Decay and Dissociation of Excitons in Colloidal Semiconductor Quantum Dots in the Presence of Small Molecules

This dissertation describes interactions between colloidal semiconductor quantum dots (QDs) and small organic molecules that affect the electronic structure of the surfaces of the QDs and influence the decay and dissociation pathways available to excitonic charge carriers (electrons and holes) in the QDs. Pathways by which electrons and holes in QDs leave conduction and valence band-edge states, respectively, include charge trapping to a state localized in the QD core or on the surface, charge transfer to a redox partner, and radiative recombination. Analysis of transient absorption and time-resolved photoluminescence (PL) spectroscopies enabled the construction of a time-resolved, charge carrier-resolved map of decay from the first excitonic state of colloidal CdSe QDs. This map reveals three different populations of CdSe QDs that differ in the timescales of available hole and electron-trapping processes. The mechanism by which a p-substituted aniline quenches the PL of CdSe QDs upon displacing native hexadecylamine ligands depends on the electronic nature of its para substituent. Anilines with electron withdrawing substituents quench PL through incomplete passivation of Cd2+ surface sites, and anilines with electron donating substituents quench PL through photoinduced hole transfer. Transient absorption measurements on both the picosecond and microsecond timescales reveal that a series of alkyl-substituted p-benzoquinone (s-BQ) molecules participate in both static and collisional photoinduced electron transfer (PET) with PbS QDs. The efficiencies of both static and collisional PET are limited by the presence of the oleate ligand shell, and depend on the size and shape of the (s-BQ) molecule. A model for the dependence of the collisional quenching efficiency on the volume of the s-BQ molecule produces a parameter that provides a quantitative measure of the permeability of the organic ligand shell of the QDs. Thermodynamically spontaneous electron transfer occurs from sulfur ions on the surfaces of PbS QDs to adsorbed tetracyanoquinodimethane (TCNQ) molecules, and creates indefinitely stable ion pairs that are characterized by steady-state visible and mid-infrared spectroscopy of TCNQ and NMR spectroscopy of the oleate ligands that coat the QDs.