La thèse a pour objet l’analyse de mécanismes d’assemblage permettant la création de structures auto-assemblées à base d’ADN, fonctionnalisées par des protéines. Les PDNA sont des molécules synthétiques associant de manière covalente une séquence d’ADN et un module protéique. Basés sur le domaine hèmique du cytochrome b5, les PDNA présentent des propriétés d’absorption optique dépendant de l’état d’oxydoréduction. Pour comparer leurs propriétés d’assemblage à celles des ADN correspondants, différentes briques ont été assemblées en ensembles finis ou ouverts. Un premier chapitre développe des approches expérimentales et de modélisation pour caractériser les paramètres contrôlant ces assemblages dans le cas des ADN. Un second chapitre transpose ces approches aux assemblages de PDNA afin de mettre en évidence l’influence des domaines protéiques. Dans les deux cas, les travaux sont menés à la fois à un niveau macroscopique et de molécule unique par AFM classique ou à haute vitesse. Une troisième partie vise à comprendre comment ces assemblages peuvent être multiplexés sur des puces au sein de matrices poreuses de dextran. Nous avons modélisé l’influence de la matrice sur l’assemblage et utilisé ces modèles pour définir les relations entre observables et paramètres microscopiques. Une dernière partie vise à lever les limitations (pièges d’assemblages) mises en évidence dans les réactions sous contrôle cinétique. Nous avons développé des assemblages dans des conditions douces et contrôlées par le pH impliquant des structures ADN en motifs-i. Leur mécanisme de formation et de polymérisation en suprastructures a été étudié en combinant biochimie et analyse structurale par AFM. / The work aimed at the analysis of assembly mechanisms allowing the creation of DNA-based self-assembled structures functionalized with proteins. PDNA are synthetic molecules covalently associating a DNA strand to a protein domain. The ones based on the heme binding domain of cytochrome b5 feature optic properties that depend on oxydoreduction state. In order to compare self-assembly properties of PDNA and corresponding DNA, different building blocks were assembled into converging or open ensembles. A first part develops experimental and modeling approaches to characterize parameters controlling such assemblies of DNA blocks. A second part extends these approaches to PDNA assemblies, bringing in evidence the influence of the protein domain on nucleic parts. Studies were both performed at macroscopic and single molecule levels using conventional and high-speed AFM. A third part describes how chip multiplexing of those assemblies onto a porous dextran matrix influences behaviors. Modeling the matrix influence on assembly allowed defining relations between experimental and macroscopic parameters. A last part aims at bypassing bottlenecks related to the formation of trapped structures when reactions are kinetically driven. We developed i-motif based DNA structures that can be assembled into mild, pH controlled conditions. Their mechanism of formation and polymerization into supramolecular structures were studied combining physico-chemical and structural analyses using AFM.

Les cellules solaires organiques continuent leur essor dans le domaine du photovoltaïque, grâce aux structures et matériaux activement étudiés, pour tendre vers le maximum de rendement et passer le cap de l'industrialisation. La séparation de phase des matériaux qui constituent la couche photo-active des cellules à hétérojonction en volume gouverne en partie les performances de la cellule, ainsi que des phénomènes de recombinaison liés à la photo-conversion. Des moyens de caractérisation spécifiques sont nécessaires pour sonder les propriétés des cellules aussi bien à l'échelle microscopique qu'à l'échelle nanométrique. Des bancs de caractérisations opto-électriques pour les cellules solaires organiques ont alors été développés. Ainsi, la technique du courant induit par faisceau lumineux (LBIC) permet de visualiser l'uniformité des cellules avec une résolution de 50µm. La microscopie à force atomique en mode conduction (C-AFM) permet quant à elle de sonder les propriétés photo-électriques des cellules à l'échelle du nanomètre. / Organic solar cells are becoming more prominent in the photovoltaic field thanks to new materials and stacked structures. The active layer of bulk heterojunction solar cells is composed of an interpenetrating network of electron donor and acceptor materials. Vertical phase separation governs cells power conversion efficiency and recombination phenomena are still being studied. Specific characterization tools are necessary to gain insights into cell properties at the nanometer scale and at the molecular level. In this context, this thesis allowed the development of electrical characterization tools for bulk heterojunction organic solar cells based on polymer/fullerene blend. Thus, the Light Beam induced Current (LBIC) technique has been developed to check the current uniformity of the cells with a 50µm resolution. Conductive-AFM (C-AFM) has been used to probe the photovoltaic properties of the cells in the nanometer range.

Ce mémoire porte sur deux aspects du traitement des surfaces de GaAs faisant appel à des plasmas, dans le but de déposer des couches contrôlées d’oxyde et de nitrure. Dans les deux cas divers moyens d’analyse ont été utilisés pour contrôler la composition chimique ainsi que l’épaisseur et la structure des couches créées. Des calculs théoriques des signaux XPS établis sur une représentation schématique des échantillons ont été à la base de la compréhension des phénomènes mis en jeu. La première étude exposée dans ce mémoire a permis de démontrer l’efficacité d’un plasma micro-ondes composé d’O2 et de SF6 pour le nettoyage de substrats de GaAs ayant subis un ou plusieurs processus technologiques. La variation de paramètres comme la composition ou la puissance du plasma et le temps d'exposition à celui-ci nous a permis de mieux comprendre les mécanismes d’oxydation se déroulant sur la surface. Notamment, la présence de SF6 dans le plasma diminue la concentration d’arsenic sur la surface et améliore ainsi la stabilité de l’oxyde. La seconde étude réalisée dans ce travail, qui présente la nitruration de substrats de GaAs suivant différentes orientations, a mis en évidence les avantages que procure l’utilisation d’une source GDS à faible puissance pour la création d’une couche surfacique de GaN de très bonne qualité. Ce processus optimisé amène à une couche de nitrure exempte de composés dus à l’inter-diffusion de l’arsenic et de l’azote, et montre une quasi-saturation de l’épaisseur de la couche de nitrure en fonction du temps d’exposition. De plus cette couche se cristallise par recuit en une maille cubique de paramètre proche de celui du GaN. / This thesis focuses on two aspect of GaAs surface treatment using plasma in order to deposit controlled oxide and nitride layers. In both cases, various means of analysis were used to control the chemical composition and the thickness and the structure of produced layers. Theoretical calculations of the XPS signals established on a schematic representation of the samples allow the understanding the involved phenomena. The first study reported in this thesis has demonstrated the efficiency of a microwave plasma composed of O2 and SF6 for the cleaning of GaAs substrates having undergone one or several technological processes. The variation of plasma parameters such as composition, power and exposure time enables us to better understand the mechanisms of oxidation occurring on the surface. Particularly, the presence of SF6 in the plasma induces the decrease of the concentration of arsenic on the surface and thus improves the stability of the oxide. The second study of this work presents the nitridation of GaAs substrates with different orientations. More the benefits of using a low power GDS source to create high quality GaN layer on the surface is highlighted. This optimized process leads to an As-free nitride layer formed by the inter-diffusion of arsenic and nitrogen, and shows a near saturation of the nitride layer thickness as a function of exposure time. Furthermore, this layer is crystallized by annealing in a cubic lattice parameter close to that of c-GaN.

Les caoutchoucs, ou plus généralement, les polymères subissent de façon néfaste les agressions du milieu environnant au cours de leur utilisation. Deux facteurs sont connus comme étant parmi les plus importants impliqués lors du vieillissement : l’oxygène atmosphérique et les rayonnements UV-visibles solaire, conduisant au phénomène de photo-oxydation. Sachant que le vieillissement dans ce cas est régi par la pénétration de la lumière et la diffusion de l’oxygène, il y a au cours de l’irradiation formation d’une couche d’oxydation sur les premiers microns de la surface du matériau. L’objectif majeur de cette thèse est de mettre en évidence un lien entre l’évolution de la structure chimique et la perte des propriétés mécaniques dans le cadre de matériaux vulcanisés au cours du photo-vieillissement, en présence de charges telles que le dioxyde de titane et un colorant organique, au moyen d’une approche multi-techniques et multi-échelles.Afin d’y parvenir nous avons tout d’abord simplifié le matériau vulcanisé et nous nous sommes focalisés sur la matrice et les charges. Cette première étape nous a permis de déterminer l’influence des charges sur les mécanismes de photo-oxydation des caoutchoucs non vulcanisés, et nous a servi de base à la compréhension des matériaux vulcanisés plus complexes.Dans la deuxième étude, la caractérisation physico-chimique de la couche dégradée formée au cours de l’irradiation des composites vulcanisés a été effectuée. Nous avons par la suite confronté ces résultats avec la chute des propriétés mécaniques observée au cours du vieillissement. Nous avons ainsi mis en évidence une corrélation directe entre la structure chimique liée aux propriétés de la couche oxydée et la chute des propriétés mécaniques. / Rubbers or mostly polymers are exposed to different attacks from the surroundings during their uses. Two factors are known to be among the most important involved during aging: atmospheric oxygen and UV-visible radiation from the sun, leading to the phenomenon of photo-oxidation. Photo-ageing is governed by the light penetration and diffusion of oxygen, which involve the formation of an oxidative layer on the first microns at the surface of the material. The main objective of this thesis is to point out the relationship between the changes in the chemical structure due to the formation of the oxidative layer and the loss of mechanical properties during photo-aging of vulcanised rubber in the presence of fillers such as titanium dioxide and organic dye by means of a multi-techniques and multi-scale approach.To achieve this goal, we first simplified the vulcanized material and we focused only on the matrix and fillers. This first step allowed us to determine the influence of fillers on the mechanisms of photo-oxidation of unvulcanised rubber. This study helped to better understand more complex materials such as vulcanised rubbers. In the second study, we focused on the physic-chemical characterization of the degraded layer formed during irradiation of vulcanised rubber. After that, we compared the results with the loss of the mechanical properties observed during aging. This study highlighted a link between the changes of the chemical structure related to the properties of the oxidized layer and the loss of the mechanical properties.

Atomic force microscopy (AFM) is a technique that is part of a series of scanning probe microscopies (SPM). It is a powerful tool due to its potential use in conducting, semiconducting and biological materials without the need of pretreatment of the samples, being applied in areas such as Chemistry and Healthy Science. The use of AFM technique is growing exponentially in the last years and can be evidenced by the large number of articles published in the literature, c.a. 58.000 (until September, 2009). AFM resolution level reaches the nanometric scale with an increase of 109 times. The image acquired is built through of a software supplied by the equipment and converge exactly to the real image. During the execution of this work, we used AFM to characterize tiophene and pyrrole derivatives deposited on the electrode surface of indium tin oxide (ITO) using different experimental conditions and deposition charges. We also verified the morphological aspects of the deposition of dansyl film by chemical and electrochemical methods. The use of AFM in dental acts allowed to define the best method of inserting dental material into cavity of dental tissue damage – single or incremental increase followed the use of such lights – halogena or LED – to the polymerization process. The analysis of the enamel surface of the tooth was also researched to verify the effect of toothbrushes using dentrify or not. We used commercial toothbrushes and experimental dentrify with RDA 60 provided by Colgate-Palmolive Co. AFM appeared to be a useful tool to obtain images and statistic parameters to conducting polymers, to the systems between enamel and resin and to the enamel submit to action of toothbrushes bristles with and without an experimental toothpastes. The main parameters obtained were analysis of the surface of several materials and acquisition roughness, Ra, Rms and relative surface area. In all the experiments, the AFM was a technically viable, efficient, economically advantageous technique and without the necessity of special sample treatment. / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / A microscopia de força atômica (AFM) é uma das técnicas que faz parte da grande família de microscópios de sonda de varredura mecânica (SPM). É uma ferramenta poderosa por sua possibilidade de uso em materiais condutores, semicondutores e até materiais biológicos sem a necessidade de pré-tratamento das amostras, encontrando aplicação em várias áreas do conhecimento, inclusive na Química e nas Ciências de Saúde. O uso da técnica de AFM nos últimos anos vem aumentando exponencialmente, sendo constatado pelo grande número de artigos publicados, cerca de 58.000 (até setembro, 2009). Seu nível de resolução alcança a escala nanométrica com aumento da ordem de 109 vezes. A imagem fornecida é formada através da interação entre uma sonda e a superfície da amostra por meio de programa do próprio equipamento e converge exatamente para a imagem real. No presente trabalho, utilizamos o AFM para caracterizar polímeros condutores derivados de tiofeno e pirrol depositados sobre a superfície de eletrodo de óxido de índio dopado com estanho (ITO) utilizando condições experimentais diferentes. Ainda, verificamos os aspectos morfológicos da deposição de filmes de dansila por métodos químicos e eletroquímicos. A AFM foi utilizada para verificar o efeito das cerdas das escovas dentárias na superfície do esmalte do dente na presença ou não de dentrifício. Foram utilizadas escovas comerciais e dentrifícios experimentais com uma abrasividade relativa da dentina de 60 cedidos pela Colgate-Palmolive Co. A utilização da AFM nos procedimentos dentários permitiu definir qual o melhor método de inserção de revestimento na cavidade de tecidos dentários danificados – incremento único ou incremental seguido da utilização de luzes do tipo – halógena ou luz emitida por diodo - para o processo de polimerização. A AFM mostrou ser uma ferramenta útil na obtenção de imagens e parâmetros estatísticos para os filmes poliméricos, para os sistemas entre esmalte dental e resinas poliméricas e para os esmaltes dentários submetidos a ação das cerdas das escovas com e sem dentrifício. Em todos os experimentos propostos a AFM se mostrou tecnicamente viável, eficiente, economicamente vantajosa e sem necessidade de tratamento especial das amostras.

This thesis is focused on monitoring attributes of ettringite in long term horizon, especially on his thermodynamic stability. Ettringit was prepared in two ways. Firstly, it is a method of hydration of yeelimite, secondly, ettringit is prepared by addition of aluminium sulphate and calcium hydroxide.

The thesis describes surface topography of a-CSi:H films deposited by continuous wave plasma enhanced chemical vapor deposition (PECVD) based on tetravinylsilane monomer (TVS). Thin films are completely used in many fields of modern technologies and their physical and mechanical properties are affected by thin film preparation techniques. In this thesis the thin films were deposited by PECVD method on silicon wafers with the pure TVS monomer. Deposited samples were topographically described and analyzed using atomic force microscopy (AFM). The main characteristics which were described are RMS roughness, autocorrelation function and a size distribution of grains on the thin film surface. Analysis was realized with two sets of samples with different powers and thickness. The main results were statistically evaluated like a mixture of object on the surface prepared in different deposition conditions.

This master's thesis is focused on in situ observation of the negative electrode of the lead acid accumulator using atomic force microscopy AFM. Discussed topics are lead acid accumulator, atomic force microscopy, cyclic voltammetry and current knowledge of the in situ observation of the lead acid accumulator using AFM. The main task of this project is assembling the experimental cells, make in situ observation of the negative electrode surface of the lead acid accumulator. In the end evaluate if this method is suitable for the lead acid battery observation.

Tato Diplomová práce se zabývá povrchovou analýzou nanokompozitní folie polyetherimidu (PEI) vyztuženého exfoliovanými grafitickými nanodestičkami (xGnP). Analyzovány byly take vzorky nevyztužené PEI folie a samostatné nanodestičky. Vzorky nanokompozitu a PEI folie byly plazmaticky leptány s využitím argonového plazmatu po dobu 1, 3 a 10 hod. Skenovací elektronová mikroskopie (SEM) byla použita pro charakterizaci samostatných nanodestiček rozptýlených na křemíkovém substrátu, původních či leptaných vzorků PEI folie a nanokompozitu. Nanodestičky byly identifikovány při povrchu leptané nanokompozitní folie. Mikroskopie atomárních sil (AFM) byla použita pro zobrazení povrchové topografie separovaných nanodestiček a odkrytých destiček při povrchu leptaného kompozitu. Povrchová drsnost (střední kvadratická hodnota, vzdálenost nejnižšího a nejvyššího bodu) leptaného nanokompozitu narůstala s prodlužující se dobou leptání. Akustická mikroskopie atomárních sil (AFAM) byla použita pro charakterizaci elastické anizotropie leptaných kompozitních vzorků. Nanoindentační měření umožnila charakterizaci lokálních mechanických vlastností PEI a nanokompozitních folií.

Proposed diploma thesis is focused on preparation and characterization of the plasma polymer thin films based on tetravinylsilane monomer (TVS). Plasma enhanced chemical vapour deposition (PECVD) method involving pulse and continual plasma discharge modes were used for thin film deposition on silicon wafer pieces. Reactive plasma composition was containing pure TVS or mixtures of TVS and argon or oxygen gas. Atomic force microscopy was used for surface topography and roughness characterization. Cyclic nanoindentation was involved to measurements to determine the Young’s modulus and hardness of prepared films and scratch test was performed to evaluate the degree of adhesion. Special attention was drawn to the characterization of films with a Young’s modulus below 10 GPa. Tip geometry of indenter influence on scratch test was also commented. Surface and mechanical properties of thin films in relation to the deposition conditions were correlated to the obtained results and final analysis of deposition conditions influence is proposed.