Ga-doped ZnO transparent electrodes with TiO2 blocking layer/nanoparticles for dye-sensitized solar cells
© Kim et al; licensee Springer. 2012
Received: 10 September 2011
Accepted: 5 January 2012
Published: 5 January 2012
Ga-doped ZnO [GZO] thin films were employed for the transparent electrodes in dye-sensitized solar cells [DSSCs]. The electrical property of the deposited GZO films was as good as that of commercially used fluorine-doped tin oxide [FTO]. In order to protect the GZO and enhance the photovoltaic properties, a TiO2 blocking layer was deposited on the GZO surface. Then, TiO2 nanoparticles were coated on the blocking layer, and dye was attached for the fabrication of DSSCs. The fabricated DSSCs with the GZO/TiO2 glasses showed an enhanced conversion efficiency of 4.02% compared to the devices with the normal GZO glasses (3.36%). Furthermore, they showed better characteristics even than those using the FTO glasses, which can be attributed to the reduced charge recombination and series resistance.
Dye-sensitized solar cells [DSSCs] have been recognized as an alternative to the conventional p-n junction solar cells because of their simple fabrication process, low production cost, and transparency. A typical DSSC consists of a transparent conductive oxide [TCO] electrode, a dye-sensitized oxide semiconductor nanoparticle layer, a liquid redox electrolyte, and a Pt counter electrode [1, 2]. Generally, fluorine-doped tin oxide [FTO] is commonly used for DSSCs as TCO due to its good thermal stability. However, FTO films have some drawbacks including high cost, insufficient conductivity, and low optical transmittance. Therefore, new TCO materials are required to replace FTO glasses .
ZnO-based materials have emerged as a promising material for transparent electrodes in solar cell applications. Since undoped ZnO shows high resistivity owing to low carrier concentration, group-III elements are doped into ZnO. Among them, Ga-doped ZnO [GZO] has several advantages such as higher resistance to oxidation and less lattice deformation compared to the other materials [4, 5]. Nevertheless, little effort has been spent on attempts to use GZO as TCO for DSSCs since the surface structure of the ZnO-based materials may be destroyed when they are immersed in the acidic dye solution containing a Ru complex for a long time. Besides, the electrical conductivity of GZO films can deteriorate after thermal annealing at high temperature which is required to form the TiO2 semiconductor nanoparticle layer .
In this paper, we suggest the use of GZO transparent electrodes with a TiO2 blocking layer for DSSCs. The TiO2 blocking layer can protect the GZO electrodes from the acidic dye solution and the oxidation at high temperature. The use of a thin TiO2 blocking layer can also reduce the recombination of electrons at the electrode/electrolyte interface.
GZO thin films were deposited on glass substrates by using a pulsed laser deposition [PLD] system for transparent electrodes. A ZnO ceramic target containing 2 wt.% Ga2O3 was ablated using a Q-switched Nd:YAG laser with a wavelength of 355 nm (Surelite III; Continuum, Santa Clara, CA, USA). During the deposition, oxygen partial pressure and substrate temperature were kept at the optimal conditions, which were 20 mTorr and 400°C, respectively. The electrical properties of the deposited GZO thin films were investigated by the van der Pauw Hall measurement system. After the deposition of the GZO films, a thin TiO2 layer was also deposited on the GZO surface for the blocking layer by a PLD method. A metal Ti target was ablated in oxygen atmosphere at a substrate temperature of 400°C. The structural and optical properties were examined by X-ray diffraction [XRD] and UV-Vis spectroscopy.
Using the fabricated GZO glasses, DSSCs were manufactured. Anatase TiO2 slurry (colloid) was prepared with a conventional method  and coated for a TiO2 nanoparticle layer. The coating was carried out on the TiO2 blocking layer with an active area of 0.36 cm2 by doctor blading. For comparison, the GZO without the blocking layer and commercially used FTO glasses were also employed to fabricate the DSSCs. After being sintered at 510°C, they were immersed into the solution of N719 ruthenium-based dye. Pt-coated counter electrodes were prepared by screen printing on the GZO-deposited glasses and heated at 400°C. The surface morphologies of the TiO2 nanoparticles on the GZO and GZO/TiO2 glasses were observed by scanning electron microscopy [SEM]. Then, the DSSC cells were assembled by sealing the TiO2 electrode and Pt electrode together using a hot melt film (Bynel; DuPont, Wilmington, DE, USA), and an electrolyte was injected into the space between the electrodes through a predrilled hole in the counter electrode. Finally, the hole was sealed with Bynel and a cover glass. The photovoltaic performance of the DSSCs was evaluated using a solar simulator at one sun (AM1.5, 100 mWcm-2) condition. In order to investigate the electron transport properties of the DSSCs, electrochemical impedance spectroscopy analysis was performed.
Results and discussion
Photovoltaic parameters of the fabricated DSSCs
GZO thin films were deposited on glass substrates for DSSC applications. The GZO films showed a low resistivity of 5.95 × 10-4 Ω cm. A TiO2 blocking layer was inserted between the GZO and TiO2 nanoparticles to protect the GZO and enhance the photovoltaic properties. The fabricated DSSCs with the GZO/TiO2 glasses showed a conversion efficiency of 4.02%, which was 19.6% higher compared to 3.36% of the DSSCs using the GZO glasses. Furthermore, they showed slightly better characteristics than those using the commercially used FTO glasses. These results can be ascribed to the reduced charge recombination and series resistance caused by the influence of the TiO2 blocking layer. Therefore, it can be concluded that the GZO films have the ability to be employed to the high-efficiency DSSCs as transparent electrodes.
This work was supported by Korea University Grant and the New & Renewable Energy of the Korea Institute of Energy Technology Evaluation and Planning (KETEP) grant funded by the Korea government Ministry of Knowledge Economy (No. 20103030010040-11-1000).
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