Charging of quantum dots by sulfide redox electrolytes reduces electron injection efficiency in quantum dot...

In quantum dot (QD) sensitized solar cells (QDSSCs), redox electrolytes act as hole scavengers to regenerate the QD ground state from its oxidized form, thus enabling a continuous device operation. However, unlike molecular sensitizers, QDs also have redox-active trap states within the band gap, which can be charged in the presence of redox electrolyte. The effects of electrolyte induced charging of QDs on the performance of QDSSCs have not been reported. Here, using steady-state and time-resolved absorption and emission spectroscopy, we show that CdSe/CdS3MLZnCdS2MLZnS2ML core/multishell QDs are charged in the presence of sulfide electrolytes due to the reduction of surface states. As a result, exciton lifetimes in these QDs are shortened due to an Auger recombination process. Such charging induced fast Auger recombination can compete effectively with electron transfer from QDs to TiO2 and reduce the electron injection efficiency in QDSSCs. We believe that the reported charging effects are present for most colloidal nanocrystals in the presence of redox media and have important implications for designing QD-based photovoltaic and photocatalytic devices.