Dans cette thèse, nous proposons une étude détaillée des mécanismes responsables de la perte de données dans les mémoires à changement de phase enrichies en germanium (Ge-rich PRAMs), à savoir la dérive de la résistance au cours du temps et la recristallisation de la phase amorphe. Nous commençons par une présentation du contexte dans lequel s'inscrit cette étude an donnant un aperçu rapide du marché des mémoires à semiconducteur et une comparaison des mémoires non volatiles émergentes. Les principes de fonctionnement de la technologie PRAM sont introduits, avec ses avantages, ses inconvénients, ainsi que la physique régissant le processus de cristallisation dans les matériaux à changement de phase, avant de décrire les problèmes de fiabilité qui nous intéressent.Une caractérisation électrique complète de dispositifs intégrant des alliages de GST enrichi en germanium est ensuite proposée, en commençant par la caractérisation des matériaux utilisés dans nos cellules, introduisant alors les avantages des alliages enrichis en Ge sur le GST standard. Les performances électriques des dispositifs intégrant ces matériaux sont analysées, avec une étude statistique des caractéristiques SET & RESET, de la fenêtre de programmation, de l'endurance et de la vitesse de cristallisation. Nous nous concentrons ensuite sur le thème principal de cette thèse en analysant la dérive en résistance de l'état SET de nos dispositifs Ge-rich, ainsi que les performances de rétention de l'état RESET.Dans la dernière partie, nous étudions les mécanismes physiques impliqués dans ces phénomènes en fournissant une étude détaillée de la structure des cellules, grâce à l'utilisation de la Microscopie Électronique en Transmission (MET). Les conditions et configurations expérimentales sont décrites, avant de présenter les résultats qui nous ont permis d'aller plus loin dans la compréhension de la dérive en résistance et de la recristallisation de la phase amorphe dans les dispositifs Ge-rich. Une discussion est finalement proposée, reliant les résultats des caractérisations électriques avec ceux des analyses TEM, conduisant à de nouvelles perspectives pour l'optimisation des dispositifs PRAMs. / In this thesis we provide a detailed study of the mechanisms responsible for data loss in Ge-rich Ge2Sb2Te5 Phase-Change Memories, namely resistance drift over time and recrystallization of the amorphous phase. The context of this work is first presented with a rapid overview of the semiconductor memory market and a comparison of emerging non-volatile memories. The working principles of PRAM technology are introduced, together with its advantages, its drawbacks, and the physics governing the crystallization process in phase-change materials, before describing the reliability issues in which we are interested.A full electrical characterization of devices integrating germanium-enriched GST alloys is then proposed, starting with the characterization of the materials used in our PCM cells and introducing the benefits of Ge-rich GST alloys over standard GST. The electrical performances of devices integrating those materials are analyzed, with a statistical study of the SET & RESET characteristics, programming window, endurance and crystallization speed. We then focus on the main topic of this thesis by analyzing the resistance drift of the SET state of our Ge-rich devices, as well as the retention performances of the RESET state.In the last part, we investigate on the physical mechanisms involved in these phenomena by providing a detailed study of the cells' structure, thanks to Transmission Electron Microscopy (TEM). The experimental conditions and setups are described before presenting the results which allowed us to go deeper into the comprehension of the resistance drift and the recrystallization of the amorphous phase in Ge-rich devices. A discussion is finally proposed, linking the results of the electrical characterizations with the TEM analyses, leading to new perspectives for the optimization of PRAM devices.

The effect of substrate surface treatment (substrate sputter cleaning) in a cathodic arc plasma prior to unbalanced magnetron deposition of transition metal nitride coatings on the performance of the coated components has been investigated. In particular the influence of parameters such as ion species, ion energy and exposure time on the changes in substrate surface topography, microstructure and micro-chemistry were studied employing transmission electron microscopy, energy dispersive X-ray analysis, electron energy loss spectroscopy, X-ray diffraction, atomic force microscopy and optical microscopy. The consequences for both the microstructure of subsequently grown transition metal nitride coatings and their adhesion were elucidated. The relevance for practical applications was demonstrated using the example of dry high-speed milling tests, which showed that an appropriate choice of substrate surface pre-treatment parameters can double the life time of the coated tools. This was found to be due to an improved adhesion as a result of a combina-tion of reduced oxygen incorporation at the interface between coating and substrate and local epitaxial growth of the coating. The latter is promoted by certain sub-strate surface pre-treatment procedures, which provide clean surfaces with preserved crystallographic order.

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Le but de cette thèse est d'étudier l'effet de l’alignement et le contrôle de la morphologie de films minces de polythiophènes et de les corréler avec les propriétés optiques, de transport de charges et thermoélectriques. Puisque les polymères semiconducteurs sont intrinsèquement anisotropes, il est essentiel de les aligner afin de comprendre leur propriétés. Cette étude a été réalisée en employant deux techniques qui ont permises d’obtenir des films minces orientés. Le brossage à haute température et la cristallisation épitaxiale directionnelle (CED) ont conduit à des films de polythiophène hautement orientés avec des paramètres d'ordre allant jusqu'à 0.87 et des taux de crystallinité jusqu'à 65%. La technique de brossage nous a permis de contrôler avec précision les tailles des domaines cristallins dans des films de P3HT brossés. Par cette méthode, nous avons pu également déterminer les températures de fusion à l'équilibre de différents poly(3-alkyl-thiophène). Nous avons appris que la largeur de bande du couplage excitonique W dépend des dimensions des cristaux dans les films minces brossés. Cette étude à aussi montrer l’importance de la planarité des chaînes pontant les domaines cristallins à travers les zones amorphes sur les propriétés de transport de charges. Nous avons également mis en évidence la morphologie particulière du poly (3-butylthiophène) (P3BT) et le rôle des groupements butyles. La méthode de cristallisation epitaxialle a été utilisée pour orienter des films de poly(3-dioctylphenyl-thiophène) (PDOPT). Nous avons examiné l'effet de la masse moléculaire du PDOPT sur le degré de cristallinité et l'alignement. Ceci nous a permis de proposer un modèle structural montrant l’absence de pi-stacking dans ce polythiophène. Finalement, nous proposons une méthode en deux étapes d’élaboration de films minces conducteurs alignés. Le brossage des films puis le dopage des polymères semiconducteurs de type-P a permis d’obtenir des propriétés thermoélectriques anisotropes améliorées.Cette thèse démontre l'importance du contrôle de la morphologie et de l'alignement des polymères semiconducteurs et conducteurs pour comprendre leurs propriétés fortement anisotropes. / The aim of this thesis is to study the effect of alignment and morphological control on polythiophene thin films and to correlate this control with the optical, charge transport and thermoelectric properties. Since semiconducting polymers are inherently anisotropic by nature, studying these polymers in the aligned state was essential to understand their properties. This study could be achieved by employing two techniques that are successful in orienting polymers in thin films. High-temperature rubbing (HTR) along with directional epitaxial crystallization (DEC) produced highly oriented polythiophene thin films with order parameters reaching 0.87 and crystallinities up to 65%. HTR was a successful method to control crystal sizes in rubbed poly(3-hexyl-thiophene) P3HT films. By this method, the equilibrium melting temperatures of other poly(3-alkyl-thiophene) P3ATs were calculated. We learned that the free excitonic bandwidth depends on the crystal dimensions in the rubbed thin films. We also learned that the planarity of tie-chains linking consecutive crystalline domains plays a very important role in field-effect mobility. We also discuss the peculiar morphology of poly(3-butyl-thiophene) (P3BT) and the role of the butyl side groups. Then DEC method was proposed to orient poly(3-dioctylphenyl-thiophene) (PDOPT) thin films. We examined the effect of molecular weight of PDOPT on the level of crystallinity and alignment. Consequently, this relation provided fundamental information that helped us refine the crystal structure of PDOPT. Finally, a versatile method to produce highly aligned conducting polymers was proposed. HTR followed by P-type doping proved to be an excellent way to produce highly aligned conducting thin films with enhanced thermoelectric properties. This thesis brings value to the importance of morphology control and the alignment of semiconducting thin films to understand the various properties of these highly anisotropic systems.

Two isoforms of the tick Ixodes ricinus digestive peptidases cathepsins L1 and L3 are expressed also in salivary glands. In order to assess their role in this tissue, the specific antibodies against these peptidases were prepared by affinity chromatography and used for their detailed immuno-localization using cutting-edge methods of electron microscopy.

De par leurs propriétés physico-chimiques spécifiques, les nanomatériaux attirent de plus en plus la communauté scientifique. Dans ce contexte, il est important d'améliorer les techniques de caractérisation à l'échelle nanométrique. Ce travail de thèse est basé sur le développement de techniques de diffraction électronique pour l'étude de matériaux bi-dimensionnels et tri-dimensionnels.La diffraction électronique en faisceau convergent contient de nombreuses informations sur la structure l'échantillon. Ces informations, portées par les lignes de HOLZ, permettent de déterminer l'épaisseur de l'échantillon, le facteur de structure, la direction d'observation, la tension d'accélération des électrons, ainsi que la longueur de caméra. Des ambiguïtés existent dans la détermination de l'état de contraintes car un cliché expérimental est une projection bi-dimensionnelle d'une information tri-dimensionnelle. Il a été possible au cours de cette thèse de réduire ces ambiguïtés et de déterminer ainsi les composantes diagonales du tenseur de déformation à partir d'une seule direction d'observation. En étudiant l'élargissement des lignes de HOLZ, dû à une déformation non uniforme dans le sens de propagation des électrons, il a été possible de remonter au champ de déplacement suivant l'axe du faisceau d'électrons.La seconde partie de cette thèse s'intéresse aux matériaux bi-dimensionnels comme le Graphène, le Nitrure de Bore (BN) et le disulfure de Molybdène (MoS2). L'interprétation du contraste d'une image de microscopie électronique en transmission haute résolution est discutée, notamment sur l'importance de l'orientation de l'échantillon et des aberrations. Une méthode de mesure de l'orientation d'un échantillon bi-dimensionnel basée sur la projection des tâches de diffraction est présentée. Enfin, trois techniques de mesure d'épaisseur sont comparées en les appliquant à quelques couches atomique de MoS2 et BN. / The small dimensions of nanomaterials give them remarkable properties attracting the scientific community. In order to understand and control these properties, it is essential to characterize them at the nanometer scale. This thesis work is based on the development of electron microscopy diffraction techniques for the study of two and three dimensional materials.Convergent Beam Electron Diffraction patterns contain large amount of information on the sample geometry. This information, carried by HOLZ lines, allows to determine the sample thickness, the structure factor, the direction of observation, the electron acceleration voltage and the camera length. Ambiguities in strain measurement arise from the experimental two-dimensional projection of three-dimensional information. During this thesis, it has been possible to reduce these ambiguities and therefore to measure the diagonal components of the deformation gradient tensor from one direction of observation only. By studying the HOLZ lines broadening, due to a non-uniform strain along the electron beam direction, it has been possible to retrieve the displacement field along the beam direction.The second part of this thesis is focused on the study of two-dimensional materials such as Graphene, Boron Nitride (BN) or Molybdenum disulfide (MoS2). The delicate interpretation of the contrast of high-resolution transmission electron microscopy images and especially the importance of aberrations and sample tilt on this contrast is discussed. A method to quantify two-dimensional sample orientation using diffraction spots projection effect is presented. Finally, three thickness measurement techniques are compared by applying them to few-layered MoS2 et BN.

Destacam-se as semelhanças entre os nutrientes boro (B) e cálcio (Ca) quanto às formas e as funções que eles exercem nos vegetais. Partindo do princípio que a interação Ca - B afeta os atributos morfológicos, ultraestruturais e bioquímicos, bem como a nodulação nas plantas leguminosas, objetivou-se com esse estudo determinar a relação Ca:B mais adequada para a produção de grãos e matéria seca de soja, bem como avaliar os efeitos da interação B e Ca na fixação biológica de N2 (atividade da nitrogenase -N-ase [EC 1.18.6.1]), na morfologia de raízes (comprimento e superfície total), anatomia de raízes (nódulos) e de folhas, assim como as avaliações ultraestruturais dos mesófilos foliares, rendimento do teor de óleo nos grãos das plantas de soja (cultivar BRS 284), crescidas em solução nutritiva. Foram avaliadas ainda a produção de massa seca das plantas, as concentrações e os acúmulos de Ca, B, Mg, K e N na parte aérea e raízes. Foi empregado um esquema fatorial 5² incompleto, perfazendo treze combinações de doses de Ca (mmol L-1) e B (µmol L-1), as quais foram distribuídas segundo o delineamento experimental de blocos ao acaso, com quatro repetições. As maiores atividades da N-ase foram obtidas com as maiores doses de Ca e B (7,25 mmol L-1 de Ca e 50 µmol L-1 de B). A menor dose de Ca resultou na inibição da N-ase em cerca de 90%. Os maiores comprimentos e superfícies totais de raízes foram obtidos na combinação de doses de 7,25Ca e 12,5B, enquanto que para a combinação das menores doses de Ca e B observou-se uma redução de cerca de 70% e 60% para comprimento e superficial de raízes, respectivamente. A maior produção de biomassa seca das plantas e de grãos, os maiores acúmulos de Ca, B, N, K e Mg nas folhas e o maior rendimento de óleo foram obtidos com o fornecimento de 4,25 mmol L-1 de Ca e 12,5 µmol L-1 de B, observando-se relação Ca:B na solução nutritiva próxima de 350:1 e nas folhas de 700:1. O teor de óleo nos grãos incrementou cerca de 20% com o aumento das doses de B de 3,125 para 50 µmol L 1. O número de camadas de células do córtex dos nódulos aumentou com o incremento das concentrações de Ca e B na solução. Observou-se ruptura da membrana dos cloroplastos no mesófilo foliar e elevado número de bactérias fixadoras de N2 penetrando o interior dos tecidos nodulares quando as plantas foram submetidas ao menor suprimento de Ca e maior de B. A combinação da menor dose de B junto a maior dose de Ca provocou ruptura da parede celular e o espessamento da lamela média das folhas. O aumento no fornecimento de Ca ameniza os efeitos negativos do baixo suprimento de B na produção de biomassa das plantas e de grãos, no comprimento e superfície de raízes e na atividade da nitrogenase. A relação Ca:B, tanto na solução, quanto no tecido vegetal, não pode ser entendida como parâmetro exclusivo de equilíbrio nutricional / Regarding mineral nutrition of plants, we highlight the similarities between nutrients boron (B) and calcium (Ca) in relation to similar functions they play in plant physiology. However, the mechanisms involved in the interaction between these nutrients are not very well known. Assuming that the interaction Ca - B affects the morphological, ultrastructural and biochemical attributes, as well as the nodulation in leguminous plants, the objective with this study was to determine the optimum Ca:B ratio, in the solution and plan tissue as well for dry matter yield of grain and dry matter of soybean, and to evaluate the effects of B - Ca interaction in the biological N2 fixation (nitrogenase activity - N-ase [EC 1.18.6.1]), root morphology (total root length and total root surface area), root anatomy (nodules), as well as in the ultrastructural evaluation of foliar mesophilic, and yield of oil content of soybean (cultivar BRS 284), grown in nutrient solution. Dry matter yield of plants, Ca-concentrations and amounts of Ca, B, Mg, K and N in shoots and roots were also evaluated. The experimental arrange used was an incomplete 5² factorial, making thirteen combinations of Ca (mmol L-1) and B (µmol L-1) rates, which were set in a randomized block design, with four replications. The highest N-ase activity was obtained with the highest doses of Ca and B (7,25 mmol L-1 of Ca and 50 µmol L-1 of B). The lowest Ca rate resulted in approximately 90% inhibition of N-ase. The highest total root length and total root surface area were obtained with combination of 7,25Ca and 12,5B rates, whereas the combination of the lowest Ca and B rates caused reduction of approximately 70% and 60% on root length and area, respectively. The highest dry matter and grain yield, highest accumulations of Ca, B, N, K and Mg on the leaves and the highest oil content in grains were obtained when 4,25 mmol L-1 of Ca and 12,5 µmol L-1 of B were supplied, resulting in a Ca:B ratio of approximately 350:1 on nutrient solution and 700:1 on leaves. The oil content in grains raised about 20% increasing B rates from 3,125 to 50 µmol L-1. The number of cell layers of nodule cortex raised with increasing Ca and B levels in the solution. It was observed membrane rupture of chloroplasts in leaf mesophyll and high number of N2-fixing bacteria entering the interior of nodular tissues when plants were supplied with the lowest Ca rate (1,75Ca) and the highest B (50B). The combination of the lowest B rate (3,125B) and the highest Ca rate (7,25) caused cell wall rupture and thickening of the middle lamella on the leaves. The increase of Ca levels on the solution mitigates the negative effects of the low B supply in plant biomass and grain yield, in root length and root surface area and in N-ase activity. The Ca:B ratio either in the solution or plant tissue, cannot be understood as an exclusive parameter of nutritional status

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