Irradiation damage structures induced in pure Fe and Fe-Cr (up to 14%Cr) alloys by 2 MeV Fe+ ion irradiations in the temperature range 300-460°C were investigated by transmission electron microscopy. Specimens were irradiated in bulk to doses of 1.5 x 1019 Fe+/m2 (about 2.5 displacements per atom: dpa) and 4.5 x 1019 Fe+/m2 (about 7 dpa). In most cases, damage took the form of dislocation loops with diameters from 2-100nm; the loops were distributed uniformly within all the samples. At higher irradiation temperatures (400°C, 460°C), complex microstructures such as finger loops (50nm in width and 1 micron in length) and perpendicular <100> loop clusters, were observed in both pure Fe and Fe-Cr samples. Loop sizes and densities were seen to change as a function of irradiation temperature and dose. Loop sizes were seen to increase as the increase of irradiation temperatures and doses, while loop densities only increased with increasing doses and decreased as increasing temperatures. Loops with both types of Burgers vectors (<100> and ½<111>) were observed in all the samples. The proportion of <100> loops was higher in Fe than that in Fe-Cr alloys at the same irradiation condition, which has can be attributed to the high mobility of ½<111> loops in Fe, so that a large proportion of them will escape to the (001) foil surface. A transition in loop Burgers vectors as a consequence of increasing temperature was observed. In Fe, the proportion of <100> loops increased with increasing irradiation temperature from 40% at 300°C to 60% at 460°C. A similar trend was found in the Fe-Cr alloys, but due to the higher proportion of ½<111> loops in these alloys, the increase of <100> loops was not that obvious, being from 30% at 300°C to 45% at 460°C(Fe-11Cr). The effects of irradiation dose rate on the formation of dislocation loops by 2 MeV Fe+ ions were also investigated. These irradiations were carried out at 300°C with two different implantation dose rates: 6 x 10-4 dpa/s and 3 x 10-5 dpa/s. The implantation dose for both implantations was 0.38 x 1019 Fe+/m2 (0.5 dpa). Both the average loop size and loop densities for the Fe-Cr specimens subjected to the high dose rate irradiation were higher than that in the low dose rate irradiations. Take Fe-14Cr as an example, that the loop densities in high dose rate irradiation increased about 90% compared to that in low dose rate, and the average loop size in high dose rate irradiation was 30% larger than that in low dose rate irradiation. The ‘inside-outside contrast’ method was applied to determine the loop nature in all the samples. It was found that all the large loops (>5nm) are of interstitial type. Any vacancies are believed to exist in the form of small dislocation loops (<5nm) or sub-microscopic voids.

Among the commercial aluminum alloys, aluminum 319 (Al-7wt%Si-4wt%Cu) type alloys are popularly used in automobile engine parts. These alloys have good casting characteristics and excellent mechanical properties resulting from a suitable heat treatment. To get a high strength in the 319 type alloys, grain refining, reducing the porosity, solid solution hardening, and precipitation hardening are preferred. All experimental variables such as solidification condition, composition, and heat treatment are influence on the precipitation behavior; however, precipitation hardening is the most significant because excess alloying elements from supersaturated solid solution form fine particles which act as obstacles to dislocation movement. The challenges of the 319 type alloys arise due to small size of precipitate and complex aging response caused by multi components. It is important to determine the chemical composition, crystal structure, and orientation relationship as well as precipitate morphology in order to understand the precipitation behavior and strengthening mechanism. In this study, the mechanical properties and microstructure were investigated using transmission electron microscopy and three dimensional atom probe tomography. The Mn and Mg effects on the microstructure and mechanical properties are discussed with crystallographic study on the iron intermetallic phases. The microstructural evolution and nucleation study on the precipitates in the low-Si 319 type aluminum alloys are also presented with sample preparation and analysis condition of TEM and 3DAP tomography.

Ce travail porte sur la caractérisation structurale et optique d'échantillons de SiC. Les échantillons étudiés ont été répartis en trois groupes : des échantillons massifs, des couches épitaxiales épaisses et enfin des couches minces. La croissance des échantillons massifs a été réalisée avec la technique CF-PVT, utilisant une géométrie « d'étranglement ». L'objectif était de filtrer les défauts afin de créer des germes de 3C de haute pureté. La croissance de des couches épaisses par sublimation avait comme objectif la maitrise d'un dopage résiduel faible de type n et p pour des applications composants. Enfin, dans le but de réaliser des composants de type LED blanche des impuretés Ga ont été introduites dans des couches minces épitaxiées par VLS afin de créer des échantillons fortement dopé de type p. Tous ces échantillons ont été étudiés par photoluminescence, micro-Raman, SIMS et microscopie électronique à transmission. Il a été possible de déterminer la concentration d'impuretés et d'identifier le caractère n ou p de ces échantillons. L'analyse des échantillons a été faite en utilisant à la fois l'observation des défauts structurels et les informations obtenues à partir des techniques de caractérisation optique. Nous avons pu obtenir des informations sur les paramètres physiques de 3C-SiC, comme l'énergie de liaison de Ga et Al, la structure fine des excitons liés à l'Al et celle des paires donneurs accepteurs Al-N et Ga-N. Enfin l'apparition d'un nouveau défaut de structure appelée le « fourfold twin » a été observée. / The main topic of this thesis is the structural and optical characterization of SiC samples. The samples were divided in three groups: bulk, thick and thin epilayers. The bulk samples were grown with the CF-PVT technique and used a modified crystal holder geometry. The objective was to filter the defects to and create high purity and quality seeds of 3C-SiC. The thick epilayers were grown with the sublimation epitaxy technique, trying to demonstrate the creation of low impurity n and p type layers for device applications. Finally the thin epilayers were grown with the vapour-liquid-solid technique and doped with Ga impurities in an effort to create either heavily p-type doped samples and components for white LED applications. The samples were studied with low temperature photoluminescence, micro-Raman, SIMS and transmission electron microscopy. With the help of these techniques it was possible to determine the impurity concentration and identif y the n or p character of these samples. A qualitative analysis of the quality of the samples was done using both the observation of the structural defects and the information from the optical characterization techniques. We were able to acquire information about physical parameters of 3C-SiC like the binding energy of Ga and Al, the Al bound exciton fine structure and the Al-N and Ga-N donor acceptor pair fine structure. The appearance of a new structural defect called the fourfold twin was observed and presented.

Background: Separation science is heavily reliant on materials to fulfill ever more complicated demands raised by other areas of science, notably the rapidly expanding molecular biosciences and environmental monitoring. The key to successful separations lies in a combination of physical properties and surface chemistry of stationary phases used in liquid chromatographic separation, and this thesis address both aspects of novel separation materials. Methods: The thesis accounts for several approaches taken during the course of my graduate studies, and the main approaches have been i) to test a wild-grown variety of published methods for surface treatment of fused silica capillaries, to ascertain firm attachment of polymeric monoliths to the wall of microcolumns prepared in silica conduits; ii) developing a novel porogen scheme for organic monoliths including polymeric porogens and macromonomers; iii) evaluating a mesoporous styrenic monolith for characterization of telomers intended for use in surface modification schemes and; iv) to critically assess the validity of a common shortcut used for estimating the porosity of monoliths prepared in microconduits; and finally v) employing plasma chemistry for activating and subsequently modifying the surface of rigid, monodisperse particles prepared from divinylbenzene. Results: The efforts accounted for above have resulted in i) better knowledge of the etching and functionalization parameters that determine attachment of organic monoliths prepared by radical polymerization to the surface of silica; ii) polar methacrylic monoliths with a designed macroporosity that approaches the desired "connected rod" macropore morphology; iii) estab¬lishing the usefulness of monoliths prepared via nitroxide mediated polymerization in gradient polymer elution chromatography; iv) proving that scanning electron microscopy images are of limited value for assessing the macroporous properties of organic monoliths, and that pore measurements on externally polymerized monolith cocktails do not represent the porous properties of the same cocktail polymerized in narrow confinements; and v) showing that plasma bromination can be used as an activation step for rigid divinylbenzene particles to act as grafting handles for epoxy-containing telomers, that can be attached in a sufficiently dense layer and converted into carboxylate cation exchange layer that allows protein separations in fully aqueous eluents.

Correlative light and electron microscopy (CLEM) is a powerful approach to investigate the molecular ultrastructure of labeled cell compartments. However, quantitative CLEM studies are rare, mainly due to small sample sizes and the sensitivity of fluorescent proteins to strong fixatives and contrasting reagents for EM. Here, we show that fusion of a self-labeling protein to insulin allows for the quantification of age-distinct insulin granule pools in pancreatic beta cells by a combination of super resolution and transmission electron microscopy on Tokuyasu cryosections. In contrast to fluorescent proteins like GFP organic dyes covalently bound to self-labeling proteins retain their fluorescence also in epoxy resin following high pressure freezing and freeze substitution, or remarkably even after strong chemical fixation. This enables for the assessment of age-defined granule morphology and degradation. Finally, we demonstrate that this CLEM protocol is highly versatile, being suitable for single and dual fluorescent labeling and detection of different proteins with optimal ultrastructure preservation and contrast.

The chorda tympani nerve, also known as the taste nerve, runs uncovered through the middle ear cavity, a localization that exposes the nerve to pathological processes and surgical trauma in the middle ear. People operated on for otosclerosis tend to complain more about postoperative taste disturbances than those operated on for chronic otitis media. It has been suggested that this difference may be explained by gradual deterioration of chorda tympani nerve function caused by chronic otitis media infection and that further impairment caused by surgery is less noticeable in these patients. This thesis aimed to evaluate the function of the chorda tympani nerve, the effects of middle ear disease on taste and complications resulting from ear surgery for chronic otitis media or otosclerosis. This information will help to improve the ear surgeon’s ability to predict the prognosis of iatrogenic taste disturbances in patients with middle ear disease and after ear surgery. Taste was assessed using electrogustometry and the filter paper disc method before and after surgery for chronic otitis media or otosclerosis. Patients also completed questionnaires about symptoms and quality of life. The status of the chorda tympani nerve upon surgical opening of the ear and grading of the trauma to the nerve during the surgery were recorded. The ultrastructure of the chorda tympani nerve from healthy ears and from ears with chronic otitis media was examined. Electrogustometry and the filter paper disc method were evaluated. The results of electrogustometry and the filter paper disc method were highly reproducible, although their correlation was moderate. Patients with chronic otitis media, patients with a more traumatized nerve, female patients and younger patients were more likely to report postoperative taste disturbances. Most of the patients recovered their taste after 1 year. The quality of life study showed only minor changes after surgery. Electron microscopic observations of nerves from ears with chronic otitis media showed signs of structural degeneration, although signs of regeneration, such as sprouting were also observed. This results may explain the recovery of taste postoperatively and indicate that the nerve should be carefully handled during surgery.

Afin de réaliser des traitements locaux sur des données de diverses natures (volumes, images ou signaux) contenant des éléments informatifs dans certaines bandes de fréquence, nous nous intéressons dans cette thèse à l’étude de bancs de filtres (BdF). Plus précisément, nous étudions l’existence et la synthèse de BdF de réponses impulsionnelles finies (RIF) inverses d’un BdF d’analyse RIF redondant complexe fixé. Nous proposons en particulier des méthodes testant l’inversibilité de la matrice d’analyse et la construction d’un inverse explicite à l’aide de la formulation polyphase. À partir de ce dernier, nous proposons une paramétrisation réduite de l’ensemble des BdF de synthèse permettant d’optimiser leurs réponses selon différents critères. Cette étude est étendue au cas multidimensionnel notamment par l’utilisation de la notion de résultant. Ces outils permettant de représenter efficacement certaines informations structurées dans des données, il devient possible de les préserver tout en rejetant d’éventuelles perturbations. Le premier cadre considéré est celui du bruit gaussien. Nous avons utilisé le principe de Stein pour proposer deux méthodes de débruitage : FB-SURELET-E et FBSURELET-C. Elles sont comparées à des méthodes récentes de débruitage conduisant à de bons résultats en particulier pour des images texturées. Un autre type d’application est ensuite considéré : la séparation des structures orientées. Afin de traiter ce problème, nous avons développé une méthode de filtrage anisotrope. Les algorithmes réalisés sont finalement testés sur des données issues de différents domaines applicatifs (sismique, microscopie, vibrations) / Our main purpose in this PhD thesis is to perform local frequential (or directional) processing in different kind of data (volumes, images or signals). To this end, filter banks (FBs) are studied. More precisely, we first investigate the existence and the construction of synthesis FBs inverse to a given FIR complex analysis FB. Through the study of the polyphase analysis matrix, we are able to propose methods to test the invertibility and to build one inverse FB. Using this inverse, we provide a parametrization of the set of synthesis FB, with which we optimize filter responses with different criteria. The same study is performed in the multidimensional case. Since FBs provide an efficient representation of structured information in data, it is then possible to preserve them while rejecting unwanted perturbations. By associating Stein’s principle and those FB, we proposed two methods to denoise signals and images corrupted by Gaussian noise. These methods, named FB-SURELET-E and FB-SURELET-C, are compared to recent denoising methods and are found to offer good results, especially for textured images. Another type of application is then investigated : separation of oriented structures. To this end, we have developed an anisotropic filtering method. The different proposed methods are finally applied on images and signals from various fields : seismic images and cubes, transmission electron microscopy (TEM) images of catalysts and vibration signals from car engines

A probe for measuring the specific heat of superconductors at low temperatures and in high magnetic fields has been built and commissioned. The probe has been tested using the relaxation method on samples of copper and the accuracy of the data is 1.3 % between 5 K and 30 K, data taken using the long range pulse method has a resolution of 10 mK. Specific heat measurements have been performed on members of the series (Pb(_1)-(_x))Cu(_1.8x)Mo(_6)S(_8), (Sn(_1-x))Eu(_x)Mo(_6)S(_8) and (Pb(_1-x)M(_x))Mo(_6)S(_8) where M = Gd and Eu, from 3 K up to 30 K and in magnetic fields up to 15 T. Additional results from resistivity, susceptibility, magnetisation. X-ray diffraction, transmission electron microscopy and electron dispersive-ray measurements are also presented. These data have been compared to results from other authors and are analysed in terms of the BCS and GLAG theories of superconductivity and the magnetic properties of these materials. The mean field model has been used to calculate numerically the magnetic contribution to the specific heat (cm) of both ferromagnetic and antiferromagnetic systems as a function of temperature and applied field both above and below the ordering temperature. In addition an approximate analytic form for the magnetisation has been used to calculate Cm above the ordering temperature. Expressions have been derived for the saturation value of the peak in C(_m): C(^sat)(_m) = 1.1245n(_cell)RJI(J+1) and the temperature dependence of the peak with applied field ȡ(μ(_o)H(_ext))/ȡT(_peak)=6.540/g(_J)(J+1). They allow the simple calculation of the values of J and g(_J)(J + 1) from specific heat data. The magnetic contribution to the specific heat of the samples (Sn(_0.65)Eu(0.35)Mo(_6)S(_8)) and (Sn(0.50)Eu(_0.50)Mo(_6)S(_8)) have been modelled using these calculations and excellent agreement is found by considering the magnetic ions as free ions. The sample is accurately modelled by including an additional minority phase (Gd(_2)S(_3)). The approximate expressions have also been used to analyse data on high temperature superconductors producing values of J and g(_J)}{J + 1) consistent with a doublet ground state. The properties of Chevrel phase materials have been determined as a function of doping level. The critical temperature is degraded by doping but an increase in the critical current density is observed in the series (Pb(_1-x)Cu(_1-8x)Mo(_6)S(_8) for very low levels of doping. Increases of up to 28 % in the upper critical field, that are probably due to the compensation effect and an increase in the normal state resistivity, are also observed in the series (Sn(_1-x)Eu(_x)Mo(_6)S(_8)) at high levels of doping and in the series (Pb(_1-x)Gd(_x)Mo(_6)s(_8) for low levels of doping.

De nos jours, l'essor des produits électroniques nomades requièrent une capacité de stockage de données croissante et imposent la fabrication de composants mémoire performants, denses et fiables. Cela implique une grande robustesse des cellules mémoires élémentaires dont les dimensions caractéristiques sont régulièrement réduites. L'objectif principal de la thèse est d'appréhender les mécanismes de claquage d'oxydes minces voire ultraminces intégrés dans des empilements métal/oxyde/semiconducteur. Un intérêt particulier a été porté à la croissance d'îlots cristallins épitaxiés se formant lors de certaines sollicitations électriques et associée aux mécanismes de DBIE (Dielectric Breakdown Induced Epitaxy). L'étude des différents dispositifs (cellules mémoires à grille continue ou discrète, transistors, condensateur) a permis de proposer des corrélations entre la défaillance électrique de ces dispositifs et les défauts microstructuraux générés. Ce travail a été réalisé selon une méthodologie intégrant (i) la sollicitation électrique ; (ii) une préparation d'échantillons adaptée ; (iii) l'identification, l'observation et la caractérisation des défauts par microscopie électronique en transmission (TEM). L'ensemble des études menées a permis d'isoler deux paramètres électriques principaux ayant un rôle prépondérant sur la formation d'îlots de silicium épitaxiés, en lien avec le mécanisme de DBIE : la charge injectée et le courant de compliance. Ces deux paramètres apparaissent comme des facteurs limitant l'emballement thermique qui conduit, en général, à un claquage diélectrique franc de l'oxyde et semblent, par conséquent, retarder la défaillance irréversible d'un dispositif. / Nowadays, the microelectronic industry had to take up ambitious challenges to satisfy the strong economic demand because of the mobile electronic products booming like smartphones, tablets, or more recently "phablets". These high added value products requires the growth of data storage capacity and, subsequently, to produce high-performance, dense and reliable components. That implies a great cell memories robustness whose critical dimensions are regularly reduced. In this context, the thesis issue is to better understand the breakdown mechanisms of the thin and ultra-thin oxides embedded in metal/oxide/semiconductor stacks. Actually, epitaxial growth of crystalline silicon hillocks was pinpointed. These hillocks grown under electrical stresses and were associated to DBIE mechanisms (Dielectric Breakdown Induced Epitaxy). Device studies allowed to correlate electrical stress conditions and microstructural defects thanks to a 3-steps methodology : (i) electrical stresses leading to microstructural defects ; (ii) sample preparation including defect localization and extraction ; (iii) identification, observation and characterization of defects by transmission electron microscopy (TEM). Two main electrical parameters were identified with factors responsible for hillocks growth linked to DBIE : the injected charge and the compliance current. These parameters seem to limit the thermal runaway inducing hard breakdown. Consequently, it is possible that delays the irreversible device degradation. In addition, hillocks seem to grow preferentially under polysilicon grain boundaries over the SiO2/Si stacks.

Au cours de ces travaux de thèse, nous avons étudié la redistribution atomique de contaminantsmétalliques dans le silicium et au voisinage d'une interface SiO2/Si. Pour mener à bien cetteétude, trois techniques de caractérisation complémentaires ont été utilisées (TEM,APT,SIMS).Nous avons dans un premier temps étudié la diffusion ainsi que la ségrégation d'équilibre de contaminants à une interface SiO2/Si, et plus particulièrement, la diffusion du W et du Mo. Le Wprésente une cinétique de diffusion extrêmement lente. Les caractérisations réalisées par TEM et APT nous ont permis de discuter les profils de concentrations mesurés par SIMS et nous ont guidés dans le choix du modèle de diffusion proposé. L'étude de la diffusion du Mo révéle que cette espèce présente une limite de solubilité faible dans le silicium et une forte interaction avec des défauts d'irradiation, provoquant sa précipitation.Dans un second volet, nous nous sommes intéressés à l'effet d'une interface mobile, lors d'une réaction, sur la redistribution atomique des contaminants proches de cette interface. Nous avons ainsiréalisé une étude comparative des comportements du Fe et W lors de procédés d'oxydation.Le tungstène précipite dans le volume et est progressivement rejeté par l'oxydation. Le ferprécipite à l'interface SiO2/Si, provoquant un effet de masquage dont nous avons montré qu'il étaitresponsable de la formation de défauts pyramidaux d'interface, caractéristiques d'une contaminationen fer du silicium. Le procédé de germano-siliciuration de nickel, réalisé à basses températures a également été investigué. Cette réaction provoque le rejet 3D du germanium à l'interface NiSiGe/SiGe. / During this thesis work, we studied the atomic redistribution of metallic contaminantsin silicon and near a SiO2/Si interface. To conduct this study, we used three complementary characterisation techniques : transmission electron microscopy (TEM), atomic probe tomography (APT) and secondary ion mass spectrometry (SIMS).We first studied the diffusion and equilibrium segregation of various contaminants at a SiO2/Si interface, and more particularly, the diffusion of W and Mo. W exhibits a very slow diffusion kinetic.Physico-chemical characterizations performed by TEM and APT allowed discussing the concentrationprofiles obtained by SIMS leading to the diffusion model that we proposed. The study of Mo diffusionrevealed that this specy exhibits a low solubility limit in silicon and strongly interacts with irradiation-induced defects, leading to its precipitation.In a second phase, we studied the effect of a mobile interface, during a reaction, on the atomic redistribution of contaminants near this interface. We performed a comparative study of the behaviourof Fe and W during oxidation processes. W precipitates in the silicon substrate and is progressivelyrejected (snowplow) by the oxidation. Fe preferentially precipitates at the SiO2/Si interface. Theseprecipitates mask a part of the silicon substrate and thus hinder its oxidation, leading to the formation of characteristics pyramidal-shaped defects at the interface. Low temperature nickel germano-silicide formation have also been investigated. This reaction leads to the 3D snowplow of germanium atoms at the NiSiGe/SiGe interface.