El presente trabajo tiene como objetivo desarrollar en solución acuosa y a tem-peratura ambiente, rutas de síntesis química coloidal de nanopartículas de plata y nano-partículas compuestas estables. Se obtienen nanopartículas de plata reproducibles, con un control morfológico de tamaño y forma durante el proceso de síntesis. Llevamos a cabo el estudio de las propiedades ópticas (espectros de absorción de las resonancias de plasmones superficiales (SPR)) que caracterizan a una determinada forma y tamaño. El análisis incluye estructuras nanométricas de plata de diferentes tamaños, en ambientes diversos y formas diferentes, como esferas, prolates, y prismas de diferente sección transversal, etc Se ha demostrado que la síntesis química produce coloides de nanopartículas de plata esféricas y anisotrópicas estables. La morfología y estabilidad de las nanopartícu-las coloidales son estudiadas mediante técnicas de espectroscopia y microscopía elec-trónica. El rol y concentración necesaria de cada uno de los reactivos para producir co-loides estables mediante síntesis química son determinadas. Se ha demostrado que, con-trariamente a las opiniones actualmente expresadas en la literatura, es posible controlar el tamaño de las nanopartículas de plata y obtener coloides de nanopartículas de plata esféricas y anisotrópicas estables por largo tiempo, utilizando una ruta de síntesis quí-mica sencilla y una baja concentración de reactivos estabilizadores (PVP). Recubrimientos de nanopartículas esféricas de plata estabilizadas con polivinilpirroli-dona (PVP) sobre substratos de vidrio óptico son preparados mediante el proceso de spin-coating y un posterior tratamiento térmico. Diferentes morfologías tipo core-shell de Ag@SiO2 son preparados mediante un método químico simple y rápido, sin necesidad de adicionar reactivos de acoplamiento o modificadores superficiales de la sílice. Proponemos mecanismos de reacción para la preparación de diferentes nano-estructuras tipo core-shell de plata-sílice. Las nanopartí-culas compuestas de sílice-plata muestran unas propiedades de absorción de resonancia plasmónica muy evidentes. El trabajo de éste capítulo ha sido realizado en colaboración con Juan C. Flores, quien desarrolló la ruta de síntesis como parte de sus estudios de doctorado. Por último, una modificación del método sol-gel es empleada para la prepara-ción de nanopartículas de TiO2, y partículas compuestas de Ag@TiO2, SiO2@TiO2-Ag y SiO2@Ag@TiO2. Diferentes morfologías tipo core-shell son preparadas mediante un método químico simple y rápido sobre un substrato óxido, sin necesidad de adicionar agentes de acoplamiento o modificaciones superficiales. Las evidentes propiedades de absorción plasmónica de las nanopartículas de plata mostradas por las partículas com-puestas han demostrado la presencia de plata metálica sobre la titania, sin la posterior oxidación de la capa de plata por el contacto directo con la titania (TiO2). Esta evidencia es confirmada por la técnica de microscopía electrónica de alta resolución. Las propie-dades de absorción plasmónica de las partículas compuestas hacen a estos materiales muy prometedores para aplicaciones foto-catalíticas. / The present work aims to develop chemical synthesis routes of stable colloidal silver nanoparticles and composites nanoparticles in aqueous solution at room tempera-ture. We obtain reproducible morphological control of silver nanoparticles size and shape during synthesis solely by solution chemistry and carry out the study of the opti-cal properties (surface plasmon resonances (RPS) absorption spectra) which character-ize a specific shape and size. The analysis includes silver nanosized bodies of different size, in diverse environments and of various shapes, as spheres, prolates, and prisms of different transversal section, etc. Synthetic wet chemistry routes yielding stable colloids of spherical and aniso-tropic silver nanoparticles are demonstrated, and the morphology and stability of the colloidal nanoparticles studied extensively through spectroscopy and electron micros-copy techniques. The role of each reagent and the concentrations required to obtain sta-ble colloid via these wet chemical routes is determined. It was shown that, contrary to commonly expressed opinions in the literature, it is possible to control the particle size of silver nanoparticles and obtain long-term sable colloids of both spherical and aniso-tropic silver nanoparticles using simple chemical routes and low concentration of stabi-lizing agent (PVP). Films of polyvinylpyrrolidone (PVP) stabilized spherical silver nanoparticles are also prepared, by using spin coating on standard optical glass plates and subsequent thermal processing. Different core-shell type morphologies of Ag@SiO2 are also produced using a simple and rapid chemical method, without using added coupling agents or surface modifications of silica. We propose reaction mechanisms for the formation of the dif-ferent silica-silver core-shell nanostructures. The silica-silver composite nanoparticle display clear plasmonic resonance absorption properties. This chapter work has been done in collaboration with PhD student Juan C. Flores who developed the synthesis route as part of his doctoral studies. Finally, a sol-gel chemistry approach was used to fabricate nanoparticles in the systems TiO2, Ag@TiO2, Ag@TiO2-SiO2 and TiO2@Ag@SiO2. Different core-shell morphologies are produced using a simple and rapid chemical method. without using added coupling agents or surface modifications of the oxide substrate. Clear silver na-noparticle plasmonic absorption properties shown by the composite nanoparticles demonstrate the formation of metallic Ag, without the oxidation of Ag nanoshell in di-rect contact with TiO2, evidence confirmed also by high resolution electron microscopy. The plasmonic absorption properties of the composites nanoparticles make them a promising material for photocatalytic applications.

The purpose of this thesis is to make a broadband antireflection coating configuration known as a quarter-wave stack consisting of one layer of titania and of one layer of silica nanoparticles. We utilize much that is already known about silica nanoparticle deposition. The first objective of this thesis is deposition and characterization of titania nanoparticle films deposited on glass microscope slides by a technique known as Ionic Self-Assembled Multilayers or ISAM deposition. This technique takes advantage of the electrostatic attraction between oppositely charged materials and ideally results in a uniform nanoparticle film whose thickness and optical properties can be tightly controlled. Deposition of a quarter-wave stack based on ISAM deposition of silica and titania nanoparticles is significantly simpler and less expensive than alternative deposition methods. Initial attempts to deposit titania films were unsuccessful because of excess diffuse scattering due to inhomogeneities in the film. In order to reduce diffuse scattering, two approaches were considered. The first approach was to improve the deposition process itself by experimenting with different values of deposition parameters such as solution pH and solution molarity. The other approach focused on removing the large nanoparticle aggregates from the colloidal solutions of titania nanoparticles that were suspected to be responsible for rough film surfaces resulting in diffuse scattering. This approach was successful. In addition, evidence suggested that surface roughness contributed more to diffuse scattering than the bulk of the films. After minimizing diffuse scattering from titania nanoparticle films, we used known results from research on silica nanoparticle films to deposit quarter-wave stacks consisting of one layer of titania nanoparticles with high refractive index and one layer of silica nanoparticles with low refractive index. This contrast in refractive indices is a desirable characteristic of quarter-wave stacks. The thicknesses and refractive indices of the two layers in the quarter-wave stacks were measured by ellipsometry and compared to the nominal thicknesses of these layers. Finally, the reflectance was derived from a model of the quarter-wave stack and was compared to the measured reflectance. It was found that construction of a quarter-wave stack by ISAM is possible but that it will be necessary to acquire data from more experiments. / Ph. D.