Influence of Hole-Sequestering Ligands on the Photostability of CdSe Quantum Dots

Chalcogenide nanocrystals or quantum dots (QDs) such as CdSe and PbSe have great potential as absorbers for QD-sensitized solar cells, but their practical utility is limited by fast degradation when exposed to ambient environments. Here we present results showing that small organic molecules acting as hole-accepting ligands can be very effective in reducing photooxidation of CdSe QDs. The aromatic amine, 4-dimethylaminothiophenol (DMATP), is shown to be especially effective in enhancing stability of CdSe QDs when illuminated in air or in aqueous environments. Using photoluminescence and density functional theory (DFT) calculations, we show that the enhanced stability results from hole transfer from the QD to the ligand and delocalization of the resulting positive charge on the aromatic ring and amino group instead of the sulfur atom that links the molecule to the CdSe