Functionalization to control microstructural, optical, electronic and wetting properties of metal oxide surfaces

This thesis focuses on engineering the surface chemistry of oxide surfaces in order to control their microstructural, optical, electronic and wetting properties. Several different types of experiments have been performed to tailor the properties of silicon oxide, titanium dioxide, and zinc oxide surfaces. Applications of this work include organic electronics, sensors and nanomanufacturing.;Adsorption of 3-mercaptopropyltrimethoxysilane (MPS) on hydroxylated silicon oxide substrates by immersion in MPS solution or exposure to MPS vapor has been compared using X-ray photoelectron spectroscopy (XPS). To aid the interpretation, MPS has also been cryogenically condensed in ultrahigh vacuum (UHV) onto gold surfaces. Condensation of MPS vapor on gold in the absence of water does not result in MPS polymerization, as evidenced by multilayer desorption upon warming to room temperature. The C1s XPS spectrum has been used to infer the relative abundance of methoxy groups. Vapor-deposition on hydroxylated silicon oxide leads to an unpolymerized MPS monolayer consisting of molecules with two methoxy groups.;UV induced hydrophilicity of titanium dioxide surfaces could possibly be used to provide a means of registration and alignment in high-rate nanomanufacturing applications or to induce transfer of nanoelements. In order to understand the nature and magnitude of intermolecular forces, force-distance curves have been measured on TiO2. Toward the goal of possibly using light to induce nanoparticle transfer, force curves have been recorded using an SiO2 colloidal probe before and after irradiating the TiO 2 surface with UV light. In order to eliminate the effects of capillary forces, the relative humidity has been kept below 1% by flowing either N 2 or N2/O2 (1:1) into the AFM chamber. In a dry nitrogen environment, no difference is observed in adhesive forces measured with and without UV exposure.;Gold-coated atomic force microscope (AFM) tips functionalized with amine-, hydroxyl, carboxylic acid, and methyl-terminated alkanethiol molecules have been used to probe the adhesive forces of polystyrene and poly(acrylic acid) films in dry air (relative humidity < 0.5%). XPS and contact angle measurements confirm the quality and uniformity of similarly treated gold surfaces and the polymer films. XPS indicates that the amine-functionalized thiol films are protonated and comprised of multilayers.;Toward the goal of modifying its optical properties, ZnO nanorod surfaces have been modified using 3-mercaptopropyltriethoxysilane (MPTES) and 1-propanethiol (PPT), and XPS has been used to investigate the changes occurring on the nanorods after surface modification. XPS reveals that in the case of MPTES-modified nanorods, bonding occurs via both S-Zn and Si-O-Zn bond formation. For comparison, 3-mercaptopropyltrimethoxysilane (MPTMS), dodecanethiol and methanethiol have been adsorbed on sputter-cleaned Zn-terminated ZnO (0001) in ultrahigh vacuum (UHV). In this case, XPS indicates that bonding of thiols on ZnO surfaces occurs via S-Zn bond formation. Photoluminescence spectroscopy has been used to study the effect of surface functionalization on the optical properties of the nanorods. MPTES- and PPT-functionalized nano-ZnO show an increase in intensity of the UV emission peak relative to the unfunctionalized nanorods due to reduced probability of surface dependent non-radiative processes. A decrease in the visible peak in both cases is believed to be due to passivation of surface defects.;A simple method for encapsulating zinc oxide nanoparticles within an organic matrix has been discovered that consists of dispersing them in an ethanolic solution, adding an organothiol and stirring while heating. Electron microscopy, photoemission, Raman spectroscopy and thermal gray metric analyses demonstrate that partial dissolution of the oxide occurs accompanied by encapsulation within a matrix consisting of a 1:2 zinc-thiol complex. Using this methodology, it is possible to surround ZnO within diverse matrices, including fluorescent ones. (Abstract shortened by UMI.)...