Electron Transport and Recombination in Dye-Sensitized Mesoporous TiO2 Probed by Photoinduced Charge-Conductivity Modulation Spectroscopy with Monte Carlo Modeling

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Abstract
We present a combined experimental and theoretical investigation into the charge transport and recombination in dye-sensitized mesoporous TiO2. We electronically probe the photoinduced change in conductivity through in-plane devices while simultaneously optically probing signatures of the charge species. Our quasi-continuous wave technique allows us to build data sets of electron mobility and recombination versus charge density over a wide temperature range. We observe that the charge density dependence of mobility in TiO2 is strong at high temperatures and gradually reduces with reducing temperature, to an extent where at temperatures below 260 K the mobility is almost independent of charge density. The mobility first increases and then decreases with reducing temperature at any given charge density. These observed trends are surprising and consistent with the multiple-trapping model for charge transport only if the trap density-of-states (DoS) is allowed to become less deep and narrower as the temperature reduces. Our recombination measurements and simulations over a broad range of charge density and temperature are also consistent with the above-mentioned varying DoS function when the recombination rate constant is allowed to increase with temperature, itself consistent with a thermally activated charge-transfer process. Further to using the Monte Carlo simulations to model the experimental data, we use the simulations to aid our understanding of the limiting factors to charge transport and recombination. According to our model, we find that the charge recombination is mainly governed by the recombination reaction rate constant and the charge density dependence is mainly a result of the bimolecular nature of the recombination process. The implication to future material design is that if the mobility can be enhanced without increasing the charge density in the film, for instance by reducing the average trap depth, then this will not be at the sacrifice of comparably enhanced recombination and it will greatly increase the charge carrier diffusion lengths in dye-sensitized or mesoscopic solar cells