 0.06 sun.
632 M. Xu et al. / Organic Electronics 14 (2013) 628–634
approximate linear correlation is observed with a slope of
0.325 when the insulating layer thick exceeding 1.1 lm.
It’s reasonable to assume that electrical contact between
TiO2 and CE leads to a fast recombination rate when the
insulating layer is only 0.6 lm. However, the sn tends
shorter slightly as the insulating layer gets thicker, which
is probably due to the HTMs film exhibits poor charge con-
ductivity and the accumulation of the holes resulting in
recombination with the electrons in the conduction bands.
Therefore, ZrO2 layer plays the key role to break the electri-
cal contact between the electrodes and has significant ef-
fect on the electron lifetime. And for 1.1 lm ZrO2 layer,
the solar cell performance and electron lifetime exhibit
better than the other devices.
3.3. Analysis of the counter electrode
The characterization of carbon CE is another important
factor to the photovoltaic performance in carbon based
monolithic ss-DSC. In fact, several varieties of carbon
materials have been employed in various cells as CE, such
as carbon nanotube, active carbon, carbon black, fullerene,
graphite and graphene [13,22–30]. In our work, mesoscop-
ic graphite film could easily be deposited on the substrate
by screen printing from flake graphite paste, which con-
sists of laminated structure with high conductivity. The
addition of carbon black will increase the surface area
and offer more contact area between HTMs and CE. High
porosity and large pore diameter will facilitate spiro-OMe-
TAD solution penetrating into the TiO2 active layer through
Fig. 4. Photocurrent–voltage curves of monolithic ss-DSCs with meso-
scopic carbon counter electrodes under one sun illumination (AM 1.5,
100 mW cm2). The devices are based on various ratios of graphite: carbon
black; SC0 (1: 0), SC0.25 (1: 0.25), SC0.5 (1: 0.5), SC2 (1: 2).
Table 2
The characterization of the graphite and carbon black films with different ratio and the photovoltaic performance datum of their corresponding ss-DSCs.
Ratio Jsc/mA cm2 Voc/mV FF g/%
1:0 6.22 871 0.55 2.98
1:0.25 6.34 857 0.69 3.74
1:0.5 6.30 848 0.65 3.49
1:2 6.18 817 0.63 3.18
the CE. Meanwhile, the interfacial electron transfer resis-
tance would be decrease due to the large active surface
area. Hence, we fabricate cells with several ratios of graph-
ite to carbon black as CE and optimize carbon compounds
electrode, where the mass ratios of graphite to carbon
black are controlled to 1:0, 1:0.25, 1:0.5 and 1:2 (which
marked as device SC0, SC0.25, SC0.5 and SC2, respectively),
and the thickness of the TiO2 layer and the ZrO2 layer are
controlled to 1.5 lm and 1.1 lm, respectively. The J–V
curves of different graphite/carbon black CE based ss-DSC
devices under full sunlight are presented in Fig. 4, and
the parameters of J–V curves and the characterization of
carbon CEs are summarized in Table 2. With the increase
of carbon black, Voc presents a downward trend from
871 mV to 817 mV while Jsc keeps in the small range of
6.18–6.34 mA cm2. Indeed, the most obvious impact
parameter is FF within the devices based on the different
graphite/carbon black CE. Compared to the FF and g of
SC0 (0.55 for FF and 2.98% for g), the corresponding param-
eter of SC0.25 are increased to 0.69% and 3.74%, respec-
tively, which exhibits an enhancement of nearly 25% in
FF and g. This improvement could be attributed to the in-
crease of contacts between CE and HTMs after the addition
of carbon black. The N2 adsorption/desorption analysis
indicates that the addition of carbon black could raise
BET surface area and porosity remarkably (Table 2), conse-
quently higher FF and g are obtained. However, the Voc
goes down quickly when further increase the content of
carbon black in CE. These could be attributed to the in-
crease of sheet resistance (Rsr) and low lateral conductivity
of carbon CE, result in high series resistance of ss-DSCs.
Meanwhile, the small size carbon black particle would
diminish the pore in CE and cause pore filling degree de-
creased, which is an undesirable disturb in the perfor-
mance of ss-DSC. It has been reported that the strongest
deterioration is appeared in Jsc when the PFF decreases
[16]. However, Jsc display negligible variation when chang-
ing the CEs, indicating the different CEs have little effect on
PFF in this structure. As a result, adding a certain ratio of
carbon black into the graphite CE could dramatically en-
hance FF and the power conversion efficiency of the
spiro-OMeTAD based ss-DSC and the optimum ratio for
graphite to carbon black is 1:0.25.
The characterization of charge transfer at the interface
between the HTM and CE with different ratios of graphite
to carbon black was carried out with electrochemical
impedance spectra (EIS) analysis. The EIS transmission-line
model of solid-state HTM based cell has been proposed to
understand charge transfer processes by some groups [31–
33]. However, spiro-OMeTAD presents high transport
resistance and complicated electrochemical property in
Rsr/X Rct/X BET/m2 g1 Porosity/% Pore/Å
33.55 234.4 16.67 12.2 416.5
52.70 84.2 64.39 17.2 131.4
71.49 128.8 85.41 22.5 100.4
135.40 152.3 247.68 37.3 54.5
 M. Xu et al. / Organic Electronics 14 (2013) 628–634
Fig. 5. Electrochemical impedance spectra of CE/HTM/CE dummy symmetric cells with various ratios of graphite to carbon black CE; DC0 (1: 0), DC0.25 (1:
0.25), DC0.5 (1: 0.5), DC2 (1: 2). Inset: Equivalent circuit for the impedance spectrum, W: Nernst diffusion impedance; Rct: charge-transfer resistance; C:
double layer capacity; Rs: serial resistance.
the air under illumination, which makes the fitting model
too complex. Hence, we fabricate CE/HTM/CE dummy sym-
metric cells with the ratio of graphite to carbon black 1:0,
1:0.25, 1:0.5 and 1:2 (marked as device DC0, DC0.25, DC0.5
and DC2, respectively) as electrode. The EIS were measured
at frequency ranging from 100 mHz to 1 MHz under dark
condition and the Nyquist plot was presented in Fig. 5. It
could be found that two distinct frequency semicircles
are observed in the measured frequency range from
1  101 Hz to 1  106 Hz. The first arc at the high fre-
quency range of the Nyquist plot is assigned to the charge
exchange process between HTM and CE, demonstrating the
present of the RC network at the interface, which consists
of the charge transfer resistance (Rct) and constant phase
element (CPE). The CPE reflects the interfacial capacitance,
taking into account the roughness of the electrodes causing
a depression of the semicircle to an ellipse in the Nyquist
plots. The low frequency arc corresponds to transmission
resistance in the HTM, and the radiuses of the semicircles
display negligible variation in this investigation. It’s obvi-
ous that DC0 shows the highest value at the first arc, which
is up to 234.4 X. This is mainly caused by the low electro-
chemical active surface area of pure graphite electrode.
After the addition of carbon black, DC0.25, DC0.5, DC2 pre-
sents 84.2, 128.8 and 152.3 X, respectively. It’s interesting
that device DC0.25 exhibits the smallest radius at the first
arc and promises the lowest charge transfer resistance be-
tween CE and HTM. However, when the content of carbon
black further increases, Rct between CE and HTM is also in-
creased, which indicated that more carbon black will raise
charge transfer resistance and lead to a lower hole injec-
tion efficiency. This could be attributed that more carbon
black in carbon electrode would cause poor conductivity
and friable film. These results are in accordance with N2
adsorption/desorption analysis and I-V curves. This indi-
cates that the introduction of porous structure is an effi-
cient approach to improve the performance of CE, and
633
promises a tremendous potential for the DSC commercial
application with this monolithic ss-DSC containing low-
cost mesoscopic carbon CE.
Obviously, g of ss-DSC based on mesoscopic carbon CE
highly depends on the property of porous structure and
FF is the most significant influence parameter. In our work
g of ss-DSC was obtained after light soaking for dozens of
minutes and no significant drop was observed after one
week under the dark condition without any sealing protec-
tion. A promising efficiency up to 4.03% was obtained un-
der 1 sun (AM1.5 global, 100 mW cm2) with the
parameters Voc, Jsc, FF of 856 mV, 7.25 mA cm2, 0.65,
respectively, which is comparable to the efficiency ob-
tained by the conventional ss-DSC based on the noble CE
[12].
4. Conclusion
A low-cost carbon based screen printable electrode was
used to replace the conventional noble metal for the CE of
monolithic ss-DSC. The distance between the photoanode
and the counter electrode could be controlled precisely
by the thickness of spacer layer. IMVS characterization
demonstrated that electron lifetime is highly depends on
the thickness of insulating layer. The influence of meso-
scopic carbon CE to charge transfer process was investi-
gated by EIS with a dummy symmetric cell, indicating
that the porous structure had a significant effect in reduc-
ing the charge transfer resistance between HTM and CE.
With the optimal ratio of 1:0.25 between graphite and car-
bon black, a considerable efficiency of 4.03% was obtained
in the monolithic ss-DSC combining with spiro-OMeTAD
and the organic dye D102. Meanwhile, the process in con-
structing the device could be performed by full screen
printing technology, which shows the unique advantage
of reducing the preparation process cost. Further improve-
ments in the monolithic ss-DSC with this low-cost carbon
634 M. Xu et al. / Organic Electronics 14 (2013) 628–634
based screen printable cathodes could be expected by
selecting more suitable sensitizer and HTM.
Acknowledgements
This work was supported by the National Natural Sci-
ence Foundation of China (Grant No. 61106056), the Nat-
ure Science Foundation of Hubei Province (2008CDA042),
Scientific Research Foundation for Returned Scholars, Min-
istry 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].
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