Surface Enhanced Raman Scattering (SERS) is a process by which molecules near certain special metal surfaces exhibit Raman scattering that is measurably more intense than is the normal Raman scattering exhibited by molecules in the absence of the surface. The majority of SERS-active metal substrates, such as roughened electrodes and colloidal sols, are fabricated from coinage metals, Au, Ag and Cu. The principal subject of this thesis is the surface enhanced Raman spectroscopic study of the adsorbates; pyrazinamide, 2- and 4-mercaptopyridine. A range of SERS-active Ag substrates was used, viz., Ag colloids, metal liquid-like films (MELLFs), and roughened Ag electrodes. In addition, an original technique that encompasses both SERS and waveguide Raman spectroscopy (WRS), known as integrated optics, evanescent wave, surface enhanced Raman spectroscopy (IOEW-SERS) was developed. For this technique, a waveguide heterostructure was fabricated on nano-scale dimensions by self-assembly of silver colloidal particles on thin glass slides. The unique optical behaviors of both SERS and WRS systems are combined such that optically guided light propagates in the thin film, with an evanescent wave and couples with surface plasmon modes of metal particles. A comparative SERS study of 2- and 4-mercaptopyridine (MPy) was undertaken using all of the above methods. The purpose of this comparison was to determine the similarities between IOEW-SERS and other Ag SERS-active systems. These studies were extended by using a 4-MPy modified SERS-active optical waveguide as a thin film chemical sensor. Intermolecular interactions between probe ions, Cu$ sp{2+}$ and H$ sp+,$ with 4-MPy were observed by vibrational perturbations to the IOEW-SERS spectrum. X-ray photoelectron spectroscopy (XPS) allowed a layer-by-layer examination of the 4-MPy derivatized waveguide from the substrate to the Cu$ sp{2+}$ ion. A potential dependent SERS study of 4-MPy modified Ag electrodes, including the interact
| Identifer | oai:union.ndltd.org:LACETR/oai:collectionscanada.gc.ca:QMM.40315 |
| Date | January 1996 |
| Creators | Baldwin, Jean A. |
| Contributors | Butler, Jan S. (advisor), Andrews, Mark P. (advisor) |
| Publisher | McGill University |
| Source Sets | Library and Archives Canada ETDs Repository / Centre d'archives des thèses électroniques de Bibliothèque et Archives Canada |
| Language | English |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
| Format | application/pdf |
| Coverage | Doctor of Philosophy (Department of Chemistry.) |
| Rights | All items in eScholarship@McGill are protected by copyright with all rights reserved unless otherwise indicated. |
| Relation | alephsysno: 001536645, proquestno: NN19707, Theses scanned by UMI/ProQuest. |
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