Can Exciton-Delocalizing Ligands Facilitate Hot Hole Transfer from Semiconductor Nanocrystals?

Exciton-delocalizing ligands (EDLs) are of interest to researchers due to their ability to allow charge carriers to spread into the ligand shell of semiconductor nanocrystals (NCs). By increasing charge carrier surface accessibility, EDLs may facilitate the extraction of highly photoexcited carriers from NCs prior to their relaxation to the band edge, a process that can boost the performance of NC-based photocatalysts and light harvesting systems. However, hot carrier extraction must compete with carrier cooling, which could be accelerated by the stronger interaction of charge carriers and EDLs. This report describes the influence of the EDL phenyl­dithiocarbamate (PTC) on the electron and hole cooling rates of CdSe NCs. Using state-resolved transient absorption spectroscopy, we find that PTC treatment accelerates hole cooling by a factor of 1.7. However, upon further treatment of these NCs with cadmium­(II) acetate, the hole cooling rate reverts to the value measured prior to PTC treatment, yet these NCs maintain a red-shifted absorption spectrum indicative of PTC bound to the NC surface. This result provides strong evidence for the existence of two distinct surface-bound PTC species: one that traps holes before they cool and can be removed by cadmium­(II) acetate, and a second species that facilitates exciton delocalization. This conclusion is supported by both DFT calculations and photoluminescence measurements. The outlook from our work is that EDLs do not necessarily lead to an acceleration of carrier cooling, suggesting that they may provide a path for hot carrier extraction.