Wan, Albert (2011-08). Self-Assembly of Organic Nanostructures. Doctoral Dissertation.
This dissertation focuses on investigating the morphologies, optical and photoluminescence properties of porphyrin nanostructures prepared by the self-assembly method. The study is divided into three main parts. In the first part, a large variety of porphyrin nanostructures, including nanoplates, nanofibers, nanoparticles and nanowires, were obtained through direct acidification of tetra(p-carboxyphenyl)porphyrin (TCPP) in aqueous solution. Protonation of the carboxylate groups of TCPP resulted in the formation of nanoplates through the J-aggregation of the porphyrin. Further protonating the core nitrogens of TCPP formed the porphyrin diacids which organized into well-defined structures through their interactions with counter-anions in the solution. The structures of the resulting assemblies were found to be counterion dependent. In the second part of this work, we explored the optical memory effect of the porphyrin thin film. We found that the morphology and the emission of the porpyrin thin film on Si can be changed by varying the pH of its surrounding solution. The changing in morphology and light emission of the thin film resulted from the protonation or deprotonation of TCPP'S core nitrogens. By selectively deprotonating the TCPP dications in a confined region utilizing the water meniscus between an AFM tip and the surface, Fluorescence patterns can be generated on the thin film. The fluorescence patterns can be easily erased by re-protonating the porphyrin. In the third part of this study, porphynoid nanoparticles were deposited on a surface energy gradient, and then characterized by AFM in order to investigate how the surface energy influences thier morphologies. The surface energy gradient was prepared by selectively oxidizing a self-assembly monolayer of octadecyltrichlorosilane (OTS) by UV-ozone. The nanoparticles disassemble into smaller nanoparticles with narrower size distribution on the surface with higher surface energy. Lastly, we engaged in characterizing the morphologies of polymer nanocomposites prepared by layer-by-layer assembly for wettability control. The surface roughness of the nanocopmosite in air and in salt solutions was also measured to study the correlation between the wettability of the polymer surface and its surface roughness.