This thesis describes the mechanisms by which organic surfactants, particularly thiophenols and phenyldithiocarbamates, reduce the confinement potential experienced by the exciton of semiconductor quantum dots (QDs). The reduction of the confinement potential is enabled by the creation of interfacial electronic states near the band edge of the QD upon ligand adsorption. In the case of thiophenols, we find that this ligand adsorbs in two distinct binding modes, (i) a tightly bound mode capable of exciton delocalization, and (ii) a more weakly bound mode that has no discernable effect on exciton confinement. Both the adsorption constant and reduction in confinement potential are tunable by para substitution and are generally anticorrelated. For tightly bound thiophenols and other moderately delocalizing ligands, the degree of delocalization induced in the QD is approximately linearly proportional to the fractional surface area occupied by the ligand for all sizes of QDs. In the case of phenyldithiocarbamates, the reduction in the confinement potential is much greater, and ligand adjacency must be accounted for to model exciton delocalization. We find that at high surface coverages, exciton delocalization by phenyldithiocarbamates and other highly delocalizing ligands is dominated by ligand packing effects. Finally, we construct a database of electronic structure calculations on organic molecules and propose an algorithm that combines experimental and computational screening to find novel delocalizing ligands.
|Advisor:||Weiss, Emily A.|
|Commitee:||Hupp, Joseph T., Schaller, Richard D.|
|School Location:||United States -- Illinois|
|Source:||DAI-B 77/05(E), Dissertation Abstracts International|
|Subjects:||Physical chemistry, Quantum physics, Nanotechnology|
|Keywords:||Computational screening, Delocalization, Machine learning, Quantum confinement, Quantum dots|
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