This thesis described the development of new strategies for the preparation of micro- and nano-structured polymer materials. In particular, this thesis focused on: i) the synthesis of polymer particles in microreactors, and ii) the self-assembly of inorganic nanorods. First, this thesis presented the synthesis of polymer particles and capsules with pre-determined sizes and narrow size distributions (CV<2%) in continuous microfluidic reactors. The method includes (i) the emulsification of monomers in a microfluidic flow-focusing device and (ii) in-situ solidification of droplets via photopolymerization. This microfluidic synthesis provides a novel strategy for the control over the shapes, compositions, and morphologies of polymer particles. In particular, we demonstrated the control over particle shapes by producing polymer ellipsoids, disks, rods, hemispheres, plates, and bowls. We produced polymer particles loaded with dyes, liquid crystals, quantum dots, and magnetic nanoparticles. We generated core-shell particles, microcapsules, Janus and three-phasic polymer particles. Control over the number of cores per droplet was achieved by manipulating the flow rates of liquids in the microchannels. We further investigated the hydrodynamic mechanism underlying the emulsification of droplets, which helps in guiding scientists and engineers to utilize this technique. Second, we described the self-assembly of inorganic nanorods by using a striking analogy between amphiphilic ABA triblock copolymers and the hydrophilic nanorods tethered with hydrophobic polystyrene chains at both ends. We organized metal nanorods in structures with various geometries such as nanorings, nanochains, bundles, bundled nanochains, and nanospheres by tuning solely the quality of solvents. The self-assembly was tunable and reversible. This approach paved the way for the organization of anisotropic nanoparticles by using the strategies that are well-established for the self-assembly of block copolymers. We further described a systematic study of the self-assembly of polymer-tethered gold nanorods as a function of solvent composition in the system and the molecular weight of the polystyrene blocks. We found that the structure of the polymer pom-poms played an important role on the organization of polymer-tethered gold NRs. The 'supramolecular' assembly was governed by the competition between the end-to-end and side-by-side association of NRs and resulted in the controlled variation of the plasmonic properties of NRs, reflected in a 3-D plasmonic graph.

This thesis described the development of new strategies for the preparation of micro- and nano-structured polymer materials. In particular, this thesis focused on: i) the synthesis of polymer particles in microreactors, and ii) the self-assembly of inorganic nanorods. First, this thesis presented the synthesis of polymer particles and capsules with pre-determined sizes and narrow size distributions (CV<2%) in continuous microfluidic reactors. The method includes (i) the emulsification of monomers in a microfluidic flow-focusing device and (ii) in-situ solidification of droplets via photopolymerization. This microfluidic synthesis provides a novel strategy for the control over the shapes, compositions, and morphologies of polymer particles. In particular, we demonstrated the control over particle shapes by producing polymer ellipsoids, disks, rods, hemispheres, plates, and bowls. We produced polymer particles loaded with dyes, liquid crystals, quantum dots, and magnetic nanoparticles. We generated core-shell particles, microcapsules, Janus and three-phasic polymer particles. Control over the number of cores per droplet was achieved by manipulating the flow rates of liquids in the microchannels. We further investigated the hydrodynamic mechanism underlying the emulsification of droplets, which helps in guiding scientists and engineers to utilize this technique. Second, we described the self-assembly of inorganic nanorods by using a striking analogy between amphiphilic ABA triblock copolymers and the hydrophilic nanorods tethered with hydrophobic polystyrene chains at both ends. We organized metal nanorods in structures with various geometries such as nanorings, nanochains, bundles, bundled nanochains, and nanospheres by tuning solely the quality of solvents. The self-assembly was tunable and reversible. This approach paved the way for the organization of anisotropic nanoparticles by using the strategies that are well-established for the self-assembly of block copolymers. We further described a systematic study of the self-assembly of polymer-tethered gold nanorods as a function of solvent composition in the system and the molecular weight of the polystyrene blocks. We found that the structure of the polymer pom-poms played an important role on the organization of polymer-tethered gold NRs. The 'supramolecular' assembly was governed by the competition between the end-to-end and side-by-side association of NRs and resulted in the controlled variation of the plasmonic properties of NRs, reflected in a 3-D plasmonic graph.

Conducting polymer nanocomposites composed of metal oxides and polythiophene was synthesized by chemical polymerization in colloidal suspensions. The electrochemical and photoelectrochemical properties of such nanocomposites have been studied. For these investigations films of nanocomposites were prepared by an electrophoretic deposition process. The deposition process was studied in greater detail and kinetic details were determined. The high voltage electrophoretic deposition process was combined with a quartz crystal microbalance (QCM). Then the films were characterized by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and photocurrent spectroscopy.

Im Rahmen dieser Arbeit wurden schalenartig aufgebaute Nanoheterostrukturen aus CdTe, CdS und CdSe hergestellt und insbesondere im Hinblick auf ihre optischen Eigenschaften untersucht. Eine neue Variante der CdTe Nanokristallsynthese in ODE als hochsiedendem, nicht koordinierendem Lösungsmittel wurde entwickelt. Diese weist deutliche Vorteile im Bezug auf Reproduzierbarkeit und Wachstumskinetik gegenüber der älteren Synthese in TOP/TOPO auf, da durch ein deutlich verlangsamtes Wachstum die gezielte Synthese von Nanokristallen definierter Größe deutlich erleichtert wird. Diese CdTe Nanokristalle wurden sowohl mit CdS als auch mit CdSe beschichtet. Dabei wurden für beide Arten der Beschichtung verschiedene Methoden getestet und es konnte jeweils eine Synthesemethode gefunden werden, welche Kern-Schale Nanokristalle mit geringer Polydispersität und guten optischen Eigenschaften (schmale Emissionssignale und hohe Quantenausbeuten) liefert. Weiterhin wurden Kern-Schale-Schale Nanokristalle aus CdTe/CdS/CdSe synthetisiert. Dieses System besitzt besonders interessante Eigenschaften, die sich vor allem in Form einer über die eingebettete CdS Schicht einstellbare Ladungsträgertrennung im angeregten Zustand der Nanokristalle und der damit einhergehenden verlängerten Emissionslebensdauer zeigen. Die optischen Eigenschaften (erster elektronischer Übergang) der hergestellten Kern-Schale und Kern-Schale-Schale Teilchen wurden mit theoretischen Berechnungen im Rahmen der „Effektive-Masse-Näherung“ verglichen. Dieser Vergleich ergab für die mit CdSe beschichteten Teilchen eine gute, für die mit CdS beschichteten Teilchen allerdings nur eine mäßige Übereinstimmung. Auch die transmissionselektronenmikroskopischen Aufnahmen legen nahe, dass insbesondere die Beschichtung mit CdS nicht quantitativ im Bezug auf die eingesetzte Precursormenge abläuft. Die Emissionslebensdauern der verschiedenen Systeme zeigen nichts desto trotz, dass die theoretisch zu erwartende Ladungsträgertrennung im angeregten Zustand der CdTe/CdS/CdSe Kern-Schale-Schale Nanokristalle tatsächlich eintritt. Durch Einführen der CdS Schicht konnte eine Verlängerung der Emissionslebensdauer der Nanokristalle erreicht werden. Insbesondere wurde gezeigt, dass es möglich ist, verschiedene Nanoheterostrukturen herzustellen, deren Emissionslebensdauern unterschiedlich sind, obwohl sie bei derselben Wellenlänge Licht emittieren. Diese Eigenschaft kann mit Nanokristallen aus nur einem Material nicht erreicht werden. Durch die richtige Kombination von Halbleitermaterialien ist es also möglich, neben der bereits lange bekannten Möglichkeit der Einstellbarkeit der Emissionswellenlänge von Nanokristallen nun auch die Emissionslebensdauer der Nanokristalle zu beeinflussen.

The main goal of this work is design and synthesis of novel composite hydrogel-based core-shell microparticles and their application for fabrication of coatings, which provide the “inverse-switching” behaviour to the surface, namely, to become more hydrophobic in water environment. Since contact angle of heterogeneous surfaces is dependent on the nature and ratio of surface components, an increase of amount of more hydrophobic component on the surface will cause the reducing of surface wettability. It was suggested that core-shell particles having water-swellable hydrogel core and hydrophobic, but permeable for water shell when deposited on the hydrophilic substrate should increase the total amount of hydrophobic component on the surface when the cores of particles will swell in water. During the work different approaches to obtain freely dispersed and surface-immobilized core-shell particles with required structure were developed. Obtained particles were applied for preparation of coatings with ability to display “inverse-switching” behaviour. It was demonstrated that properly designed and properly prepared core-shell particles could be successfully used for creation of smart adaptive coatings having the ability to alter the surface properties upon changing of the environment.

Ce travail de thèse porte sur la caractérisation à l'échelle du fil unique des propriétés de fils GaN de taille micronique (µfil), en vue du développement d'une technologie de diodes électroluminescentes (LEDs) à base d'une assemblée de µfils GaN crûs par épitaxie en phase vapeur aux organométalliques. Chaque µfil est lui-même une LED constituée d'un cœur de type n et d'une coquille de type p, entre lesquels est insérée une zone active composée de multi-puits quantiques InGaN/GaN. En premier lieu, les propriétés électriques des différentes régions du cœur de type n ont été analysées par des mesures de résistivité à l'échelle du fil unique. Le µfil GaN:Si fortement dopé possède une conductivité électrique jamais rapportée dans le cas de couches planaires comparables. Une approche originale combinant une mesure de résistivité et de propriétés thermoélectriques a alors été développée pour séparer les contributions de la densité d'électrons et de leur mobilité à température ambiante dans ces µfils. Des mesures optiques résolues spatialement de cathodoluminescence (CL) et µRaman confirment ces valeurs de densités d'électrons. Une seconde partie détaille une étude résolue spatialement des jonctions p-n cœur-coquille par des techniques à base d'un faisceau électronique. Sur un µfil clivé, la jonction tridimensionnelle (axiale et radiale) existante dans ces structures est mise en évidence par une cartographie du champ électrique (courant induit par faisceau électronique, EBIC) ou du potentiel électrostatique (contraste de tension des électrons secondaires). Ces techniques renseignent alors sur les niveaux de dopage donneur et accepteur et les longueurs de diffusion des porteurs minoritaires à proximité de la jonction. La cartographie EBIC décrit également l'état d'activation des dopants Mg dans la coquille p-GaN:Mg. Finalement, la combinaison de mesures EBIC et CL avec une étude des propriétés électro-optiques d'un µfil LED, fournit des voies d'optimisation pour la réalisation de LEDs à base de µfils plus efficaces. / This thesis deals with the characterization of GaN microwires (µwires) at the single wire level,toward the development of a light-emitting diode (LED) technology based on an ensemble of standing GaN µwires grown by metal organic vapour phase epitaxy. Each µwire is actually an LED consisting of an n-type core and a p-type shell, between which an InGaN/GaN multiquantum well active region is inserted. First, the electrical properties of the different parts of the n-type core were determined using resistivity measurements at the single wire level. The GaN:Si µwire exhibits conductivity values never reported by the planar layer counterparts. An original technique combining resistivity and thermoelectric measurements was developed to infer the electron density and mobility in these µwires. Spatially resolved optical measurements such as cathodoluminescence (CL) and µRaman confirmed the electron density values. The second part describes a spatially resolved study of the core-shell p-n junction using electron beam probing techniques. On a cleaved wire, the tridimensional (axial and radial) junction was highlighted by mapping the electric field (electron beam induced current, EBIC) or the electrostatic potential (secondary electron voltage contrast). These techniques yielded the donor and acceptor doping levels as well as the minority carriers diffusion lengths in the vicinity of the junction. EBIC mapping also provided the activation state of Mg dopants in the p-GaN:Mg shell. Finally, a study of the electro-optical properties of a single µwire LED, combined with EBIC and CL measurements, paves the way to the fabrication of more efficient µwire-based LED.

This work details the synthesis and growth mechanisms of 1D magnetic and semiconducting nanostructures. Specifically, magnetic iron oxide and ZnS-SiO2 nanowires are examined. These materials are chosen due to their promise for biomedical and electronic applications and the perceived need to both create these structures as tools for these applications and to understand their formation processes so that they can be manufactured at a scale and efficiency suitable for commercialization. The current state and impact of nanotechnology is discussed through the lens of continuing technological advances and environmental factors, and the term is defined according to a specific set of criterion involving size, utility, and uniqueness. Details of synthesis and characterization of Fe3O4, ε-Fe2O3, and ZnS-SiO2 core-shell nanowires are presented. Observations regarding the growth of these structures are paired with additional experiments, simple simulations, and other literature to discuss the classical VLS growth process in general, and its applicability to these structures in particular. Finally, some exciting future applications are discussed, with details for initial experimental work presented in the appendix.

Le développement des moteurs électromagnétiques nécessite des matériaux magnétiques possédant une forte induction à saturation, une perméabilité magnétique importante, ainsi que de faibles pertes magnétiques lorsque le matériau est utilisé à des fréquences allant jusqu’à 20 kHz.Pour réduire ces pertes, le matériau doit alors posséder une résistivité électrique la plus élevée possible. Les composites magnétiques doux ont été développés dans ce contexte, en associant du fer (ou un alliage) à un matériau isolant. Historiquement, ceux-ci étaient présents sous forme de couches laminées, mais des matériaux coeur-écorce se sont développés ces dernières années.Au cours de ces travaux, nous avons développé l’enrobage de particules de fer par un matériau isolant et magnétique : le ferrite NiZn. L’enrobage de ferrite a été réalisé par voie liquide. De cette manière, il a été possible de réaliser un enrobage homogène d’épaisseur contrôlée sur des particules de fer sphériques.L’étude de la mise en forme de ces particules coeur-écorce, par métallurgie des poudres, a montré qu’en frittant le matériau composite à une température supérieure à 580°C, une réaction d’oxydoréduction a lieu entre les deux composés. Cette réaction mène à la formation d’une phase type FexNi1-x et d’une solution solide FeO-FeZnO. Ces deux phases font alors chuter les propriétés magnétiques du matériau final.Pour éviter cette réaction d’oxydoréduction, nous avons montré qu’il est possible d’ajouter une barrière de diffusion : la silice, ou bien de fritter le matériau à l’aide de techniques type FAST. De cette manière, nous avons obtenu un matériau possédant des pertes magnétiques comparables à celles de poudres industrielles mais avec une perméabilité magnétique supérieure. / Magnetic materials with high saturation induction, high magnetic permeability and low magnetic losses, are necessary for the development of electromagnetic motors used at frequencies up to 20 kHz.The electric resistivity of these materials must be as high as possible to reduce iron losses. To increase the resistivity of ferromagnetic materials, soft magnetic composites (SMC) were developed combining a ferromagnetic material with an insulating one. Firstly, laminated steel sheets were developed but during the last years core-shell materials were investigated.In this work, we have studied the coating of iron particles by an insulating and a magnetic material: NiZn ferrite. These coatings were deposited by an aqueous solution to obtain a homogenous coating with a controlled thickness on spherical iron particles.A study of composite shaping by powder metallurgy shows a redox reaction between ferrite and iron at a sintering temperature above 580°C. This reaction leads to the formation of a FexNi1-x and a FeO-FeZnO solid solution. These two phases deteriorate the magnetic properties of the final material.To avoid this redox reaction, we have shown that a silica layer can be used as a diffusion barrier. Another solution is to sinter the composite with a Field Assisted Sintering Technique (FAST) as Spark Plasma Sintering. A material with properties similar to industrial material and with a superior magnetic permeability was obtained with Spark Plasma Sintering

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Foram sintetizadas microesferas poliméricas com propriedades magnéticas e morfologia casca-núcleo por meio da técnica de polimerização em suspensão em duas etapas. O núcleo foi constituído por poli(estireno-co-divinilbenzeno) e magnetita modificada com ácido oleico. Foi avaliada a influência da velocidade de agitação e da concentração de iniciador sobre as características das microesferas utilizadas como núcleo (morfologia, tamanho de partículas, propriedades magnéticas e estabilidade térmica). A casca foi constituída por poli(estireno-co-divinilbenzeno) sem material magnético. Foi avaliado o método de adição da emulsão dos monômeros formadores da casca e o tempo de inchamento dos núcleos na emulsão. As microesferas casca-núcleo foram caracterizadas quanto ao seu aspecto morfológico e à estabilidade térmica. Os núcleos não apresentaram ciclos de histerese, estando assim próximos de um material com propriedades superparamagnéticas. O copolímero sintetizado com a maior velocidade de agitação e a menor concentração de iniciador foi o que apresentou o maior teor de ferro incorporado (3,317 %), a maior magnetização de saturação (2,99 emu/g) e o menor diâmetro médio de partículas (81 &#61549;m). As microesferas casca-núcleo apresentaram apenas um estágio de degradação e as suas Tmáx foram menores do que a do núcleo. O mapa composicional de ferro confirmou a presença de magnetita na superfície das microesferas casca-núcleo / Polymeric microspheres with magnetic properties and core-shell morphology were synthesized by the technique of suspension polymerization in two stages. The core was constituted by poly(styrene-co-divinylbenzene) and magnetite coated with oleic acid. The influence of stirring rate and initiator concentration on microspheres characteristics (morphology, particle size, magnetic properties and thermal stability) was studied. The shell was constituted by poly(styrene-co-divinylbenzene) without magnetic material. It was also evaluated the methods of the monomers emulsion addition and the coress swelling time in the emulsion.. The microspheres were characterized by morphologic aspect and thermal stability. The cores did not presented hysteresis cycles, thus proving the superparamagnetic properties. Copolymer synthesized with the higher stirring rate and lower initiator concentration presented the higher incorporated iron content (3.317 %), higher saturation magnetization (2.99 emu/g) and the lower average particle diameter (81 &#61549;m). Core-shell microspheres presented only one stage of degradation and the Tmáx were smaller than temperature of the cores. Iron compositional map confirmed the presence of magnetite on the surface of core-shell microspheres

Ce travail de thèse porte sur la caractérisation à l'échelle du fil unique des propriétés de fils GaN de taille micronique (µfil), en vue du développement d'une technologie de diodes électroluminescentes (LEDs) à base d'une assemblée de µfils GaN crûs par épitaxie en phase vapeur aux organométalliques. Chaque µfil est lui-même une LED constituée d'un cœur de type n et d'une coquille de type p, entre lesquels est insérée une zone active composée de multi-puits quantiques InGaN/GaN. En premier lieu, les propriétés électriques des différentes régions du cœur de type n ont été analysées par des mesures de résistivité à l'échelle du fil unique. Le µfil GaN:Si fortement dopé possède une conductivité électrique jamais rapportée dans le cas de couches planaires comparables. Une approche originale combinant une mesure de résistivité et de propriétés thermoélectriques a alors été développée pour séparer les contributions de la densité d'électrons et de leur mobilité à température ambiante dans ces µfils. Des mesures optiques résolues spatialement de cathodoluminescence (CL) et µRaman confirment ces valeurs de densités d'électrons. Une seconde partie détaille une étude résolue spatialement des jonctions p-n cœur-coquille par des techniques à base d'un faisceau électronique. Sur un µfil clivé, la jonction tridimensionnelle (axiale et radiale) existante dans ces structures est mise en évidence par une cartographie du champ électrique (courant induit par faisceau électronique, EBIC) ou du potentiel électrostatique (contraste de tension des électrons secondaires). Ces techniques renseignent alors sur les niveaux de dopage donneur et accepteur et les longueurs de diffusion des porteurs minoritaires à proximité de la jonction. La cartographie EBIC décrit également l'état d'activation des dopants Mg dans la coquille p-GaN:Mg. Finalement, la combinaison de mesures EBIC et CL avec une étude des propriétés électro-optiques d'un µfil LED, fournit des voies d'optimisation pour la réalisation de LEDs à base de µfils plus efficaces. / This thesis deals with the characterization of GaN microwires (µwires) at the single wire level,toward the development of a light-emitting diode (LED) technology based on an ensemble of standing GaN µwires grown by metal organic vapour phase epitaxy. Each µwire is actually an LED consisting of an n-type core and a p-type shell, between which an InGaN/GaN multiquantum well active region is inserted. First, the electrical properties of the different parts of the n-type core were determined using resistivity measurements at the single wire level. The GaN:Si µwire exhibits conductivity values never reported by the planar layer counterparts. An original technique combining resistivity and thermoelectric measurements was developed to infer the electron density and mobility in these µwires. Spatially resolved optical measurements such as cathodoluminescence (CL) and µRaman confirmed the electron density values. The second part describes a spatially resolved study of the core-shell p-n junction using electron beam probing techniques. On a cleaved wire, the tridimensional (axial and radial) junction was highlighted by mapping the electric field (electron beam induced current, EBIC) or the electrostatic potential (secondary electron voltage contrast). These techniques yielded the donor and acceptor doping levels as well as the minority carriers diffusion lengths in the vicinity of the junction. EBIC mapping also provided the activation state of Mg dopants in the p-GaN:Mg shell. Finally, a study of the electro-optical properties of a single µwire LED, combined with EBIC and CL measurements, paves the way to the fabrication of more efficient µwire-based LED.