Table of Contents Author Guidelines Submit a Manuscript
Journal of Nanomaterials
Volume 2008, Article ID 271631, 4 pages
Research Article

Low-Temperature Preparation of Amorphous-Shell/ Nanocrystalline-Core Nanostructured Electrodes for Flexible Dye-Sensitized Solar Cells

1Department of Chemical and Materials Engineering, University of Cincinnati, Cincinnati, OH 45221-0012, USA
2Institute of Micro and Nano Science and Technology, Shanghai Jiaotong University, Shanghai 200240, China
3Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 10080, China
4The Institute for Advanced Materials and Nano Biomedicine, Tongji University, 67 Chifeng Road, Shanghai 200092, China

Received 2 June 2007; Accepted 26 February 2008

Academic Editor: Hongchen Gu

Copyright © 2008 Dongshe Zhang et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.


An amorphous shell/nanocrystalline core nanostructured electrode was prepared at low temperature, in which the mixture of powder and aqueous solution was used as the paste for coating a film and in this film amorphous resulted from direct hydrolysis of at sintering was produced to connect the particles forming a thick crack-free uniform nanostructured film (12  m), and on which a photoelectrochemical solar cell-based was fabricated, generating a short-circuit photocurrent density of 13.58  , an open-circuit voltage of 0.647 V, and an overall 4.48% light-to-electricity conversion efficiency under 1 sun illumination.

1. Introduction

Dye-sensitized solar cells (DSSCs) [13] have been extensively studied more than a decade because they presented high-efficient, cost-effective, and environmentally friendly advantages. In the cell dye-sensitized semiconductor, photoelectrode plays an essential role, and conventionally nanocrystalline porous TiO2 electrode is prepared by coating a paste containing organic additives on a rigid conductive glass substrate, following a procedure of high-temperature sintering to remove the organic additives [1, 2], which are necessary to form a thick crack-free uniform film and optimize the microstructure of the electrode for photosensitization [14].

Flexible DSSCs [514], based on the substrates of indium tin oxide (ITO) coated polyethylene terephthalate (PET), or polyethylene naphthalate (PEN) substituting for rigid glass substrates, are regarded as one possible breakthrough in the field of DSSC regarding their commercialization, because flexible DSSCs have presented great advantages of low cost of production and wide application. Conductive plastic substrates, such as ITO/PET or ITO/PEN, can be processed by a continuous process like roll-to-roll production for porous nanocrystalline film coating, therefore, greatly decreasing the production cost of the solar cells. Meanwhile, flexible DSSCs can become part of a variety of every-day products and turn them into energy sources. The possibility to produce the flexible DSSCs in any shapes would open almost endless opportunities to the designers of such products. In addition, it is light weight, having portable character.

Underlying the flexible DSSCs, the necessary low-temperature preparation of porous nanocrystalline metal oxides semiconductor films has been a well-highlighted and on-going challenge up to today, because the conventional method of high-temperature preparation cannot be applied to prepare films on flexible plastic substrates, which only endure temperature of up to around 150°C. So far, there have been a number of efforts concerned with the preparation of nanoporous films at low temperature. The methods reported were low-temperature heating [5, 6], compression [7, 8], microwave irradiation [9, 10], electron-beam annealing [11] and chemical-vapor deposition with UV irradiation [12], and hydrothermal crystallization [13, 14]. However, the conversion efficiencies of the flexible DSSCs achieved so far are lower than those obtained by high-temperature sintering. One main reason is that low-temperature films have low level of crystallization of interconnection between particles comparing with high-temperature film [514]. It is showed that low-temperature film has poor interconnection between nanocrystalline particles, because the above-mentioned methods that have been developed so far cannot result in as perfect interconnection as high-temperature sintering did [514]. In fact, the part of low level of crystallization worked as the interconnection of nanocrystalline particles in the low-temperature film existed in all flexible DSSCs. So the part of low level of crystallization in the low-temperature film played an important role in the chemical reaction at interface of the cell. To well understand how it works and further improve the performance of low-temperature film, therefore, in this study, we developed a simple method and prepared an amorphous shell/nanocrystalline core nanostructured film under 100°C sintering. The amorphous shell not only is responsible for the interconnection between nanocrystalline particles, but also plays an important role in the interface chemical reaction. The as-prepared films were mechanically stable. It is showed that amorphous TiO2 can work effectively in DSSCs. Its performance was compared with that of nanocrystalline porous film prepared at both high and low temperature.

2. Experimental

Nanostructured TiO2 electrode with the structure of amorphous shell/nanocrystalline core was prepared by the following method. 0.8 g P25 (Degussa, Germany, 30% rutile and 70% anatase, BET surface area 55 m2/g, particle size 25 nm) and 0.5 M TiCl4 water solution were ground in an agate mortar for about 2 hours to get viscous paste, then coated on the fluorine doped SnO2-coated conductive glass (sheet resistance ca. 10  ) by doctor-blade technique. Subsequently, the film was sintered at 100°C for 12 hours. The resulting film thickness was 12 μm but can be varied by changing the paste concentration or the adhesive tape thickness. The electrode was directly immersed in an ethanol solution of cis-bis(4, -dicarboxy-2, -bipyridine)bis(thiocyanato)ruthenium(II), N3 dye (0.05 mM) overnight at room temperature. This dye-sensitized electrode was employed as a working electrode and platinized conductive glass as a counter electrode for assembling a sandwich-type dye cell. The electrolyte was 0.5 M KI and 0.03 M I2 in ethylene carbonate-acetonitrile (4 : 1 by volume). No special efforts were made to optimize the composition of the electrolyte. Photoelectrochemical measurements were performed on the TiO2 film electrodes under white light illumination by a 500 W Xe lamp equipped with IR and <420 nm cutoff filters from the side of the conductive glass back contact. Surface morphology of the electrode was observed by a Topcon ABT-150FS scanning electron microscope (SEM). X-ray diffraction patterns (XRD) of the electrodes were measured by a Rigaku RAD-2R using Cu Kα radiation at 40 kV and 20 mA by scanning at 2° 2θ min-1.

3. Results and Discussion

The SEM photographs of the TiO2 electrodes before and after sintering at low temperature of 100°C are presented in Figure 1. It revealed morphological homogeneity of both electrodes with micropores and interconnected particles, but before sintering at low temperature of 100°C the average particle size was approximately like the one of P25, while after sintering it was increased obviously and the connection between particles was also improved. The XRD patterns of the TiO2 electrodes before and after sintering at low temperature of 100°C are shown in Figure 2. No new peak was observed after sintering at low temperature of 100°C and, even both the relative intensity and line width of crystal peak were not changed before and after sintering, showing neither new compound nor crystal TiO2 was formed in the film during the sintering. According to the Scherrer equation [ λ/B(2θ) cosθ, where L is the crystallite size and B(2θ) is the line width] together with the results of XRD measurement, the crystal size should not be changed before and after sintering at low temperature of 100°C. Therefore, it conflicted with the results of SEM measurement. Figure 2 also shows XRD pattern of TiO2 resulted from 0.5 M TiCl4 water solution sintered at 100°C for 12 hours. From Figure 2, one can see no any crystal TiO2 peaks were observed, showing that amorphous TiO2 was formed during the sintering. So we can think that in the film TiCl4 was condensed at the surface of the crystal TiO2 of P25 before sintering and, during the sintering at low temperature of 100°C amorphous TiO2 resulted from TiCl4 grew on the surface of crystal TiO2 of P25 forming amorphous shell/nanocrystalline core particles, resulting in increments of the sizes of particles as well as improvement of the connection between particles in the film. So the formed electrode was crack free, robust, and uniform.

Figure 1: SEM photographs of the TiO2 electrodes (a) before and (b) after sintering.
Figure 2: XRD patterns of the TiO2 electrodes (a) before and (b) after sintering as well as (c) the TiO2 resulted from 0.5 M TiCl4 water solution sintered at 100°C for 12 hours (small peaks resulted from SnO2 conductive glass).

The amount of adsorbed N3 dye on the nanostructured TiO2 electrode was  mol/cm2,2 and from this data the calculated surface roughness factor was about 1000,15 showing that the electrode had large surface area and the dye of N3 can also strongly adsorb on the amorphous TiO2 surface. The photocurrent-voltage characteristic of the cell based on this nanostructured TiO2 electrode after sintering at low temperature of 100°C is presented in Figure 3. Under 1 sun illumination, a short-circuit photocurrent density (Isc) of 13.58 mA/cm2, an open-circuit voltage (Voc) of 0.647 V, and a fill factor of 51% were obtained, yielding an overall 4.48% light-to-electricity conversion efficiency. Figure 4 shows the dependence of Voc on illumination intensity. Within the range of the measurement the open-circuit voltage versus incident light intensity was a liner relationship and its slope was 130 mV per decade, yielding a rectification coefficient of 2.5. This value was higher than that of 1 to 2 [1517] of dye-sensitized solar cell based on the nanocrystalline TiO2 electrode sintered at 450°C for 30 minutes, meaning the density of surface state in this amorphous electrode was higher which may result in larger recombination [15]. However, this value was lower than that of 3.2 [5] of the cell based on TiO2 electrode sintered at 100°C for 24 hours, showing that amorphous TiO2 improved the connection between particles in the film and decreased some recombination therefore, larger Isc and conversion efficiency was observed. All these experiments showed that the dye of N3 can inject electrons into amorphous TiO2 effectively and the recombination rate was lower and amorphous TiO2 can also collect and transport electrons effectively. Therefore, the cell based on the amorphous shell/nanocrystalline core nanostructured TiO2 electrode prepared at low temperature had high-conversion efficiency up to 4.48%. However, when this amorphous electrode was further sintered at 450°C the amorphous became into well crystal, which was confirmed by XRD measurement of TiO2 from the decomposition of TiCl4 with 450°C sintering. A DSSC based on it presented a short-circuit photocurrent density of 20.2 mA/cm2, an open-circuit voltage of 0.69 V, and a fill factor of 51% were obtained, yielding an overall 7.1% light-to-electricity conversion efficiency under 1 sun illumination. Obviously, both photocurrent and photovoltage were improved with the improvement of the level of nanocrystalline interconnection, suggesting that amorphous interconnection has lower collection efficiency of electrons and higher recombination rates of electrons. The unchanged fill factor implies that amorphous interconnection has close resistance in the real cell when it works. The lower photocurrent and photovoltage should come from the higher surface states in the amorphous shell which worked as interconnection.

Figure 3: Photocurrent-voltage characteristic of a cell based on the amorphous shell/nanocrystalline core nanostructured TiO2 electrode after sintering. Light intensity was 100 mW/cm2. Electrode area was 0.28 cm2.
Figure 4: Open circuit voltage as a function of incident light intensity for N3-sensitized amorphous shell-nanocrystalline core nanostructured TiO2 electrode.

In summery, amorphous TiO2 can effectively work as interconnection to form robust nanostructured films, however, it is not effective for electron collection. It presented large recombination rate of electrons comparing with nanocrystalline porous films with nanocrystalline interconnection. It is suggested that low-temperature preparation methods should improve the crystal lever of the interconnection, which plays essential roles in the forming of film and chemical reaction in the interface, while it is not easy to achieve at low temperature. The flexible DSSCs would present as high conversion efficiency as that of sintered DSSCs when it would be achieved.


The research fund from Chemat Technology Inc. is acknowledged. Donglu Shi and Lifeng Li are grateful to the support from the Chinese Academy of Sciences, and Chinese Oversea Outstanding Scholar Foundation (2005-2-9).


  1. B. O'Regan and M. Grätzel, “A low-cost, high-efficiency solar cell based on dye-sensitized colloidal TiO2 films,” Nature, vol. 353, no. 6346, pp. 737–740, 1991. View at Publisher · View at Google Scholar
  2. M. K. Nazeeruddin, A. Kay, I. Rodicio et al., “Conversion of light to electricity by cis-X2bis(2,2'-bipyridyl-4,4'-dicarboxylate)ruthenium(II) charge-transfer sensitizers (X = Cl-,Br-,I-,CN-, and SCN-) on nanocrystalline TiO2 electrodes,” Journal of the American Chemical Society, vol. 115, no. 14, pp. 6382–6390, 1993. View at Publisher · View at Google Scholar
  3. T. Yoshida, K. Terada, D. Schlettwein, T. Oekermann, T. Sugiura, and H. Minoura, “Electrochemical self-assembly of nanoporous ZnO/Eosin Y thin films and their sensitized photoelectrochemical performance,” Advanced Materials, vol. 12, no. 16, pp. 1214–1217, 2000. View at Publisher · View at Google Scholar
  4. C. J. Barbé, F. Arendse, P. Comte et al., “Nanocrystalline titanium oxide electrodes for photovoltaic applications,” Journal of the American Ceramic Society, vol. 80, no. 12, pp. 3157–3171, 1997. View at Google Scholar
  5. F. Pichot, J. R. Pitts, and B. A. Gregg, “Low-temperature sintering of TiO2 colloids: application to flexible dye-sensitized solar cells,” Langmuir, vol. 16, no. 13, pp. 5626–5630, 2000. View at Publisher · View at Google Scholar
  6. C. Longo, A. F. Nogueira, M.-A. De Paoli, and H. Cachet, “Solid-state and flexible dye-sensitized TiO2 solar cells: a study by electrochemical impedance spectroscopy,” Journal of Physical Chemistry B, vol. 106, no. 23, pp. 5925–5930, 2002. View at Publisher · View at Google Scholar
  7. H. Lindström, A. Holmberg, E. Magnusson, S.-E. Lindquist, L. Malmqvist, and A. Hagfeldt, “A new method for manufacturing nanostructured electrodes on plastic substrates,” Nano Letters, vol. 1, no. 2, pp. 97–100, 2001. View at Publisher · View at Google Scholar
  8. S. A. Haque, E. Palomares, H. M. Upadhyaya et al., “Flexible dye sensitised nanocrystalline semiconductor solar cells,” Chemical Communications, no. 24, pp. 3008–3009, 2003. View at Publisher · View at Google Scholar
  9. T. Miyasaka, Y. Kijitori, T. N. Murakami, M. Kimura, and S. Uegusa, “Efficient nonsintering type dye-sensitized photocells based on electrophoretically deposited TiO2 layers,” Chemistry Letters, vol. 31, no. 12, p. 1250, 2002. View at Publisher · View at Google Scholar
  10. S. Uchida, M. Tomiha, H. Takizawa, and M. Kawaraya, “Flexible dye-sensitized solar cells by 28 GHz microwave irradiation,” Journal of Photochemistry and Photobiology A, vol. 164, no. 1–3, pp. 93–96, 2004. View at Publisher · View at Google Scholar
  11. T. Kado, M. Yamaguchi, Y. Yamada, and S. Hayase, “Low temperature preparation of nano-porous TiO2 layers for plastic dye sensitized solar cells,” Chemistry Letters, vol. 32, no. 11, p. 1056, 2003. View at Publisher · View at Google Scholar
  12. T. N. Murakami, Y. Kijitori, N. Kawashima, and T. Miyasaka, “UV light-assisted chemical vapor deposition of TiO2 for efficiency development at dye-sensitized mesoporous layers on plastic film electrodes,” Chemistry Letters, vol. 32, no. 11, p. 1076, 2003. View at Publisher · View at Google Scholar
  13. D. Zhang, T. Yoshida, and H. Minoura, “Low-temperature fabrication of efficient porous titania photoelectrodes by hydrothermal crystallization at the solid/gas interface,” Advanced Materials, vol. 15, no. 10, pp. 814–817, 2003. View at Publisher · View at Google Scholar
  14. D. Zhang, T. Yoshida, and H. Minoura, “Low temperature synthesis of porous nanocrystalline TiO2 thick film for dye-sensitized solar cells by hydrothermal crystallization,” Chemistry Letters, vol. 31, no. 9, p. 874, 2002. View at Publisher · View at Google Scholar
  15. Y. Liu, A. Hagfeldt, X.-R. Xiao, and S.-E. Lindquist, “Investigation of influence of redox species on the interfacial energetics of a dye-sensitized nanoporous TiO2 solar cell,” Solar Energy Materials and Solar Cells, vol. 55, no. 3, pp. 267–281, 1998. View at Publisher · View at Google Scholar
  16. S. Y. Huang, G. Schlichthörl, A. J. Nozik, M. Grätzel, and A. J. Frank, “Charge recombination in dye-sensitized nanocrystalline TiO2 solar cells,” Journal of Physical Chemistry B, vol. 101, no. 14, pp. 2576–2582, 1997. View at Publisher · View at Google Scholar
  17. S. Sodergern, A. Hagfeldt, J. Olsson, and S.-E. Lindquist, “Theoretical models for the action spectrum and the current-voltage characteristics of microporous semiconductor films in photoelectrochemical cells,” Journal of Physical Chemistry, vol. 98, no. 21, pp. 5552–5556, 1994. View at Publisher · View at Google Scholar