Effects of Geometrical Order on the Linear and Nonlinear Optical Properties of Metal Nanoparticles

Abstract

This dissertation describes experimental and computational studies of the effects of ordered arrangement on the linear and nonlinear optical properties of metal nanoparticles. The principal result is that second-harmonic light may be generated and observed from nanoparticle gratings having maximum in-plane symmetry, provided that one looks at non-normal observation angles. These measurements are made possible by a custom-built variable-angle microscope, and enable a variety of studies of the second-order nonlinear response of nanoparticles that were not previously feasible. In addition, the surface plasmon resonance of metal nanoparticles is studied by linear spectroscopy. A comparison of experimental data with computational modeling shows that under normal ambient conditions, Ag nanoparticles tarnish by a sulfidation reaction more readily than bulk silver, and that even a very thin surface layer of corroded material (Ag2S) considerably redshifts and weakens the localized surface plasmon resonance of a nanoparticle.