Nanostructured silver for applications in surface enhanced Raman spectroscopy and photoelectrochemical reactions

Initial work focused on characterizing silver and its surface enhanced Raman spectroscopy (SERS) capabilities. Silver nanowires were chosen as an ideal material and scanning confocal microscopy studies were performed to identify hot spots. The silver nanowires were found to exhibit fluorescence blinking that was attributed to small silver clusters undergoing rapid interchange from Ag0 to Ag2O. Control of this blinking was accomplished through the removal of oxygen and through electrochemical control of the system. SERS was also recorded from these nanowires. Deconvolution of the SERS signal from the fluorescence was accomplished either by increasing the SERS analyte concentration or increasing the total number of "hot spots" in the focus volume.;Silver applications were studied by performing a SERS study of Rhodamine 6G (R6G) and Poly(3-hexylthiophene-2,5-diyl) (P3HT). A Tollens' silver substrate was utilized as the SERS substrate and similar blinking effects were found to arise. P3HT was cast from 4 different solvents:dichloromethane, chlorobenzene, THF, and toluene. The solvent effects were studied, with kinking of the polymer noted in the non-chlorinated solvents. Single molecule studies in conjunction with polarization control indicated that the P3HT formed in an overlapping manner with only partial charge transfer within the molecule.;Finally silvers interactions with TiO2 were studied. Micron scale single crystal anatase TiO2 was synthesized by using HF in a hydrothermal process forming a truncated bipyramidal structure consisting of [101] and [001] faces. Fluorine was present in small amounts on the surface of the TiO2 as confirmed by x-ray photoelectron spectroscopy (XPS). An annealing process was used to remove the fluorine. Nitrogen doping was attempted, but was not found to occur in significant amounts. Visible light sensitivity was noted in annealed samples but did not occur in the bulk as demonstrated through photoelectrochemical measurements. Silver photoreduction directly on the surface of the TiO2 crystals revealed visible light sensitivity at surface defects. No facial preference was noted for the silver growth through energy-dispersive X-ray spectroscopy (EDX) images. A secondary method of silver attachment through a linker molecule showed that on-resonance silver structures provided greater SERS enhancement dependent upon the direction of the linker molecule.