Growth and Assembly of Gold Nanorods and Their Interactions with Fluorophores and Photochromic Molecules.

摘要

Noble metal nanocrystals have drawn great attention in a wide range of research fields due to their extraordinary localized surface plasmon resonances, which are essentially collective charge density oscillations confined in metallic nanostructures. Their applications range from bioimaging, sensing and therapy in life sciences to plasmonic circuits and optical data storage in micro-optoelectronics. More attractively, they can be used to enhance light harvesting in solar energy conversion systems. In this thesis, I will systematically describe the preparation and assembly of gold nanorods and their interactions with fluorophores and photochromic molecules, both experimentally and theoretically.;I will first introduce my studies on high-index-faceted gold nanocrystals. Elongated tetrahexahedral (THH) gold nanocrystals have been prepared in high yields using a seed-mediated growth method. Structural characterizations reveal that they are single crystals enclosed by 24 high-index {037} facets. Electrochemical measurements have proven that these THH Au nanocrystals are more chemically active than octahedral Au nanocrystals that are enclosed by low-index {1111} facets. Next, I will demonstrate the formation of large-area, 3D ordered assemblies of Au nanostructures that have different sizes and shapes, including nanorods, polyhedra, nanocubes, and bipyramids, by droplet evaporation. The nature of the resultant assemblies is strongly dependent on the shape of Au nanostructures for single-component systems; while the assembly of binary nanorod mixtures is dependent on the relative diameters of two nanorod samples for the nanorods used in our experiments.;Most applications of plasmonic nanostructures are based on their interactions with other chemical/physical species. In my research work, gold nanorods interacting with photochromic molecules and fluorophores are extensively studied. For the case of photochromic molecules, I have demonstrated a plasmonic switch on the basis of the resonance coupling between single Au nanorods and photochromic molecules. An individual plasmonic switch is composed of a single nanorod and the surrounding photochromic molecules. Its modulation depth reaches 7.2 dB. The estimated power and energy required for operating such a single-nanorod plasmonic switch are ∼13 pW and ∼39 pJ. For the case of fluorophores, I will give a systematic description of my research on plasmon-fluorophore interactions. Excitation polarization-dependent plasmon-enhanced fluorescence, polarized emission, and modulation of fluorophore emission spectra by localized plasmon resonances will be experimentally demonstrated. The interactions between the plasmonic nanorods and the fluorophore molecules can be temporally separated into plasmon-enhanced excitation and coupled emission processes under unsaturated excitation conditions. Finite-difference time-domain (FDTD) method will be employed to explain the origin of the excitation and emission polarization dependence. A term "plasmophore", which is corned by Lakowicz et al., is quoted to describe the artificially prepared quantum emitters that are composed of plasmonic structure and fluorophore.;I believe that my research work will provide an in-depth understanding of the basic chemical and physical properties of plasmonic gold nanorods. These works can inspire future applications of plasmonic nanostructures on biotechnology, optoelectronics and solar energy conversion. -.