Exciton delocalization and hot hole extraction in CdSe QDs and CdSe/ZnS type 1 core shell QDs sensitized with newly synthesized thiols

The present work describes ultrafast thermalized and hot hole transfer processes from photo-excited CdSe quantum dots (QDs) and CdSe/ZnS core-shell QDs (CSQDs) to newly synthesized thiols. Three thiols namely 2-mercapto-N-phenylacetamide (AAT), 3-mercapto-N-phenylpropanamide (APT) and 3-mercapto-N-(4-methoxyphenyl) propanamide (ADPT) were synthesized and their interaction with both CdSe QDs and CdSe/ZnS CSQDs was monitored. Steady state absorption study suggests the exciton delocalization from CdSe QDs in the presence of the thiols. However similar features were not observed in the presence of a ZnS shell over a CdSe core, instead a broadening in the excitonic peak was observed with both APT and ADPT but not with AAT. This exciton delocalization and broadening in the excitonic peak was also confirmed by ultrafast transient absorption studies. Steady state and time resolved emission studies show hole transfer from photo-excited QDs and CSQDs to the thiols. A signature of hot hole extraction was observed in transient absorption studies which was confirmed by fluorescence upconversion studies. Both hot and thermalized hole transfer rates from CdSe QDs and CdSe/ZnS CSQDs to the thiols were determined using the fluorescence up-conversion technique. Experiments with different ZnS shell thicknesses have been carried out which suggest that hole transfer is possible till 2.5 monolayer of the ZnS shell. To the best of our knowledge we are reporting for the first time the extraction of hot holes from CdSe/ZnS type I CSQDs by a molecular adsorbate.