Doctor of Philosophy / Department of Physics / Christopher M. Sorensen / Nano-size materials are new materials in an intermediate state between the bulk and atomic or molecular states. Nanoparticles in colloidal solution and their assemblies have the great attention of researchers to investigate the novel fundamental properties and numerous applications. In this dissertation, we investigated the solubility phase transition behavior of gold nanoparticles in colloidal solution. We used the nearly monodisperse gold nanoparticles synthesized by either the inverse micelle or the solvated metal atom dispersion methods followed by digestive ripening. The gold nanoparticles were ligated with alkyl chains, which were dodecanethiol, decanethiol, or octanethiol for individual samples. They dispersed in toluene or t-butyl toluene like large molecules at room temperature. In analogy to molecular solutions, the colloidal solution had thermally reversible phase transitions between a dissolved phase of dispersed single nanoparticles and dispersed-aggregation co-existing phase. A more polar solvent, 2-butanone, was added to the colloidal solution for changing the solubility of gold nanoparticles and adjusting the phase transition temperatures to accessible temperatures. Superclusters formed by the nanoparticles when the colloidal solutions were quenched from a one-phase regime at high temperature to a two-phase regime at low temperature. Solubility phase diagrams were obtained for gold nanoparticles with different ligands in the mixtures of different ratios of 2-butanone and toluene or t-butyl toluene. The explanation from classical ideal solution theory gave the fusion enthalpy of superclusters. Temperature quenches from the one-phase to the two-phase regime yielded superclusters of the nanoparticle solid phase with sizes that depended on the quench depth. Classical nucleation theory was used to describe these sizes using a relative small value of the surface tension for the nanoparticle solid phase. This value is consistent with molecule size scaling of the surface tension. In total these results show that the solubility behavior of nanoparticles in colloidal solution is similar to the behavior in molecular solutions.

Cette thèse est consacrée à l’étude de processus de concentration de solutions colloïdales par voie microfluidique, pour former des matériaux denses et structurés. A partir d’un outil basé sur la perméation de l’eau à travers le PDMS : le microévaporateur, nous proposons de contrôler le séchage de solution pour maîtriser la concentration de solutés afin de former des états denses organisés au choix, alternant cristaux et états amorphes de colloïdes. En adaptant les outils de microévaporation à différentes techniques d’observations, la nucléation et la croissance d’états denses ont été finement étudiées et correlées à un modèle simple de la microévaporation. Ces études expérimentales ont montré le contrôle précis qu’apporte le microévaporateur sur les cinétiques de concentration d’espèces chimiques pour la formation d’états denses de particules.Des études complémentaires ont aussi mis en évidence l’existence d’une dynamique de construction de cristaux colloïdaux avec des réorganisations au niveau du front ainsi qu’un effet de compaction présents lors de la croissance de l’état dense. / This work is devoted to studying processes of colloidal solutions concentration by microfluidic way to shape dense and organized states. Using a tool based on the water permeation through the PDMS: the microevaporator, we propose to control drying of solution for controlling solute concentration to form dense states as one chooses, alternating crystals and amorphous states of colloids.By adapting microevaporation tool at different observation techniques, nucleation and growth are particularly studied and correlated to a simple microevaporation model. This experimental work demonstrates the good control on kinetics of chemical species concentration offered by microevaporation, in order to shape dense states of particles.Further studies also reveal existence of a dynamic construction of colloidal crystal with some reorganization in the front growth and a compaction effect of the dense state during the growth.

Основной целью данной работы являлось исследование условий, необходимых для роста наноструктур на основе водного коллоидного раствора с наночастицами, созданными с помощью лазерной абляции мишени металлического цинка. Исследования проводились при помощи различных методик, включая СЭМ, ПЭМ, РФЭС и оптическое поглощение, позволяющих исследовать форму и состав полученных наночастиц. В первой части работы содержится обзор литературных источников, посвященный механизму формирования наночастиц, принципиальной схеме синтеза наночастиц методом лазерной абляции в жидкости и основным характеристикам наночастиц оксида цинка. Вторая часть работы включает в себя цели и задачи, поставленные в данной работе. В третьей части описаны методики получения и исследования наночастиц. Четвертая часть посвящена данным, полученным в ходе синтеза, описанию характеристик и свойств наночастиц, а также сформулированным выводам. В результате проведения исследования показано, что импульсная лазерная абляция цинка в воде позволяет создавать наночастицы оксида цинка способные к ориентированному росту. / The main goal of this work was to investigate the conditions necessary for the growth of nanostructures in water based colloid produced by laser ablation of metallic zinc. The studies were carried out using various techniques, including SEM, TEM, XPS, and optical absorption, which made it possible to study the shape and composition of the nanoparticles. The first part of the work contains a review of literature sources devoted to the mechanism of nanoparticle formation, the principle scheme of the nanoparticle synthesis by laser ablation in liquid, and the main characteristics of zinc oxide nanoparticles. The second part of the work includes the goals and objectives set in this work. The third part describes methods for obtaining and studying nanoparticles. The fourth part is devoted to the obtained data, the characteristics and properties of nanoparticles, and the conclusions. It was shown that pulsed laser ablation of zinc in water allows to create zinc oxide nanoparticles capable of oriented growth.

Dans ce travail de thèse, la synthèse de nanoparticules d'argent (Ag) est réalisée par une méthode simple, efficace et rapide basée sur la réduction du nitrate d'argent (AgNO3) dans un milieu organique (éthanol) sous chauffage par irradiation micro-ondes (MW) pendant quelques secondes en présence d'une émulsion aqueuse de copolymère latex. Les expériences ont été effectuées soit de manière séquentielle en faisant varier les paramètres expérimentaux les uns après les autres (approche classique) ou bien en moyennant la méthodologie des plans d'expérience qui sert à varier simultanément ces conditions expérimentales dans le but à la fois d'optimiser et d'évaluer l'impact de ces facteurs sur les propriétés physico-chimiques des particules produites. L'objectif est d'arriver à préparer un maximum de concentration en nanoparticules d'argent avec un minimum de concentration en copolymère latex et en AgNO3. Les nanoparticules préparées sont trouvées extrêmement stables en solution colloïdale avec des distributions de taille très étroites, ce qui confirme la qualité élevée et le diamètre uniforme des nanoparticules obtenues par l'approche de synthèse micro-ondes. Ceci pourrait être probablement dû à l'effet de stabilisation produit par les molécules du latex, qui est un bon environnement pour contrôler efficacement la croissance de nanoparticules métalliques d'argent. En tant que principal objectif d'une telle réalisation de la synthèse de nanoparticules d'argent par la méthode MW ouvre la voie à l'exploitation d'effets plasmoniques de surface dans des réactions photocatalytiques en utilisant des structures semi-conductrices bien définies (Bi2O3, In2O3, TiO2...). / In this thesis work, the synthesis of silver nanoparticles (Ag) is carried out by a simple, efficient and fast method based on the reduction of silver nitrate (AgNO3) in an organic medium (ethanol) under heating by micro irradiation (MW) for a few seconds in the presence of an aqueous emulsion of latex copolymer. The experiments were performed either by varying the experimental parameters one after the other (classical approach) or by means of the experimental design methodology which serves to vary simultaneously these experimental conditions in order to both optimize and evaluate the impact of these factors on the physicochemical properties of the nanoparticles. The main goal is to prepare a maximum concentration of silver nanoparticles with a minimum concentration of latex copolymer and AgNO3. The prepared nanoparticles were found to be extremely stable in colloidal solution with very narrow size distributions, which confirms the high quality and the uniform diameter of the nanoparticles obtained by the microwave synthesis approach. This could possibly be due to the stabilizing effect produced by the latex molecules, which is a good environment for effectively controlling the growth of metallic silver nanoparticles. As the main objective of such realization of the silver nanoparticle synthesis by the MW method opens the way to the exploration of surface plasmonic effects in photocatalytic reactions using well-defined semiconducting structures (Bi2O3 , In2O3, TiO2 ...).