Optical properties of graphene/GaN hybrid structure were investigated by using a variety of optical spectroscopy techniques including low-temperature photoluminescence (PL) spectroscopy, time-resolved PL (TRPL) spectroscopy, confocal scanning micro-Raman spectroscopy. Single-layer graphene grown by chemical vapor deposition was transferred to GaN epilayer surface, which is verified by the Raman spectrum with a sharp characteristic peak at ~2690 cm-1and a homogeneous Raman image. Three main band-edge emissions including the free exciton A transition (denoted as FXA), the donor bound exciton transition (denoted as DX) and the third peak (denoted as Ix) were well resolved in the PL spectra of the hybrid structure as well as the as-grown GaN epilayer at low temperatures. Interestingly, the FXA transition and Ix line of the GaN epilayer were found to be dramatically altered by the top graphene layer while the DX is almost unaffected. The intensity of Ix line substantially drops after the transfer of graphene layer on GaN, indicating surface defect nature of the Ix line. More interestingly, an unpredictable dip structure develops in the FXA peak when the temperature is beyond 50 K. Similar spectral structure change also occurred in the emission of free exciton B (referred as FXB)with higher transition energy .A free exciton dissociation and electron transfer model was proposed to explain the “dip effect”. More supporting evidence to the model was found in the time-resolved PL spectra of the hybrid structure and the control sample. The results showed the significant influence of graphene monolayer on the fundamental optical properties of GaN. / published_or_final_version / Physics / Master / Master of Philosophy

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Polymers, by virtue of their chemical composition and molecular architecture, exhibit a diverse range of microstructural features and properties. As thin films, due primarily to effects associated with confinement and interfacial interactions, their properties may be film-thickness dependent. The significance of their thicknessdependent behavior is underscored by the fact that polymer films are of technological interest in areas that include, sensors, catalysts and organic electronics. One challenge associated with the use of thin film polymers is to understand the role of confinement and interfacial interactions on thermally induced transitions, such as vitrification and various morphological transitions. To this end, the work presented in this dissertation focuses on the behavior of thermally induced transitions in two thin film polymer-based systems: (1) an A-b-B diblock copolymer which can undergo a disorder-to-order transitions (ODT), wherein the ordered state exhibits varying geometrical symmetries, depending on the relative volume fractions of the A and B components; (2) an amorphous polymer filled with particles of nanoscale dimensions. The first of three problems examined is the influence of supercritical carbon dioxide (scCO₂) on the order-disorder transition of thin film symmetric A-b-B diblock copolymer systems. We show that the transition (xN)ODT, where x is the energetic A-B Flory-Huggins interaction parameter and N is the total degree of polymerization of the copolymer, of the thin film decreased ~ 20% compared to the bulk; the decrease was more significant in scCO₂ environments. The decrease of (xN)ODT in scCO₂ is contrary to observations in bulk copolymer-scCO₂ systems where the effective A-B interactions are weaker, hence the condition for the transition increases to higher (xN)ODT values. With regard to the second problem, we show for the first time experimentally that nanoparticles induced order into thin films of a symmetric A-b-B diblock copolymer at temperatures below the bulk ODT. Finally, we examine the influence of polystyrene (PS) grafted nanoparticles on the glass transition of PS films of varying molecular weight and thickness. We demonstrate that by controlling spatial distribution of nanoparticles, through driving forces of entropic origin, the glass transition temperature of the film can be changed drastically, as much as tens of degrees.

published_or_final_version / abstract / toc / Physics / Doctoral / Doctor of Philosophy

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