Date of Award
Doctor of Philosophy
Transition metal Dichalcogenide MoS2in the monolayer and few-layer form have generated intense interest in the fundamental and applied research community due to its surprisingly strong light-matter interactions, strong excitonic effect, and unique elec-tronic and chemical activity at the edges. In this thesis work, I have conducted a series of synergistic experimental and computational investigations focused on understanding the fundamental optical properties of few-layer MoS2(experiment with supporting computational calculations) and its potential application into the electrochemical reduction of CO2(computational)In the first part of the thesis, I show that sulfur vacancies affect the optical properties of few-layer thin films deposited using magnetron sputtering. In particular, I show that sulfur vacancies can obscure the well-defined A/B excitons in MoS2. Next, while contributing with the process of developing high-quality MoS2films, I designed an approach to accurately determine the optical constants by combining transmission spectroscopy with spectroscopic ellipsometry. The method, which we call Transmission-assisted spectroscopic ellipsometry (TASE), is demonstrated on high-quality MoS2films deposited on transparent and absorbing substrates. Next, Transmission spectroscopy combined with the Kramers-Kronig consistent optical model was employed to determine the complex dielectric function of few-layer MoS2in the broadband energy range of 0.7-6.5 eV. Optical transitions leading to peaks in the dielectric functions are assigned to the band structure. In particular, a new peak is observed and assigned at 4.5 eV in few-layer MoS2. Finally, I have examined the effectiveness of doped MoS2on the catalytic activity for CO reduction using density functional theory method. The structural calculation shows that doping Mo edge site of MoS2with transition metals that have higher work function than Mo atom results a lowering in the CO adsorption energy which suppresses the dissociation reaction and enhances the hydrogenation reaction. The Bader charge analysis shows that the dopant atom does not contribute to CO adsorption directly but it reduces the charge density at the edge atom that is indicated from the Density of states.
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