This thesis describes new aspects of the synthesis and ultrafast spectroscopy of PbS nanocrystals. The first part of the thesis investigates two aspects of PbS nanocrystal synthesis: the identity and composition of oleylamine reagent and the nature of sulfur species in sulfur solutions in long-chain amines. Oleylamine, formally cis-9-octadecyl-1-amine, is a solvent, a reactant, and a ligand in the synthesis of high-quality PbS nanocrystals and other nanomaterials. It is shown that commercial oleylamine samples contain elaidylamine, trans-9-octadecen-1-amine. Sulfur solutions in long-chain amines (n-octylamine and oleylamine) are common precursors in metal sulfide nanomaterial synthesis. Resonance Raman experiments on sulfur-amine solutions established the presence of various polysulfide anions, which slowly equilibrate on the timescale of days, causing a change in reactivity of the sulfur precursor. This aging of sulfur-amine solutions is shown to be strongly correlated with irreproducibility in PbS nanocrystal syntheses.
The second part of the thesis deals with non-linear optical experiments on sensitive samples, where vibrational stability, repetitive excitation, and sensitivity to air and moisture constitute a set of challenges often preventing an experiment without photoproduct contamination. As a solution to this problem, we designed, constructed and characterized a compact spinning sample cell suitable for liquid and thin film samples. The spinning sample cell, enclosed in a copper gasket sealed enclosure, enables complete sample exchange in optical experiments with up to 100 kHz repetition rates while maintaining an oxygen and water free environment at the 1 ppm level for over a month. The spinning sample cell was successfully used in a two-dimensional electronic spectroscopy experiment on PbS nanocrystals in solution, eliminating the buildup of the long-lived photoproducts and reducing trap emission in the spinning sample.
|Advisor:||Jonas, David M.|
|Commitee:||Damrauer, Niels H., Dukovic, Gordana, Nozik, Arthur J., Rogers, Charles T.|
|School:||University of Colorado at Boulder|
|School Location:||United States -- Colorado|
|Source:||DAI-B 79/01(E), Dissertation Abstracts International|
|Subjects:||Physical chemistry, Nanoscience, Materials science|
|Keywords:||Nanocrystals, Oleylamine, Repetitive excitation, Sample cell, Sulfur, Two-dimensional spectroscopy|
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