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Environmental Science
Cite this: Energy Environ. Sci., 2012, 5, 6057
www.rsc.org/ees COMMUNICATION
High-efficiency dye-sensitized solar cell with a novel co-adsorbent†
Liyuan Han,*a Ashraful Islam,a Han Chen,a Chandrasekharam Malapaka,b Barreddi Chiranjeevi,b
Shufang Zhang,a Xudong Yangc and Masatoshi Yanagidaa
Received 9th December 2011, Accepted 3rd January 2012
DOI: 10.1039/c2ee03418b
Published on 04 January 2012 on http://pubs.rsc.org | doi:10.1039/C2EE03418B

A new record efficiency (11.4%) of dye-sensitized solar cell was alternative I
/I3
redox couple to improve open circuit voltage (VOC)
obtained by design and syntheses of donor–acceptor type co- and/or overcome the strong dip in the incident photon-to-electron
adsorbents which effectively overcome the competitive light conversion efficiency (IPCE) spectrum around 380 nm induced by the
competitive light absorption of triiodide,9–11 (iii) utilizing co-adsor-
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absorption by I
/I3
, avoid dye aggregation, and reduce the charge

recombination. This result was certified by a public research center bents to avoid the competitive adsorption and aggregation among
(AIST). dyes that may induce unfavorable charge or energy transfer and
quenching of photo-excited states,12–15 and (iv) utilizing additives to
reduce the recombination of electrons in the TiO2 film with I3
or
Dye-sensitized solar cells (DSCs) are promising next-generation other acceptor species.16 Unfortunately, in the past five years no
alternatives to conventional silicon-based photovoltaic devices owing efficiency has exceeded the certified highest value of 11.1%. In
to their low manufacturing cost and potentially high conversion contrast, certified efficiencies of more than 10% reported until now
efficiency.1,2 A typical DSC comprises a dye-sensitized nanocrystal- have all involved the use of black dye alone and I
/I3
redox
line titanium dioxide (TiO2) film deposited on a transparent con- couples.2,17–19 A feasible strategy for further improvement of the
ducting oxide (TCO) glass, a platinum (Pt) counter-electrode, and an efficiency is therefore the development of new compounds that can be
electrolyte solution with a dissolved I
/I3
ion redox couple. Until used as co-adsorbents in black dye based DSCs with advantageous
now, the certified champion efficiency of 11.1% was achieved,2 which characteristics for overcoming the aforementioned problems. The
is lower than that achieved with bulk silicon solar cells. In the ideal candidate for a co-adsorbent should have three characteristics:
approach to new record efficiency, much effort has been carried out (i) it should have a large molar extinction coefficient (3) in the infrared
to solve the problems that limit improvement, such as (i) utilizing region or around 400 nm to recover the dip in the IPCE spectra
efficient single or multi-sensitizers with broad light absorption spectra induced by I3
; (ii) the structure of the molecule should be suitable for
that extend into the visible and infrared regions,3–8 (ii) utilizing an avoiding competitive adsorption among dyes while effectively sup-
pressing the aggregation of dyes on the TiO2 surface; and (iii) it
a
Photovoltaic Materials Unit, National Institute for Materials Science, should be able to reduce the recombination of electrons in the TiO2
Tsukuba, Ibaraki, 305-0047, Japan. E-mail: HAN.liyuan@nims.go.jp; film with I3
and other acceptor species by the formation of a com-
Fax: +81 298592304; Tel: +81 298592747 pacted molecule monolayer covering the bare TiO2 surface.
b
Inorganic and Physical Chemistry Division, Indian Institute of Chemical In this work we successfully designed and synthesized two simple
Technology, Uppal Road, Tarnaka, Hyderabad, 500607, India
c
International Center for Young Scientists, National Institute for Materials donor–acceptor type co-adsorbents, denoted as Y1 and Y2, with
Science, Tsukuba, Ibaraki, 305-0047, Japan intense absorption maxima between 350 nm and 400 nm. We used
† Electronic supplementary information (ESI) available: Details of these co-adsorbents to improve the IPCE spectra by offsetting the
syntheses of the co-adsorbents. See DOI: 10.1039/c2ee03418b competitive visible light absorption due to I3
. Moreover, we

Broader context
The development of photovoltaic technology is expected to help solve problems related to energy shortages and environmental
pollution caused by the use of fossil fuels. Dye-sensitized solar cells (DSCs) fabricated with low-cost are regarded as one of the most
promising photovoltaic devices. However, the overall efficiency of I
/I3
based DSCs has been limited because light harvesting is not
fully achieved, and the photo-excited electrons always recombine with the acceptor species before the electrode collects them. Here,
we show the design and synthesis of a small donor–acceptor type co-adsorbent, which can effectively increase the short circuit
current by offsetting the competitive light absorption by I
/I3
and improve the open circuit potential by introducing butyloxyl
chains into the molecule to avoid dye aggregation and reduce the charge recombination. A certified new record efficiency of 11.4%
was achieved by using the novel co-adsorbent. This work illustrates a new pathway to achieve highly efficient DSCs for practical
applications.

This journal is ª The Royal Society of Chemistry 2012 Energy Environ. Sci., 2012, 5, 6057–6060 | 6057
 View Online

introduced butyloxyl chains into the Y1 molecule to adjust the of black dye (3 ¼ 1  104 M
1 cm
1) and I3
(3 ¼ 2.5  104 M
1 cm
1)
distance between dyes in order to study the effect of the structure of at this wavelength. Comparison to the molar extinction coefficients of
co-adsorbents on cell performance. I3
, Y1 and Y2 showed much higher light harvesting ability in this
Donor–p-acceptor (D–p-A) type compounds are particularly region. Hence we expected the loss of the light absorption by I3
to be
attractive because it is possible to readily tune their highest occupied suppressed by the use of co-adsorbent Y1 or Y2.
molecular orbital (HOMO) levels, lowest unoccupied molecular Recovering the dip in the black dye based IPCE spectra near 400
orbital (LUMO) levels, and other properties through a systematic nm due to the competitive absorption of light by I3
required that the
variation of the donor and acceptor units. We herein developed co-adsorbents could easily inject electrons from the co-adsorbents
simple and small D–p-A structure molecules, Y1 and Y2 (Fig. 1a). into the TiO2 film. The higher LUMO levels of Y1 (
2.96 eV) and Y2
The structural design of these molecules includes three key features: (
2.80 eV) compared to the TiO2 conduction band edge (
4.2 eV)
(i) butyloxyl-substituted phenyl as an electron-donating unit, thio- facilitated the injection of electrons from the co-adsorbents to the
phene as a p-spacer, and a cyanoacetic acid group as an acceptor and TiO2 film. The lower HOMO levels of Y1 (
5.82 eV) and Y2 (
6.00
anchor, the result being a Y1 molecule with a strong absorption eV) compared to the redox potential of I
/I3
(
5.1 eV) facilitated
Published on 04 January 2012 on http://pubs.rsc.org | doi:10.1039/C2EE03418B

around 400 nm that could compensate for the short wavelength dip in electron transfer from I
to the co-adsorbents.
the IPCE spectrum; (ii) a fluorine-substituted phenylene as a weak The cell with only black dye had a broad IPCE spectrum extending
donor was used in molecule Y2 to hypsochromically shift the across the whole visible range and into the near-IR region as far as
absorption peak to a wavelength region similar to that of I3
; (iii) two 950 nm and displayed the highest IPCE value (81%) in the wave-
butyloxyl groups were added in Y1 to avoid dye aggregation; and (iv) length range from 600 to 700 nm (Fig. 2), suggesting that electrons are
the molecular sizes of both Y1 and Y2 are smaller than the black dye efficiently collected in the cell which is well fabricated. As mentioned
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molecule and it makes them suitable for compact monolayer above, the decrease of the IPCE to 43% in the wavelength range
formation through covering the bare TiO2 surface during the dye 350–450 nm was due to competitive light absorption between I3
and
uptake process. For these reasons molecules Y1 and Y2 were suitable the black dye. Addition of Y1 restored the dip in the IPCE spectrum
as co-adsorbents for the black dye. more efficiently than Y2, which is in agreement with the IPCE spectra
The co-adsorbents Y1 and Y2 showed strong absorptions near 390 of devices with Y1 and Y2 alone respectively (Fig. S1†). This fact
nm and 360 nm, respectively (Fig. 1b). We assigned these absorptions indicated that the co-adsorbents had adsorbed onto the TiO2 surface
to the intramolecular charge transfer between the donors and the with efficient electron injection. Addition of co-adsorbent Y1 for the
acceptors in the co-adsorbents. Y2 with a substituted fluorine showed cell with black dye enhanced the platform of the IPCE over a large
the same absorption peak as I3
, whereas the absorption peak of Y1 spectral region at wavelengths from 300 nm to 700 nm. This result
with a substituted butyloxyl shifted to 390 nm because of the electron- was consistent with the absorption spectrum of Y1. However, in the
donating properties of the butyloxyl groups. The peak molar cell with co-adsorbent Y2, the enhancement occurred only in
extinction coefficients (3) of Y1 and Y2 were 3.0  104 M
1 cm
1 and a narrow range of wavelength from 350 nm to 420 nm. We attributed
3.1  104 M
1 cm
1, respectively, which are much higher than those this difference in the effects of co-adsorbents Y1 and Y2 to their
different light-harvesting properties. In contrast, in the spectral region
from 700 to 900 nm, the IPCE spectrum of the black dye did not
change after addition of the co-adsorbents. This result indicated that
the co-adsorbents competitively adsorbed and/or interacted with the
black dye to a negligible extent. These results suggest that it is possible
to achieve a high IPCE in the visible and infrared wavelength region
by developing suitable co-adsorbents with strong light absorption.
Addition of co-adsorbent Y1 effectively improved the conversion
efficiency (h) of the DSC up to 11.3% with a JSC of 20.88 mA cm
2
and VOC of 0.743 V (Table 1). Compared to the cell sensitized by

Fig. 1 Properties of co-adsorbents. (a) The chemical structure of co-

adsorbents. (b) UV-visible absorption spectra of co-adsorbent Y1 Fig. 2 Incident photon-to-electron conversion efficiency (IPCE) spectra.
(dashed-dotted line), Y2 (dashed line) and triiodide (solid line) in ethanol IPCE spectra of DSCs with co-adsorbent Y1 (dashed-dotted line), with
solutions. co-adsorbent Y2 (dashed line) and without co-adsorbent (solid line).

6058 | Energy Environ. Sci., 2012, 5, 6057–6060 This journal is ª The Royal Society of Chemistry 2012
 View Online

Table 1 The current–voltage performance dataa of DSCs sensitized by black dye without co-adsorbent, with co-adsorbent Y1 or Y2 measured under
one sun simulated sunlight (air mass 1.5)

Sample JSC/mA cm
2 VOC/mV FF h (%)

Black dye 20.45  0.06 727  2 0.720  0.002 10.70  0.02

Black dye + Y1 20.88  0.07 743  4 0.727  0.002 11.28  0.06
Black dye+ Y2 20.60  0.06 706  6 0.706  0.006 10.28  0.13
a
The standard deviation is calculated based on 4 samples and measured twice for the same cell composition and fabrication procedure.

black dye alone, addition of the co-adsorbents increased the JSC value
corresponding to the IPCE spectra. Interestingly, there was about
Published on 04 January 2012 on http://pubs.rsc.org | doi:10.1039/C2EE03418B

a 20 mV enhancement of the VOC in the cell with co-adsorbent Y1

compared to the cell with black dye only, whereas in the case of
addition of Y2, the VOC is decreased.
The VOC value of a DSC is related to the energy level of the TiO2
conduction band (ECB) and the conduction band electron density (n)
in the TiO2 film. The VOC can be described as follows:
 
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kB T n
VOC ¼ ln (1)
q n0
where kB is the Boltzmann constant, T is the temperature (K), q is the
elementary charge, and n0 can be estimated under vacuum conditions
as follows:
  Fig. 4 Current–voltage characteristics of DSC with black dye and co-
ECB
Eredox
n0 ¼ NC exp (2) adsorbent Y1. Results were measured at 25  C with an aperture area of
kB T
0.231 cm2 by using a black metal mask and an irradiance of 100.0 mW
where NC is the density of conduction band states and Eredox is the cm
2. Short circuit current density JSC ¼ 21.3 mA cm
2; open circuit
potential of redox species (I
/I3
). From eqn (1) and (2) we can voltage VOC ¼ 743 mV; fill factor FF ¼ 72.2%; and efficiency ¼ 11.4%.
deduce that a shift of ECB or change of the electron lifetime (s) in The upper line and lower line indicate current and power, respectively.
This measurement was independently carried out by the Research Center
TiO2 will influence the VOC because the electron density is correlated
for Photovoltaics, AIST.
with the electron lifetime. To understand the different effects of the
co-adsorbents on the VOC, we measured ECB with the charge
extraction method (CEM)20 (shown as Fig. S2 in the ESI†). We increasing electron density in a manner consistent with a power law
found that ECB was not affected by Y1 and Y2. Therefore we should relationship. At a certain charge density, the electron lifetime was
attribute the different effects of Y1 and Y2 on VOC to the influence of larger in the cell with co-adsorbent Y1 than in the cell without co-
electron lifetime, which is related to the charge recombination adsorbent and in the cell with co-adsorbent Y2. This result suggested
process. We derived the electron lifetime s as a function of the elec- that adsorption of Y1 onto the free area of the TiO2 surface exposed
tron density (Fig. 3) with the use of intensity-modulated photovoltage to the redox electrolyte had resulted in the formation of a compacted
spectroscopy (IMVS).21 The electron lifetime decreased with monolayer that could effectively suppress the recombination of
electrons in the TiO2 film with I3
, with a resultant improvement of
the VOC. This result also revealed that butyloxyl chains in the
molecular structure of the co-adsorbent played an important role in
improving the VOC. The successful exploitation of co-adsorbent Y1
provided us with a new direction for developing novel materials that
can increase not only the VOC but also the IPCE in the IR wavelength
region to further enhance solar cell efficiency.
Finally, the Research Center for Photovoltaics, the National
Institute of Advanced Industrial Science and Technology (AIST,
Japan), independently certified the current–voltage characteristics.
We achieved an overall conversion efficiency of 11.4% (Fig. 4), which
is a new record efficiency confirmed by a public test center.

Conclusions
Fig. 3 Lifetime (s) of electrons versus electron density. The s in DSCs
sensitized by black dye with co-adsorbent Y1 (open squares), without co- We succeeded in designing and synthesizing two small, simple donor–
adsorbent (open triangles) and with co-adsorbent Y2 (open circles) were acceptor type co-adsorbents. The novel co-adsorbent Y1 distin-
derived by using intensity-modulated photovoltage spectroscopy. guished itself by integration of three advantages into one small and

This journal is ª The Royal Society of Chemistry 2012 Energy Environ. Sci., 2012, 5, 6057–6060 | 6059
 View Online

simple molecule: offsetting the competitive visible light absorption photoelectron spectrometer surface analyzer under atmosphere with
due to I3
, adjusting the distance between dyes to avoid aggregation, a 0.2 ml min
1 N2 flow.
and reducing the recombination of electrons in the TiO2 film. The
distinct properties of co-adsorbent Y1 enabled DSCs sensitized with
black dye to perform with high efficiency. Both JSC and VOC values
Acknowledgements
were simultaneously higher in the cell with co-adsorbent Y1. A public This work was financially supported by Core Research for Evolu-
research center (AIST) certified the cell’s efficiency to be 11.4%, a new tional Science and Technology (CREST) of the Japan Science and
DSC efficiency record. These results emphasize the importance of the Technology Agency. We thank Dr Surya Prakash Singh and Dr
strategy that integrates multiple functions into one co-adsorbent to Chuanjiang Qin for useful help.
improve the device performance and will facilitate further improve-
ment of efficient DSCs through the enhancement of the IPCE in the
IR wavelength region. Notes and references
1 B. O’Regan and M. Gr€atzel, Nature, 1991, 353, 737–740.
Published on 04 January 2012 on http://pubs.rsc.org | doi:10.1039/C2EE03418B

2 Y. Chiba, A. Islam, Y. Watanabe, R. Komiya, N. Koide and L. Han,

Experimental Jpn. J. Appl. Phys., 2006, 45, L638.
All reagents were purchased from Sigma-Aldrich and Alfa Aesar. 3 S. Gao, A. Islam, Y. Numata and L. Han, Appl. Phys. Express, 2010,
3, 062301.
The 1H NMR and 13C NMR spectra of solutions in CDCl3 and 4 A. Islam, F. A. Chowdhury, Y. Chiba, R. Komiya, N. Fuke, N. Ikeda
DMSO were recorded on 300 and 500 MHz NMR spectrometers. and L. Han, Chem. Lett., 2005, 34, 344–345.
Chemical shifts were referenced relative to tetramethylsilane. Mass 5 R. Y. Ogura, S. Nakane, M. Morooka, M. Orihashi, Y. Suzuki and
Downloaded by SLUB DRESDEN on 13 April 2012

K. Noda, Appl. Phys. Lett., 2009, 94, 073308.

spectra were recorded on a Shimadzu Biotech MALDI-MS mass 6 J. Yum, E. Baranoff, S. M. Wenger, K. Nazeeruddin and M. Gr€atzel,
spectrometer. Absorption spectra were recorded on a Shimadzu Energy Environ. Sci., 2011, 4, 842–857.
model 3100 UV-Vis-NIR spectrophotometer. 7 R. Li, J. Liu, N. Cai, M. Zhang and P. Wang, J. Phys. Chem. B, 2010,
Nanocrystalline TiO2 films were prepared by using a variation of 114, 4461–4464.
8 B. E. Hardin, A. Sellinger, T. Moehl, R. Humphry-Baker,
a reported method.22 TCO sheet glass electrodes (Nippon Sheet Glass J.-E. Moser, P. Wang, S. M. Zakeeruddin, M. Gr€atzel and
Co., Japan) with a sheet resistance of 8–10 ohm
2 and an optical M. D. McGehee, J. Am. Chem. Soc., 2011, 133, 10662–10667.
transmission of greater than 80% in the visible range were used. The 9 M. Wang, N. Chamberland, L. Breau, J. Moser, R. Humphry-Baker,
B. Marsa, S. M. Zakeeruddin and M. Gr€atzel, Nat. Chem., 2010, 2,
TiO2 thin films of approximately 25 mm thickness (area: 0.25 cm2) 385–389.
were deposited onto the conducting glass by screen-printing. The 10 H. Nusbaumer, J. Moser, S. M. Zakeeruddin, M. K. Nazeeruddin and
films were then sintered at 500  C for 1 hour. The thickness of films M. Gr€atzel, J. Phys. Chem. B, 2001, 105, 10461–10465.
was measured with a Surfcom 1400A surface profiler (Tokyo Sei- 11 H. Tiana and L. Sun, J. Mater. Chem., 2011, 21, 10592–10601.
12 K. Kalyanasundaram and M. Gr€atzel, Coord. Chem. Rev., 1998, 77,
mitsu Co. Ltd.). The films were further treated with 0.1 M HCl 347–414.
aqueous solutions before examination.23 The dye solution is a mixture 13 M. Ikeda, N. Koide, L. Han, A. Sasahara and H. Onishi, Langmuir,
of black dye [tri(thiocyanato)(4,40 ,400 -tricarboxy-2,20 :60 ,200 -terpyr- 2008, 24, 8056–8060.
14 J. He, G. Benk€ 
o, F. Korodi, T. Polıvka, R. Lomoth, B. Akermark,
idine) ruthenium(II)] and co-adsorbent Y1 or Y2 in 0.2 mM respec-
L. Sun, A. Hagfeldt and V. Sundstr€ om, J. Am. Chem. Soc., 2002,
tively with addition of deoxycholic acid at a concentration of 20 mM. 124, 4922–4932.
To be specific, the cell performance is optimum when the molar ratio 15 A. Morandeira, I. L opez-Duarte, B. O’Regan, M. V. Martınez-Dıaz,
of black dye to Y1 or Y2 was 1 : 1. The TiO2 films were immersed in A. Forneli, E. Palomares, T. Torres and J. R. Durrant, J. Mater.
Chem., 2009, 19, 5016–5026.
the above solutions and then kept at 25  C for 30 hours. The dye- 16 H. Wang, M. Liu, M. Zhang, P. Wang, H. Miura, Y. Chenga and
deposited TiO2 film and a platinum-coated conducting glass were J. Bell, Phys. Chem. Chem. Phys., 2011, 13, 17359–17366.
separated by a Surlyn spacer (40 mm thick) and sealed by heating the 17 M. K. Nazeeruddin, P. Pechy, T. Renouard, S. M. Zakeeruddin,
polymer frame. An electrolyte consisting of a solution of 0.6 M B. Humphry, P. Comte, P. Liska, L. Cevey, E. Costa, V. Shklover,
L. Spiccia, G. B. Deacon, C. A. Bignozzi and M. Gr€atzel, J. Am.
dimethylpropyl-imidazolium iodide, 0.05 M I2, 0.1 M LiI and 0.4 M Chem. Soc., 2001, 123, 1613–1624.
tert-butylpyridine in acetonitrile was used in all the cells. 18 M. Yanagida, N. Onozawa-Komatsuzaki, M. Kurashige, K. Sayama
The current–voltage characteristics were measured using a black and H. Sugihara, Sol. Energy Mater. Sol. Cells, 2009, 94, 297–302.
19 H. Arakawa, T. Yamaguchi, A. Takeuchi and S. Agatsuma, Proc. 4th
metal mask with an aperture area of 0.231 cm2 under standard air World Conference on Photovoltaic Energy Conversion (WCPEC-4,
mass 1.5 sunlight (100 mW cm
2, WXS-155S-10: Wacom Denso Co. Hawaii), 2006, vol. 1, p. 36.
Japan).24 Monochromatic incident photon-to-current conversion 20 N. W. Duffy, L. M. Peter, R. M. G. Rajapakse and
efficiency spectra were measured with a monochromatic incident light K. G. U. Wijayantha, J. Phys. Chem. B, 2000, 104, 8916–8919.
21 G. Schlichthoerl, S. Y. Huang, J. Sprague and A. J. Frank, J. Phys.
of 1  1016 photons cm
2 in director current mode (CEP-2000BX, Chem. B, 1997, 101, 8141–8155.
Bunko-Keiki). The electrochemical impedance spectra were obtained 22 P. Wang, S. M. Zakeeruddin, P. Comte, R. Charvet, R. Humphry-
under one sun illumination with a potentiostat (Solartron1287) Baker and M. Gr€atzel, J. Phys. Chem. B, 2003, 107, 14336–
equipped with a frequency response analyzer (Solartron1255B) under 14341.
23 Z. S. Wang, T. Yamaguchi, H. Sugihara and H. Arakawa, Langmuir,
a frequency ranging from 10
1 to 106 Hz. The photoemission yield 2005, 21, 4272–4276.
curves were measured with a Riken Keiki Co. Ltd. model AC-3 24 N. Koide and L. Han, Rev. Sci. Instrum., 2004, 75, 2828–2831.

6060 | Energy Environ. Sci., 2012, 5, 6057–6060 This journal is ª The Royal Society of Chemistry 2012