Virginia Tech
Self-organization on Nanoparticle Surfaces for Plasmonic and Nonlinear Optical Applications
Abstract
dc:description.abstractThis dissertation is about fabrication and functionalization of metal nanoparticles for use in plasmonic and nonlinear optical (NLO) applications. In the first two chapters, I describe a series of experiments, where I combined silver nanoparticles fabricated by nanosphere lithography with ionic self-assembled multilayer (ISAM) films, tuning the geometry of the particles to make their plasmonic resonances overlap with the frequency of optical excitation. The designed hybrid metallic/organic nanostructures exhibited large enhancements of the efficiency of second harmonic generation (SHG) compared to conventional ISAM films, causing a modified film with just 3 bilayers to be optically equivalent to a conventional 700-1000 bilayer film. SHG responses from Ag nanoparticle-decorated hybrid-covalent ISAM (HCISAM) films were investigated as the next logical step towards high-Ï ²⁺ ISAM films. I found that the plasmonic enhancement primarily stems from interface SHG. Interface effects were characterized by direct comparison of SHG signals from PAH/PCBS ISAM films and PAH/PB HCISAM films. Though interface &chi²⁺ is substantially smaller in PAH/PCBS than in PAH/PB, plasmonically enhanced PAH/PCBS films exhibit stronger NLO response. I propose that the structure of PAH/PB film makes its interface more susceptible to disruptions in the nanoparticle deposition process, which explains our observations. During the fabrication of monolayer crystals for nanosphere lithography, I developed a variation of the technique of convective self-assembly, where the drying meniscus is restricted by a straight-edge located approximately 100 μM above the substrate adjacent to the drying zone. This technique can yield colloidal crystals at roughly twice the growth rate compared to the standard technique. I attribute this to different evaporation rates in the thin wet films in the two cases. I also found that the crystal growth rate depends strongly on the ambient relative humidity. Finally, dithiocarbamate (DTC)-grafted polymers were synthesized and employed to functionalize surfaces of Au nanopartciles. PAH-DTC shows greater stability in different environments than PEI-DTC. I also investigated the stability of PAH-DTC coated particles in suspensions with UV-Vis spectroscopy and autotitration. The covalently bonded PAH-DTC enhances the colloidal stability of the Au nanoparticles and enables subsequent ISAM film deposition onto the particles.
Degree
thesis:*- Name thesis:degree_name
- Ph. D.
- Level thesis:degree_level
- doctoral
- Discipline thesis:degree_discipline
- Physics
- Department dc:contributor.department
- Physics
- Grantor dc:publisher
- Virginia Tech
- Year dc:date.issued
- 2009
Author and committee
dc:creator, dc:contributor.*- Author dc:creator
-
- Chen, Kai
- Chair dc:contributor.committeechair
-
- Robinson, Hans D.
- Committee members dc:contributor.committeemember
-
- Davis, Richey M.
- Khodaparast, Giti A.
- Heflin, James R.
Subjects
dc:subject × 5Rights
dc:rights- Statement dc:rights
-
- In Copyright
- Licence dc:rights.uri
Identifiers
dc:identifier.*- Dc Identifier Other
- etd-12152009-191229
- OAI identifier oai:identifier
- oai:vtechworks.lib.vt.edu:10919/30111