Wavefunction engineering for efficient photoinduced-electron-transfer in CuInS2 quantum dots sensitized solar cells.

The high efficiency of quantum dot-sensitized solar cells (QDSSCs) is a benefit of the highly efficient photoinduced-electron transfer (PET) to external electrodes. Here, we investigated how the surface defects and conduction-band (CB) offsets between core and shell materials affect the PET from CuInS2 quantum dots (QDs) by means of time-resolved femtosecond transient absorption and nanosecond photoluminescence spectroscopy. The transfer of 1S excited electrons from CuInS2 QDs to TiO2 films is demonstrated and we find that the surface-electron trapping can significantly reduce the efficiency of the PET. Though the electron trapping can be suppressed after ZnS surface passivation, the PET decreases significantly to a low efficiency of similar to 33% from the type I CuInS2/ZnS core/shell QDs because of their low electron density at the surface of the QDs. The surface-electron density is increased with the strategy of wavefunction engineering by reducing the CB offset, which allows us to achieve a quasi-type II carrier confinement in CuInS2/CdS core/shell QDs. The PET efficiency appears to be as high as similar to 95% from the CuInS2/CdS core/shell QDs, which is ascribed to synergistic effects of the surface passivation and enhanced delocalization of the electron wavefunction from the CuInS2 core to the CdS shell. Finally, we demonstrate that these new mechanistic understandings of the PET processes are crucial to improving the efficiency of CuInS2 QDSSCs.