Plasmonic Enhancement of Nonlinear Optical Responses by Gold Nanorods

The increase in the magnitude of local electric fields through resonances of plasmonic excitations in metallic nanoparticles is a major area of current optical research. This dissertation is focused on plasmon-enhanced second harmonic generation of organic ionic self-assembled films via localized surface plasmon resonance of gold nanorods. By matching the plasmon resonance of the gold nanorods to the wavelength of the fundamental light, it is possible to greatly enhance the SHG efficiency. To demonstrate this, the surface of the gold nanorods was functionalized with a nonlinear-optical (NLO) polymer, PCBS, via the layer-by-layer method and deposited on a polymer thin film created on a glass substrate using the ionic self-assembled multilayer (ISAM) method.

The sample fabrication is divided into two parts: gold nanorod synthesis and functionalization. The gold nanorods were synthesized by the seed-mediated method with varying amounts of silver ions to control their LSPR wavelengths. The functionalization started by replacing the original thick CTAB bilayer on the surface of the gold nanorods by a thin PAH-DTC layer via dialysis. The nanorods were then alternately coated with PAH (polycation) and PCBS (NLO polyanion) up to three bilayers of PAH/PCBS. The number of polymer layers on the nanorods was chosen in consideration of the LSPR decay length (a few nm). The functionalized gold nanorods were then deposited on either PAH/PCBS or PAH/PSS ISAM films.

Characterization was performed via optical spectral measurement, zeta potential measurement, and field-emission scanning electron microscopy (FESEM). The LSPR wavelength shifted when the surrounding medium changed. It was red-shifted for each added polymer layer on the nanorod surface. However, when the functionalized nanorods were deposited on the ISAM film, the resonance peak blue-shifted. The zeta potential confirmed the proper electric charge of each polymer layer coated on the nanorods. Finally, FESEM was performed on the samples for visual inspection of the nanorod deposition and distribution after the SHG measurement was complete.

The SHG from the functionalized gold nanorods was measured using a Maker-like fringe method. In this method, second harmonic waves generated from the front and rear sides of the substrate interfere constructively and destructively when the sample is rotated with respect to the incoming pump wave. Electrical noise reduction techniques were implemented to improve the SHG signal readings. Signal processing was implemented using LabVIEW software in order to read a reliable SHG signal from the setup. The maximum tolerable fluence of the gold nanorods was determined in order to prevent optical damage. The interference fringe pattern was observed from the functionalized gold nanorods and compared with that from the conventional ISAM film. The enhancement from the gold nanorods was as high as 600 times compared to the bare films. Polarization dependent SHG measurements were conducted to ascertain the effect of coupling between p- or s-polarized fundamental incident light to the SH light. To further improve the SHG enhancement, the self-assembly method herein can be extended from a monolayer to multilayers of functionalized gold nanorods.