Transient optical studies of interfacial charge transfer at nanostructured metal oxide/PbS quantum dot/organic hole...

We report a transient absorption and luminescence study addressing the charge separation, recombination, and regeneration reactions at nanostructured metal oxide/PbS quantum dot/organic hole conductor heterojunctions. We show that yields of charge separation are significantly higher at PbS/SnO(2) interfaces relative to PbS/TiO(2) interfaces, and conclude that this behavior is a result of the ca. 300-500 meV lower conduction band edge in SnO(2) as compared to TiO(2). We also report a correlation between the PbS particle size and the yield of charge separation at PbS/SnO(2) interfaces, with a smaller PbS particle radius resulting a higher yield of charge separation. Finally we investigated the regeneration of the photooxidized PbS by an organic hole transporting material, namely, spiro-OMeTAD. The overall spiro-OMeTAD(+) yield is found to be 27% at a SnO(2)/PbS (approximately 3 nm diameter)/spiro-OMeTAD heterojunction. The addition of a lithium salt was found to raise the overall spiro-OMeTAD(+) yield from its initial value of 27% (where no Li(+) is present) to 50%. We believe this to be a result of an increase in the primary charge injection yield to near unity as the SnO(2) conduction band is lowered (with increasing [Li(+)]), increasing the driving force for electron injection. The present findings are discussed with relevance to the design of PbS-sensitized metal oxide layers for DSSCs.