This 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. / Ph. D.

Incorporation of silver nanoparticles (AgNPs) into an increasing number of consumer products has led to concern over the potential ecological impacts of their unintended release to the environment. Dissolution is an important environmental transformation that affects the form and concentration of AgNPs in natural waters; however, studies on AgNP dissolution kinetics are complicated by nanoparticle aggregation. Herein, nanosphere lithography (NSL) was used to fabricate uniform arrays of AgNPs immobilized on glass substrates. Nanoparticle immobilization enabled controlled evaluation of AgNP dissolution in an air-saturated phosphate buffer (pH 7, 25 °C) under variable NaCl concentrations in the absence of aggregation. Atomic force microscopy (AFM) was used to monitor changes in particle morphology and dissolution. Over the first day of exposure to ≥10 mM NaCl, the in-plane AgNP shape changed from triangular to circular, the sidewalls steepened, and the height increased by 6-12 nm. Subsequently, particle height and in-plane radius decreased at a constant rate over a 2-week period. Dissolution rates varied linearly from 0.4 to 2.2 nm/d over the 10-550 mM NaCl concentration range tested. NaCl-catalyzed dissolution of AgNPs may play an important role in AgNP fate in saline waters and biological media. This study demonstrates the utility of NSL and AFM for the direct investigation of un-aggregated AgNP dissolution. / Master of Science

Metal-based nanoparticles (MNPs) are becoming increasingly common in commercial products. Release of these materials into the environment raises concerns about the potential risks they pose to aquatic life. Predicting these risks requires an understanding of MNPs' chemical transformations. In this study, arrays of immobilized MNPs fabricated by nanosphere lithography (NSL) were used to investigate environmental transformations of MNPs. Specifically, sulfidation of silver nanoparticles (Ag NPs) and dissolution of copper-based nanoparticles (Cu NPs) were investigated. Atomic force microscopy (AFM) and transmission electron microscopy were the primary analytical techniques for these investigations. Because the MNPs were immobilized on a solid surface, the samples were field deployable, environmentally relevant metal concentrations were maintained, and the confounding influence of MNP aggregation was eliminated. Ag NP samples were deployed in a full-scale wastewater treatment plant. Sulfidation occurred almost exclusively in anaerobic zones of the WWTP, where the initial sulfidation rate was 11-14 nm of Ag converted to Ag2S per day. Conversion to Ag2S was complete within 7-10 d. Dissolution rates of Cu-based NPs were measured in situ over a range of pH by flow-cell AFM. Based on the measured rates, CuO/Cu(OH)2 NPs dissolve completely within a matter of hours at any pH, metallic Cu NPs persist for a few hours to days, and CuxS NPs do not dissolve significantly over the time scales studied. Field deployment of samples in a freshwater stream confirmed these conclusions for a natural aquatic system. This research demonstrates that environmental transformations of MNPs will be a key factor in determining the ultimate form and concentration of NPs that aquatic organisms will be exposed to. / Ph. D.

Un grand défi actuel consiste à réaliser des capteurs innovants tirant partie des propriétés singulières de nanoparticules colloïdales synthétisées par voie chimique et assemblées de manière contrôlée sur des surfaces. L’objet de cette thèse est le développement de jauges de contrainte résistives à base de nanoparticules. Ces jauges de contrainte sont constituées de lignes parallèles, de quelques micromètres de large, denses, de nanoparticules colloïdales d’or synthétisées par voie chimique et assemblées sur des substrats souples par assemblage convectif contrôlé. Le principe de ces capteurs résistifs repose sur la conduction tunnel entre les nanoparticules qui varie de manière exponentielle lorsque que l’assemblée est déformée. Des mesures électro-mécaniques couplées à des observations en microscopie électronique à balayage et à force atomique ont permis d’identifier, de quantifier et de comprendre l’impact de la taille et de la nature des ligands des nanoparticules sur la sensibilité et les phénomènes de dérive de la résistance à vide des jauges de contrainte. Ces travaux, associés à des mesures de diffusion de rayons X aux petits angles ont permis de corréler les variations macroscopiques de résistance électrique des jauges de contrainte aux déplacements relatifs des nanoparticules. Finalement, ces jauges de contrainte ultra-sensibles et miniatures, mises en matrices, ont été exploitées pour réaliser des surfaces tactiles souples multi-points et sensibles à l’intensité de l’appui / One recent big challenge is to implement innovative sensors that take advantage of the unique properties of colloidal nanoparticles chemically synthesized and assembled on various surfaces. The goal of this work is the development of nanoparticle based resistive strain gauges. These strain gauges are constructed of few micrometers wide parallel wires of close packed colloidal gold nanoparticles, chemically synthesized, and assembled on flexible substrates by convective self assembly. The principle of these resistive sensors is based on the tunnel conduction between the adjacent nanoparticles which varies exponentially as the assembly is stretched. Electro-mechanical measurements coupled with scanning electron microscopy and atomic force microscopy observations were used to identify, quantify and understand the impact of the nanoparticle size and the nature of the protecting ligands, on the gauge sensitivity and the drift of the resistance at rest of the nanoparticle based strain gauges. Coupled with small angle x-ray scattering measurements, these studies allowed us to correlate the macroscopic changes in electrical resistance of the strain gauges to the relative displacement of the nanoparticles at the nanoscale. Finally, a matrix of these miniature ultra-sensitive gauges was used to construct flexible touch screen panels capable of measuring the intensity of several touches simultaneously