Gold nanoparticles in the 1-2 mn core diameter size regime have generated a great deal of interest due to their size-dependent electronic, optical, and catalytic properties. A number of proof-of-concept experiments have demonstrated that small metal nanoparticles can be integrated into single electron transistors and optical waveguides. Still, reliable incorporation of gold nanoparticles into devices requires practical methods for their assembly on surfaces. Additionally, surface modification methods must be developed in order to control interparticle interactions and nanoparticle-environment interactions for use in sensing and catalysis.;In this research, nanoparticle-substrate interactions were utilized to assemble surface-bound gold nanoparticle monolayers with interesting electronic and catalytic properties. Gold nanoparticles (1.5 nm diameter) with a thiol ligand shell containing phosphonic acid terminal functionality were synthesized and assembled selectively onto hafnium-modified silicon dioxide substrates through bonding of the terminal phosphonate to Hf(IV) surface groups. By increasing the surface coverage of Hf, it was possible to assemble monolayers of gold nanoparticles dense enough to exhibit nonlinear current-voltage properties across a 5-mum electrode gap at room temperature. Moreover, by taking advantage of the selectivity of this ligand shell for ZnO over SiO 2, small gold nanoparticles were utilized as catalysts for selective growth of patterned, vertical ZnO nanowire arrays.;In addition to engineering nanoparticle-substrate interactions, new surface modification methods were introduced to manipulate the interaction of the as-deposited gold nanoparticle monolayers with the environment. For example, thiol-thiol ligand exchange reactions were carried out on the surface-bound nanoparticle monolayers by immersion in dilute thiol solutions. Contact angle and XPS measurements indicate that the upper, surface-exposed phosphonic acid ligands are replaced by incoming thiol ligands. TEM measurements indicate that nanoparticle monolayers remain surface-bound and are stable to this exchange process, as the average particle size and surface coverage are preserved. As another example, the ligand shell can be partially removed by UV/ozone treatment to expose bare gold cores to the surrounding environment. On metal oxide substrates, this approach activates the particles for room temperature oxidation of carbon monoxide to carbon dioxide.;This dissertation includes both my previously published and my co-authored materials.
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