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Titanium dioxide (TiO2) photoelectrodes with micro/nano hier- lytes compared to pure nanostructured films. Hierarchical
archical branched inner channels have been prepared by an elec- branched channels in the photoanodes can efficiently improve
trohydrodynamic (EHD) technique and assembled to form dye- the transport properties of redox-active species in viscous electro-
sensitized solar cells (DSSCs). Excellent penetration of ionic-liquid lytes, which is demonstrated by electrical impedance spectrosco-
electrolytes and enhanced light harvesting in the longer wave- py (EIS). The incident monochromatic photon-to-electron conver-
length region are realized within the composite-structure elec- sion efficiency (IPCE) shows that enhanced light scattering in the
trode, thus a better fill factor (ff) of 75.3 % and higher conversion composite film is of benefit for light harvesting and thus for solar
efficiency (h) of 7.1 % are obtained for viscous ionic-liquid electro- energy conversion efficiency.
Introduction
Dye-sensitized solar cells (DSSCs) have attracted much atten- As reported recently, TiO2 photoelectrodes prepared by the
tion as promising low-cost and relatively efficient devices for electrospraying method had higher photocurrents than con-
the photovoltaic conversion of solar energy.[16] Device perfor- ventional photoelectrodes because of better ionic paths in the
mance, that is, light-to-electricity conversion efficiency, is deter- TiO2 layer.[24] In our previous work, micro/nano composite pho-
mined by light collection efficiency, which is directly related to toanodes fabricated by the electrohydrodynamic technique
a given systems capability for charge separation and charge showed both better fill factors and better conversion efficiency
transport. With organic liquid electrolytes, which have high for quasi-solid-state DSSCs.[25] However, the essence of this
charge drift mobility, over 10 % conversion efficiency was ob- phenomenon was not clearly understood. Herein, instead of
tained for DSSCs,[7, 8] whereas the devices sealing and long- using the P25 TiO2 that we used as photoanode material in our
term stability with liquid electrolytes remain an important previous work, hydrothermal-synthesized anatase TiO2 nano-
issue in view of the practical application. Consequently, nonvo- particles are employed, for which a higher conversion efficien-
latile viscous ionic-liquid/polymer electrolytes, quasi-solid-state cy of 7.1 % and a fill factor of 75.3 % are attained for hierarchi-
electrolytes, and solid-state electrolytes[917] have been intro- cal thin films containing branched inner channels with viscous
duced to replace the organic liquid electrolytes. However, su- ionic-liquid electrolyte. The influence of charge transport and
perior penetration of these new electrolytes into the nanocrys- light scattering in the micro/nano composite films are investi-
talline network structure and the quick charge transport as in gated and compared to nanostructured films with and without
pure nanostructured films cannot be realized easily. On the hollow spherical voids. The EIS measurements indicate that ion
other hand, the photocurrent can be improved by increasing
the light-collection efficiency. Much effort has gone into the [a] Dr. Y. Zhao, Dr. X. Sheng, Prof. J. Zhai, Prof. L. Jiang, Prof. C. Yang,
Dr. Z. Sun, Prof. Y. Li, Prof. D. Zhu
synthesis of various sensitizers to enhance the spectral re-
Center for Molecular Science, Institute of Chemistry
sponse.[18, 19] While tuning film morphology, such as coupling Chinese Academy of Sciences
the photonic crystal layer to the electrode as a dielectric Fax: (+ 86) 10-8262-7566
mirror,[20] introducing hollow sphere voids[21] and large solid E-mail: zhaijin@iccas.ac.cn
particles[22, 23] as scattering centers is also an efficient way to [b] Dr. Y. Zhao, Dr. X. Sheng
Graduate School of the Chinese Academy of Science
improve light harvesting, and with it, conversion efficiency.
Chinese Academy of Sciences
Therefore, with porous photoanodes, where favorable penetra- Beijing 100080 (P. R. China)
tion effects of viscous and solid electrolytes predominate, fast [**] For High-Efficiency Solar Cells.
charge transport and effective light collection are attractive tar- Supporting information for this article is available on the WWW under
gets for researchers. http://www.chemphyschem.org or from the author.
856 @ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim ChemPhysChem 2007, 8, 856 861
TiO2 Porous Electrodes
ChemPhysChem 2007, 8, 856 861 @ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.chemphyschem.org 857
J. Zhai et al.
Figure 3. Schematic depiction of the pore structure of electrodes. a) Elec- versus voltage (IV) curves of DSSCs based on different photo-
trode 1; b) magnified view of a section of electrode 1; c) electrode 2; d) elec- anodes with viscous electrolyte. Three to four devices for every
trode 3 (thick line: microchannel; thin line: nanochannel). type of photoanode were tested. Table 1 summarizes the pho-
toelectrical parameters and the deviation of each average
value. The data in parentheses in Table 1 are the highest
specialties. Figure 3 a shows the micro/nano composite film values, which are shown here. The short-circuit photocurrent
formed by the EHD technique. Lots of sub-micropores are density (Jsc), open-circuit photovoltage (Voc) and fill factor (ff) of
formed among the interstices of TiO2 sub-microspheres, hence composite electrode 1 with viscous electrolyte A (see Experi-
forming the continuous microchannels (thick lines). Figure 3 b mental Section for composition) are 13.8 mA cm 2, 0.691 V, and
shows a magnified version of a section of Figure 3 a. Micro- 75.3 %, respectively, yielding an overall conversion efficiency of
spheres formed by the EHD method are composed of nanopar- 7.1 %. For electrode 2, based on pure nanostructured channels,
ticles. The nanopores between the nanoparticles form continu- the corresponding device parameters (Jsc, Voc, ff, and h) are
ous nanochannels (thin lines). The hierarchical branched inner 13.0 mA cm 2, 0.636 V, 68.4 %, and 5.7 %, respectively. For elec-
channels composed of continuous micropores (thick lines) and trode 3, containing hollow-sphere structures, the Jsc, Voc and ff
nanopores (thin lines) in electrode 1, like the blood circulation value are 12.5 mA cm 2, 0.645 V, and 72.8 %, respectively, h =
858 www.chemphyschem.org @ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim ChemPhysChem 2007, 8, 856 861
TiO2 Porous Electrodes
[a] Three or four devices for every type of photoanodes were tested. The
light intensity was 100 mW cm 2. The values reported here are the aver-
age data of four cells with deviations, while the maximum values are
given parentheses.
ChemPhysChem 2007, 8, 856 861 @ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.chemphyschem.org 859
J. Zhai et al.
Conclusions
A simple and effective hierarchical structure is introduced into
Figure 6. Measured diffuse reflectance of sensitized films. 1) electrode 1 with nanocrystalline thin films to provide a new way to improve
micro/nano composite structure. 2) nanostructured electrode 2. 3) elec-
charge transport and light harvesting, while a conversion effi-
trode 3 containing spherical voids.
ciency h = 7.1 % and a fill factor ff = 75.3 % were attained for
viscous electrolytes. This result means that photoelectrical per-
ing. After micro/nano composite structure is introduced into formance can be tuned by changing the composite porous
electrode 1, the scattering is enhanced clearly, and higher con- structure, which will give a good strategy for the fabrication of
version efficiency is obtained, because light-scattering macro- photoelectrodes suited for highly viscous electrolytes. The idea
pores are incorporated into the TiO2 thin film to extend the of film-structure modulation will provide a promising new way
photoresponse to red region. A photocurrent action spectrum to approach high-efficiency devices.
for electrodes 1 and 2 with ionic-liquid electrolyte A is shown
in Figure 7. Electrode 1 shows enhanced red-region absorption
as a result of light scattering. But it cannot be deduced that
Experimental Section
the improvement of photocurrent is only decided by the light- Preparation of Dye Sensitized Solar Cells: Two methods were em-
scattering effect; the better ionic diffusion may also decrease ployed to prepare TiO2 thin films. Method 1: Micro/nano composite
the loss of charge transport, resulting in better photocurrent electrode 1 was fabricated by the EHD technique.[25] The TiO2 col-
generation. loidal suspension was composed of ethanol (5 mL), poly(vinyl alco-
hol) (PVA, MW = 22,000) water solution (1 g, 33 wt %), titanium sol
The kinetics of ion transport and light-collection efficiency
(6.6 mL, 0.1 g mL 1; anatase TiO2 nano-particles were hydrothermal-
influence each other, and there must be a balance to achieve ly synthesized according to ref. [33]). The suspension was sprayed
the best photovoltaic performance. If the pores are too large, onto the conducting FTO glass slides with block layer (the prepara-
despite easy ion transport for viscous electrolytes and favora- tion method of which is described elsewhere[25]). Then, the TiO2
ble light-scattering, the thin films cannot absorb enough dye composite films were calcined at 450 8C for 1 hour in air. The
molecules for light harvesting; if the pores are too small, the whole EHD process was operated in air. Method 2: Nanostructured
transport kinetics of redox species limit the charge-transfer films (electrode 2) were prepared by the doctor blade technique,
rate, and the light-scattering effect is lost, even as the amount which employed the colloidal TiO2 suspension used above, spread-
ing it evenly onto the conducting glass. The 10-mm thin films were
of absorbed dye increases.[7, 32] As a result, electrode 3 shows
obtained after repeating the above procedure several times. The
the strongest scattering effect among the three types of thin nanostructured electrodes with hollow spheres (electrode 3) were
films, but it does not obtain the highest conversion efficiency. prepared according to ref. [21]: Monodisperse polystyrene (PS)
This can be ascribed to the decrease of surface area and light spheres with a radius of 200 nm were dispersed in the TiO2 colloi-
loss owing to back scattering arising from the presence of dal suspension used as above in a ratio of 1: 20 by weight using
860 www.chemphyschem.org @ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim ChemPhysChem 2007, 8, 856 861
TiO2 Porous Electrodes
an ultrasonic bath. the doctor blade method was used to prepare [4] M. Adachi, Y. Murata, J. Takao, J. T. Jiu, M. Sakamoto, F. M. Wang, J. Am.
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[11] Y. Shibata, T. Kato, T. Kado, R. Shiratuchi, W. Takashima, K. Kaneto, S.
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Hayase, Chem. Commun. 2003, 21, 2730 2731.
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the devices were measured using an electrochemical analyzer Benkstein, J. van de Lagemaat, A. J. Frank, J. Am. Chem. Soc. 2003, 125,
(CHI630B, Chenhua Instruments Co., Shanghai) under 100 mW cm 2 6306 6310.
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the solar cell was 0.20 cm2. [24] M. Fujimoto, T. Kado, W. Takashima, K. Kaneto, S. Hayase, J. Electrochem.
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This work was supported by Special Research Foundation of the
[27] R. Gomez, P. Salvador, Sol. Energy Mater. Sol. Cells 2005, 88, 377 388.
National Natural Science Foundation of China (50533030, [28] K. Hara, T. Horiguchi, T. Kinoshita, K. Sayama, H. Sugihara, H. Arakawa,
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Zhengzhong Yang at the Institute of Chemistry, Chinese Academy
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ChemPhysChem 2007, 8, 856 861 @ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.chemphyschem.org 861