We have synthesized al
kylselenide reagents to replace the native oleate ligand on PbSe quantum dots (QDs) in order to investigate the effect of surface modification on their stoichiometry, photophysics, and air stability. The al
kylselenide reagent removes all of the oleate on the QD surface and results in Se addition; however, complete Se enrichment does not occur, achieving a 53% decrease in the amount of excess Pb for 2 nm diameter QDs and a 23% decrease for 10 nm QDs. Our analysis suggests that the Se ligand preferentially binds to the {111} faces, which are more prevalent in smaller QDs. We find that attachment of the al
kylselenide ligand to the QD surface enhances oxidative resistance, li
kely resulting from a more stable bond between surface Pb atoms and the al
kylselenide ligand compared to Pb-oleate. However, binding of the al
kylselenide ligand produces a separate nonradiative relaxation route that partially quenches PL, suggesting the formation of a dar
k hole-trap.
Keywords:
quantum dots; photoluminescence; nuclear magnetic resonance; lead chalcogenides; nanoparticles