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.

L'auto-assemblage de polymères a été étudié afin d'élaborer des films multicouches possédant des propriétés conductrices. Dans un premier temps, l'influence de différents paramètres physico-chimiques (pH , force ionique, nature et charge des ions, concentrations en polymères...) sur la croissance de couche polymères isolants (PSS ou PDDA) / polymères conducteurs ( PEDOT : PSS ou P3HT-R) a été étudiée par des mesures in-situ de réflectométrie laser à angle fixe. La compréhension de ses paramètres a permis de contrôler l'assemblage des matériaux afin d'obtenir des films multicouches aux propriétés souhaitées ( épaisseur, morphologie, conductivité électrique...)les épaisseurs des films obtenus ont été déterminées par ellipsométrie ou profilométrie, la morphologie de la morphologie de la surface de ces films a été observé par MEB et leur conductivité a été mesurée par la méthode de van Pauw. Dans un second temps, des films multicouches polymères / particules composites ont été construits après avoir optimisé les conditions d'élaboration des particules composites Al2-PEDOT : PSSph ou SiO2-P3HT-R).Les films multicouches obtenus présentent des conductivités équivalentes à celles des films à base de polymères mais sont construits avec moins d'étapes d'adsorption. Enfin des couches multicouches à bases de deux polymères conducteurs (P3HT-R et PEDOT:PSS) ont été construits sur substrats souples. Ils présentent la plus haute conductivité mesurée (1,5 S.m-1) et conservent leurs propriétés électriques lorsqu'ils sont soumis à des contraintes mécaniques de flexion , ce qui est prometteur quant à leur utilisation dans le domaine de l'électronique déformable. / Self-assembly of polymers has been studied in order to produce multilayer films having conductive properties. First, the influence of various physicochemical parameters (pH, ionic strength, nature and charge of ions, polymer concentrations, etc.) on the growth of insulating polymer (PSS or PDDA) / conductive polymers (PEDOT : PSS or P3HT-R) was studied by in-situ measurements of fixed-angle laser reflectometry. The understanding of its parameters allowed to control the assembly of the materials in order to obtain multilayer films with the desired properties (thickness, morphology, electrical conductivity...) The thicknesses of the films obtained were determined by ellipsometry or profilometry, morphology Of the surface morphology of these films was observed by SEM and their conductivity was measured by the method of van Pauw. Second, polymer multilayer films / composite particles were built after optimizing the conditions for the production of the composite particles Al2-PEDOT: PSSph or SiO2-P3HT-R). The multilayer films obtained have conductivities equivalent to those of Films are based on polymers but are constructed with fewer adsorption steps. Finally, multilayer layers based on two conductive polymers (P3HT-R and PEDOT: PSS) were built on flexible substrates. They have the highest conductivity measured (1.5 Sm-1) and retain their electrical properties when subjected to mechanical bending stresses, which is promising for their use in the field of deformable electronics.