Modeling and interpretation of electrical impedance spectra of dye solar cells operated under open-circuit conditions

Electrical impedance spectroscopy (EIS) was applied in order to investigate electrochemical nanocrystalline TiO2 dye solar cells (DSC). Typically, three characteristic frequency peaks were observed in the spectra. These frequency peaks could be explained by variations of cell parameters and by comparison with intensity-modulated photovoltage spectroscopy (IMVS). It was shown that the low-frequency peak (in the mHz range) corresponds to the Nernstian diffusion within the electrolyte, while the middle-frequency peak (in the 10-100 Hz range) reflects the properties of the photoinjected electrons within the TiO2. The high-frequency peak (in the kHz range) corresponds to the charge-transfer at the platinum counter electrode. For a detailed analysis of the spectra, a model was developed which allows the evaluation of EIS spectra, measured under bias illumination and under open-circuit conditions. The influence of cell parameters such as the TiO2 layer thickness, cell thickness, charge-transfer resistance of the platinum counter electrode, and the lifetime of the photoinjected electrons, on the impedance spectra was studied both experimentally and theoretically. Finally, it is shown that EIS is a measurement method suited well for the investigation of the long-term stability of DSC, as changes of the inner cell parameters can be revealed. (C) 2002 Elsevier Science Ltd. All rights reserved.