Alkyl Chain Barriers for Kinetic Optimization in Dye-Sensitized Solar Cells

The optimization of interfacial charge transfer is crucial to the design of dye-sensitized solar cells. In this paper we address the dynamics of the charge separation and recombination in liquid-electrolyte and solid-state cells employing a series of amphiphilic ruthenium dyes with varying hydrocarbon chain lengths, acting as an insulating barrier for electron−hole recombination. Dynamics of electron injection, monitored by time-resolved emission spectroscopy, and of charge recombination and regeneration, monitored by transient optical absorption spectroscopy, are correlated with device performance. We find that increasing dye alkyl chain length results in slower charge recombination dynamics to both the dye cation and the redox electrolyte or solid-state hole conductor (spiro-OMeTAD). These slower recombination dynamics are however paralleled by reduced rates for both electron injection into the TiO₂ electrode and dye regeneration by the I^-/I₃^- redox couple or spiro-OMeTAD. Kinetic competition between electron recombination with dye cations and dye ground state regeneration by the iodide electrolyte is found to be a key factor for liquid electrolyte cells, with optimum device performance being obtained when the dye regeneration is just fast enough to compete with electron−hole recombination. These results are discussed in terms of the minimization of kinetic redundancy in solid-state and liquid-electrolyte dye-sensitized photovoltaic devices.