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.

De nombreuses propriétés étonnantes ont été récemment découvertes à l’interface de deux perovskites isolantes l’une polaire l’autre non polaire. La discontinuité de charge à l’interface LaAlO3/SrTiO3 engendre un gas d’électron quasi-bidimensionnel qui confère un caractère métallique à cette interface. Les mécanismes locaux et la quantification des propriétés ne font pas consensus car l’interdépendance de facteurs structuraux, chimiques et électroniques complexifie la résolution du problème posé. Une catastrophe polaire, des distorsions structurales, des lacunes d’oxygène, une interdiffusion cationique et une non stœchiométrie du film ont été séparément avancées pour expliquer cette conduction. Dans le cadre d’un programme international, nous avons reçu des héterointerfaces conductrices et isolantes élaborées par ablation laser pulsé (PLD). L’origine des porteurs de charge a été recherchée par une approche globale liant procédé, structure et propriétés électriques (mesurées dans le consortium). Nous avons systématiquement analysé les interfaces en combinant imagerie à haute résolution (STEM-HAADF) et spectroscopies électroniques (EELS) et ioniques (MEIS). Une non planéité des couches atomiques, une interdiffusion cationique et un transfert d’électrons permettent de réduire la divergence de potentiel, la catastrophe polaire n’a donc pas lieu. La formation de défauts donneurs à la surface du film devient favorable au-delà d’une épaisseur critique. Les électrons sont transférés à l’interface dans la bande de conduction du STO. Nous avons mis en évidence un mécanisme de compensation concurrentiel de la charge interfaciale par des lacunes de strontium chargées négativement, qui mettent le substrat en compression plane et s’opposent au confinement 2D électrons. La variation des paramètres procédés, tels que la durée du dépôt, la pression partielle en oxygène, la température et la stœchiométrie de la plume déplace l’équilibre des différents mécanismes mis en évidence. Ce travail démontre la relation complexe liant procédé, propriétés électriques et distribution des défauts autour de ces interfaces singulières. / Novel behavior at the interface between two insulating polar/non polar perovskites has been recently discovered. The polarization discontinuity at LaAlO3/SrTiO3 drives the formation of quasi two dimensional electron gas. Both the local mechanism and quantification of such behavior remain unclear due to interplay of structural, chemical and electronic factors. Several mechanisms have been proposed, such as the polar catastrophe, structural distortions, oxygen vacancies, cationic intermixing at the interface and film non-stoichiometry. In the frame of an international project conductive and insulating heterostrucutres have been synthetized by Pulsed-Laser Deposition. In this thesis, we have developed a comprehensive approach to investigate the origin of the charge carriers. The interfaces have been systematically analyzed by combining high resolution imaging (STEM-HAADF) to atomic resolved electron (EELS) and ion (MEIS) spectroscopies. The observed and quantified parameters have been related to the electrical properties of the interfaces measured in the consortium. Buckling of the atomic layers, intermixing and electron transfer reduce the polar divergence. This rules out the polar catastrophe scenario. The formation of donor defects at the film surface is favored above a critical film thickness. Electrons are transferred to interface in the STO conduction band. A competing compensation mechanism of the positive interfacial charge by negatively charged strontium vacancies has been demonstrated that generates an in plane compression of the STO, unfavorable for a strict 2D confinement of the charges. Varying the process parameters such as growth duration, oxygen partial pressure, temperature, and plume stoichiometry shift the equilibrium of the different mechanisms highlighted. This thesis emphasizes the complex relations between the process and the properties through the defects distribution around these singular interfaces.

Les plasmons de surface (SP) sont des excitations mêlant électrons et photons localisées aux surfaceset interfaces métalliques. On peut les voir classiquement comme les modes électromagnétiquespropres d’un ensemble constitué d’un métal et d’un diélectrique. Cette thèse se base sur la capacitéofferte par les techniques de spectroscopie utilisant des électrons rapides disponibles dans un microscopeélectronique à balayage en transmission (STEM), de cartographier, dans une large gammespectrale et avec une résolution spatiale nanométrique, les modes propres SP. Une telle capacitéa été démontrée séparément, durant ces dernières années, par des expériences de spectroscopie depertes d’énergie d’électrons (EELS), qui mesurent l’énergie perdue par des électrons rapides intéragissantavec un échantillon, et de cathodoluminescence (CL), qui mesurent l’énergie réémisepar l’échantillon par l’intermédiaire de photons, toutes deux résolues spatialement. Dans le cas del’EELS, ces résultats expérimentaux sont aujourd’hui interprétables à l’aide d’analyses théoriquesconvaincantes tendant à prouver que la quantité mesurée dans une telle expérience peut être interprétéede façon sûre en terme de modes propres de surface de l’échantillon. Afin d’élargir une telleinterprétation aux techniques de spectroscopies utilisant des électrons rapides en général, j’ai effectuédes expériences combinées d’EELS et de CL résolues spatialement sur une nanoparticle uniquesimple (un nanoprisme d’or). J’ai montré que les résultats offerts par ces deux techniques présententde fortes similitudes mais également de légères différences, ce qui est confirmé par des simulationsnumériques. J’ai étendu l’analyse théorique du signal EELS au signal CL, et ai montré que la CLcartographie, tout comme l’EELS, les modes de surface radiatifs du sytème, mais avec des propriétésspectrales légèrement différentes. Ce travail constitue une preuve de principe clarifiant les quantitésmesurées en EELS et CL sur des systèmes métal-dielectriques. Ces dernières sont démontrées êtrerespectivement des équivalents nanométriques des spectroscopies d’extinction et de diffusion de lalumière. Basé sur cette interprétation, j’ai utilisé l’EELS pour dévoiler les modes propres SP demilieux métalliques aléatoires (dans notre cas, des films semicontinus métalliques avant le seuil depercolation). Ces modes propres constituent une problématique de longue date dans le domainede la nanooptique. J’ai directement identifié ces modes par des mesures et le traitement de leursrésultats. J’ai complètement caractérisé ces modes propres via les variations spatiales de l’intensitéliée à leur champ électrique, une énergie propre et un taux de relaxation. Ce faisant, j’ai montré quela géométrie fractale du milieu, dont la prédominance croit au fur et à mesure que l’on s’approchede la percolation, est responsable de l’existence de modes propres de type aléatoire à basse énergie. / Surface Plasmons (SP) are elementary excitations mixing electrons and photons at metal surfaces,which can be seen in a classical electrodynamics framework as electromagnetic surface eigenmodesof a metal-dielectric system. The present work bases on the ability of mapping SP eigenmodes withnanometric spatial resolution over a broad spectral range using spatially resolved fast electron basedspectroscopies in a Scanning Transmission Electron Microscope (STEM). Such an ability has beenseparately demonstrated during the last few years by many spatially resolved experiments of ElectronEnergy Loss Spectroscopy (EELS), which measures the energy lost by fast electrons interactingwith the sample, and CathodoLuminescence (CL), which measures the energy released by subsequentlyemitted photons. In the case of EELS, the experimental results are today well accountedfor by strong theory elements which tend to show that the quantity measured in an experiment canbe safely interpreted in terms of the surface eigenmodes of the sample. In order to broaden thisinterpretation to fast electron based spectroscopies in general, I have performed combined spatiallyresolved EELS and CL experiments on a simple single nanoparticle (a gold nanoprism). I have shownthat EELS and CL results bear strong similarities but also slight differences, which is confirmed bynumerical simulations. I have extended the theoretical analysis of EELS to CL to show that CLmaps equally well than EELS the radiative surface eigenmodes, yet with slightly different spectralfeatures. This work is a proof of principle clarifiying the quantities measured in EELS and CL,which are shown to be respectively some nanometric equivalent of extinction and scattering spectroscopieswhen applied to metal-dielectric systems. Based on this interpretation, I have applied EELSto reveal the SP eigenmodes of random metallic media (in our case, semicontinuous metal films beforethe percolation threshold). These SP eigenmodes constitute a long standing issue in nanooptics.I have directly identified the eigenmodes from measurements and data processing. I havefully characterized these eigenmodes experimentally through an electric field intensity pattern, aneigenenergy and a relaxation rate. Doing so, I have shown that the fractal geometry of the medium,which grows towards the percolation, induces random-like eigenmodes in the system at low energies.Keywords: Surface plasmons, fast electron based spectroscopies, scanning transmission electronmicroscopy, disordered media

Dans les dernières années nombre de matériaux lamellaires à dimensions réduites ont démontré des propriétés optiques remarquables. Cependant, la plupart des études ont porté sur le système parfait et le rôle des défauts en tant que centres optiques actifs restent encore largement inexploré. Le nitrure de bore hexagonal (h-BN) est l'un des candidats les plus prometteurs pour les dispositifs émetteurs de lumière dans la région de l’UV lointain, présentant une forte émission excitonique à 5,8 eV. Cependant, émission n’apparaît uniquement que dans des monocristaux très purs qui peuvent difficilement être obtenus que par des procédés de synthèse complexes. Les échantillons ordinaires de h-BN présentent des spectres d'émission plus complexes qui ont été généralement été attribuée à la présence de défauts structuraux. Malgré un grand nombre d'études expérimentales jusqu'à présent il n'a pas été possible d'attribuer cette émission additionnelle à des défauts structuraux bien définis. Nous abordons ici cette question fondamentale en adoptant une approche théorique et expérimentale combinant une technique de cathodoluminescence nanométriquement résolu avec une caractérisation structural résolu atomiquement par microscopie électronique a transmission et de l'état de l'art de simulations excitoniques. Très récemment, l'équipe d'Orsay a mis au point un système de détection de cathodoluminescence intégré au sein d'un microscope électronique à transmission à balayage. Cette expérience unique est maintenant en mesure de fournir des spectres d'émission complet avec une résolution aussi faible que quelques dizaines de MeV associés à une taille de sonde électronique du nanomètre. Une image hyper-spectrale cathodoluminescence peut donc être enregistrée en parallèle avec une image HAADF. La cathodoluminescence résolu au nanomètre sur quelques-couche chimiquement exfoliée de h-BN a montré que les spectres d'émission sont fortement inhomogènes dans les feuillets individuels. Les pics d'émission à proximité de l'exciton libre apparaissent dans des régions étendues. Les examens complémentaires par microscopie électronique à transmission à haute résolution permettent d'associer ces raies d'émission avec des défauts étendue dans le cristal tels que les défauts d'empilement et les plis des facetter. Au moyen de calculs ab-initio dans le cadre de la « Many Body perturbation theory » (GW) et l'équation de Bethe-Salpeter nous fournissons une description détaillée de la structure électronique et la réponse spectroscopique du nitrure de bore hexagonal en présence de défaut d’empilements. En particulier, nous montrons un bon accord avec les résultats expérimentaux, les excitons supplémentaires sont associées à des changements de symétrie locaux qui se produisent par des fautes d'empilement dans le cristal. Ce résultat sera ensuite étendu à des nanotubes de BN à parois multiples. Des émissions supplémentaires qui apparaissent à l'intérieur du gap présentent une localisation spatiale élevée, typiquement inférieure à 100 nm, et par conséquent ils peuvent être liés à des défauts ponctuels individuels. Lorsqu’ils sont adressés individuellement à travers une sonde électronique très ciblé, ils pourraient avoir un caractère d’émetteur de photon unique. Cette hypothèse a été récemment confirmée par des expériences combinant notre système de cathodoluminescence avec un interféromètre Handburry-Brown et Twiss (HBT). / Within the latest years number of layered materials at reduced dimensions have demonstrated remarkable optical properties. However most studies focused on perfect system and the role of defects as optical active centers remain still largely unexplored. Hexagonal boron nitride (h-BN) is one of the most promising candidates for light emitting devices in the far UV region, presenting a single strong excitonic emission at 5.8 eV. However, a single line appears only in extremely pure mono-crystals that can hardly be obtained only though complex synthesis processes. Common h-BN samples present more complex emission spectra that have been generally attributed to the presence of structural defects. Despite a large number of experimental studies up to now it was not possible to attribute specific emission features to well identify defective structures. Here we address this fundamental question by adopting a theoretical and experimental approach combining few nanometer resolved cathodoluminescence techniques with high resolution transmission electron microscopy images and state of the art quantum mechanical simulations. Very recently, the Orsay team has developed a cathodoluminescence detection system integrated within a scanning transmission electron microscope. This unique experimental set up is now able to provide full emission spectra with a resolution as low as few tens of meV associated with an electron probe size of one nanometer. A cathodoluminescence hyper-spectral image can thus be recorded in parallel with an HAADF image. Nanometric resolved cathodoluminescence on few-layer chemically exfoliated h-BN crystals have shown that emission spectra are strongly inhomogeneous within individual flakes. Emission peaks close to the free exciton appear in extended regions. Complementary investigations through high resolution transmission electron microscopy allow to associate these emission lines with extended crystal deformation such as stacking faults and folds of the planes. By means of ab-initio calculations in the framework of Many Body Perturbation Theory (GW) approximation and Bethe-Salpeter equation) we provide an in-depth description of the electronic structure and spectroscopic response of bulk hexagonal boron nitride in the presence of extended morphological modifications. In particular we show that, in a good agreement with the experimental results, additional excitons are associated to local symmetry changes occurring at crystal stacking faults. These result will then be extended to faceted multiwalled BN nanotubes, they display additional emission at the same energy as characterized within the flakes.

[pt] Os tópicos mais importantes a ser tratados nesta tese de doutorado são os vários problemas envolvidos na síntese de nanotubos contendo nitrogênio. Isto é principalmente motivado pelas possíveis aplicações que podem ser dadas a este tipo de estruturas. A motivação central está relacionada ao fato da possibilidade de fazer dopagens tipo -p e -n em nanotubos de carbono, incorporando átomos como boro ou nitrogênio. Isto está muito longe de ser uma trivialidade devido a que devemos levar em conta que se os nanotubos de carbono forem pensados como bases estruturais para nanocompósitos e dispositivos nanoeletronicos, é necessário controlar cuidadosamente a reatividade das paredes, sua dureza mecânica e o gap eletrônico por meio de um controle da quantidade de átomos inseridos nas paredes ou entre elas. Portanto, do ponto de vista de diferentes aplicações, é importante ter a possibilidade de dopar controladamente os nanotubos. Neste trabalho apresentam-se o quadro descritivo da dependência dos parâmetros de síntese, assim como uma investigação detalhada da formação de outras estruturas co-produto do processo de formação de nanotubos. Como uma idéia pioneira proposta neste trabalho, é enfatizado o uso de fontes puras de C/N em processos de síntese baseados em deposição química na fase de vapor. Desta maneira foi possivel determinar os efeitos da atmosfera de reação e o pretratamento do catalizador como agentes favoráveis ou desfavoráveis para a síntese efetiva de nanotubos de carbono. / [en] The main topic of this thesis is the study of various issues related to the synthesis of nitrogen containing nanotubes. This is mainly inspired in the possible applications such structures can have. The practical background lies in the fact that defined n- and p-doping of carbon nanotubes can be achieved by substituting carbon atoms from the tube walls by heteroatoms such as boron or nitrogen (N). This is far from been a triviality because we must keep in mind that if carbon nanotubes are to be used as future building blocks in nanocomposites and nanoelectronic devices, it is imperative to fine tune their wall reactivity, mechanical strength and electronic band gap by controlling the amount of foreign atoms inserted into the tube lattices. Therefore, from an applications standpoint, it is important to be able to carefully control the insertion of different dopants into nanotubes. In this work, a complete picture of the dependence on the combined synthesis parameters is established and a fundamental insight into the formation of N doped nanotubes and other structures (co- products) is provided. As a pioneering idea of this whole work, the use of pure C/N feedstocks in chemical vapor deposition methods is emphasized. With this, it was possible to determine the effects of the reaction atmosphere and the catalyst pretreatment as either favoring or disfavoring agents towards the synthesis of N-doped nanotubes.

[pt] Oxido de zinco foi sintetizado por evaporação, condensação e oxidação de Zn metálico sob pressão atmosférica. Foram desenvolvidos dois métodos de síntese, estacionário e dinâmico. No primeiro foi utilizado um reator tubular de alumina com controle local da temperatura. A evaporação do Zn aconteceu na faixa de temperaturas 900 - 1000 °C sob pressão e gradiente térmico controlados. Zn metálico foi introduzidos no reator e, durante o processo de aquecimento, o oxigênio contido no ambiente, reage com a superfície do Zn formando uma camada de ZnO que encapsula o Zn liquido contendo o vapor de Zn gerado. Quando a pressão na cápsula supera a pressão ambiental trincas são formadas na capa de óxido permitindo a emissão do vapor de Zn, que se oxida na medida que percorre o reator e, dependendo da sua trajetória, obtém-se cristais nanometricos e micrométricos de ZnO numa variedade de morfologias. O sistema dinâmico foi desenvolvido num reator de quartzo com as extremidades fechadas e permitindo a injeção controlada de argônio e oxigênio. Em todos os experimentos, predomina a presença de tetrapodos com braços finos piramidais e dimensões na faixa desde poucas centenas de nanômetros até várias micra. Estas nanopatículas foram caracterizadas por microscopia eletrônica (MEV e MET) e as suas propriedades ópticas foram analisadas por catodoluminescência mostram que a energia de emissão UV é originada do volume, enquanto e a verde emana essencialmente da sua superfície, indicando a relação com as lacunas de oxigênio. / [en] Zinc Oxide hás been synthesized by evaporation, condensation, and oxidation of methallic zinc under atmospheric pressure. Two methods of synthesis, denominated stationary and dynamic, were developed in this study. In the stationary system has the local control of temperature and a alumina tube-furnace reactor has been used. Zn was evaporated at 900-1000 C in an alumina tube under controlled pressure and heating profile. Pieces of Zn were introduced into the alumina tube. During heating, the ambient oxygen reacted with the Zn surfcace to form a layer of ZnO, which encapsulated the liquid Zn vapor. Zinc oxidizes as it travels though air, and, depending on its trajetory, a variety of morphologies. The dynamic system was based on a quartz tube reactor seled at both ends and with controlled injection of argon and oxygen while the process takes place at 900 C. One dominant structure is in the form of tetrapods whose ends form the apices of regular tetrapodron, with dimensions ranging from a few hundred nanometers to several microns. The nature of these nanostructures was characterized by transmission electron microscopy (SEM and TEM) and their optical properties have been studied using and cathodoluminescence. Images show that the UV emission originates bulk of the legs, while the green emission emanates from the surface, indicative of it being related to oxygen vacancies. / [es] El óxido de zinc fue sintetizado por evaporación, condensación y oxidación de Zn metálico bajo presión atmosférica. Se desarrolaron dos métodos de síntesis, estacionário y dinâmico. En el primeiro se uso un reactor tubular de alúminia con control local de temperatura. La evaporación de ZnO ocurrió dentro del intervalo de temperatura 900 - 1000 C en un ambientede temperatura y presión controlados. Se introduce el Zn metálico en el reactor y durante el processo de calentamiento, el oxigênio del ambiente reacciona con la superfície de Zn creando una capa de ZnO que encapsula el Zn liquido conteniendo el vapor de Zn generando. Cuando la presión de la cápsula alcanza una presión crítica forma fisuras en la de óxido, capa permitiendo la emissión de vapor de Zn, que se oxida la medida que ocorre el reactor y dependiendo de su trayectoria se obtienen cristales nanométricos e micrométricos de ZnO con una variedad de morfologias. El sistema dinâmico fue desarollando en un reactor de cuarzo con los extremos cerrados y permitiendo la inyección controlada de argón y oxígeno (900 C). en todos los experimentos, predomina la presiencia de trepodos con brazos finos piramidales e con dimensiones desde poças centenas de nanômetros asta vários micrómetros. Estas nanopartículas fueron caracterizadas por microscopia electrónica (MEV e MET) y sus propriedades ópticas fueron analizadas por catodoluminiscencia y fotoluminiscencia. Imagines monocromáticsa de catodoluminiscencia muestran que la energia de emisión UV se origina en el volumen, mientras que la verde emana principalmente de la superfície, indicando su relación con lãs vacâncias de oxigeno.

Estruturas da glândula pineal humana foram estudadas empregando os métodos de microscopia de luz, microscopia eletrônica de varredura, microscopia de varredura por espectrometria de raio-x e difração de raio-x. As peças para microscopia de luz foram fixadas em solução de formalina a 10% durante 48h e incluídas em parafina. Para a microscopia eletrônica de varredura, as peças foram fixadas em solução de Karnovsky modificada, sendo que parte das peças foram fraturadas em nitrogênio líquido para o exame das características internas do corpo píneal. Os resultados evidenciaram que o corpo píneal apresenta formações calcáreas distribuídas no interior do tecido conjuntivo. As formações calcáreas possuem tamanhos e formas diferentes. As estruturas calcáreas apresentam uma cápsula constituída pelo tecido conjuntivo. Na porção interna, a estrutura calcárea é constituída por uma série de !ameias concêntricas, com porosidade de aspecto amorfo. Evidenciou-se pela análise de difração de raio-x, a estrutura cristalina formada pelos átomos de vários elementos que compõem a formação calc área . / The structure of human pineal gland was studied by optic microscopy, scanning eletromicroscopy, spectrometer x-ray scanning eletron microscopy with energy dispersion (EDS). The tissues to analysis by optic microscopy were fixed in formalin at 1O % during 48 h and put in parffin. For S.E.M., the tissues were fixed in modified Kamovsky solution, and a part of the material was fracturated in liquid nitrogen to analysis of internal characteristic of the pineal body. The results showed that the pineal body has calcareon concretion distributed in the connective tissue. In the internai position, the calcareon structure was made of concentrics lamelae with amorf aspect. The x-ray difractor showed the cristalin structure of the atom arrangement of the elements that compose the calcarean concretions.

Durante e após o processo de reparo alveolar pós-extração, ocorre certa remodelação óssea com reduções dimensionais deste tecido podendo comprometer a terapia em implantodontia. A fim de preservar/reconstruir tal tecido, vários métodos são propostos usando diferentes tipos de biomateriais e técnicas, os quais demonstram capacidade em formar osso. O osso autógeno ainda é considerado a referência padrão como enxerto ósseo, devido ao seu potencial osteogênico, osteoindutor e osteocondutor, mas morbidade relativa a este é conhecida. Por isso algumas biocerâmicas têm sido utilizadas, pois são sintéticas, biocompatíveis e com boas propriedades osteopreenchedoras, mas com baixa osteogenicidade. A engenharia tecidual óssea constituída de células tronco mesenquimais diferenciadas em osteoblastos é uma estratégia para o fornecimento adicional celular ao defeito ósseo em reconstrução. O objetivo deste estudo foi qualificar e quantificar a reparação óssea após o enxerto de uma associação de osso autógeno e células osteoblásticas carreadas por uma biocerâmica em defeitos ósseos produzidos pela extração dentária. Os animais foram divididos de acordo com o material implantado no alvéolo dentário pós-extração em: Controle (c), osso autógeno (oa), células osteoblásticas (co), biocerâmica (bc), osso autógeno + células osteoblásticas (oa+co), osso autógeno + biocerâmica (oa+bc), biocerâmica + células osteoblásticas (bc+co), e biocerâmica + células osteoblásticas + osso autógeno (bc+co+oa). O sacrifício ocorreu aos 7, 21 e 42 dias pós-cirurgia e as amostras teciduais foram processadas para análise em microscopia de luz e eletrônica de varredura. Através de um sistema de análise de imagens foi avaliado a qualidade dos biomateriais implantados e o volume de osso, biocerâmica, conjuntivo e coágulo no defeito ósseo. Os resultados qualitativos revelaram que a biocerâmica implantada foi biocompatível e estava intimamente unida ao osso. O uso das células osteoblásticas, do osso autógeno ou da biocerâmica não desencadearam reações imunogênicas, de corpo estranho ou formação tumoral. Histometricamente as células osteoblásticas carreadas pela biocerâmica mostraram um preenchimento ósseo 19,0% maior do que quando não carreadas. A associação biocerâmica/células osteoblásticas + osso autógeno promoveu, aos 7 dias, uma deposição óssea 56,52% mais efetiva nos arredores do biomaterial do que a enxertia da biocerâmica isoladamente (1%). Conclui-se que a biocerâmica em questão pode ser um viável carreador às células osteoblásticas a serem enxertadas em sítios de reconstrução óssea, e que este composto híbrido recebe um efeito sinérgico quando da associação ao osso autógeno, sendo capaz desta forma de acelerar o processo de neoformação óssea principalmente nos períodos iniciais da reparação alveolar. / During and after the process of alveolar repair post-extraction, bone remodeling occurs with certain dimensional reductions of this tissue that can compromise the therapy in implantology. In order to preserve/reconstruct such tissue, various methods are proposed using different types of biomaterials and techniques which demonstrate the capacity to form bone. The autogenous bone is still regarded as the gold standard bone graft, due to their osteogenic, osteoinductive and osteoconductive potential, but morbidity is known about it. Therefore some bioceramics have been used, as they are synthetic, biocompatible and with good properties of bone fill, but with low osteogenic potential. The bone tissue engineering consists of mesenchymal stem cells differentiated into osteoblasts is a strategy for providing additional cell in the bone defect reconstruction. The aim of this study was to qualify and quantify bone healing after grafting of an association of autogenous bone and osteoblastic cells carried by a bioceramic in bone defects produced by tooth extraction. The animals were divided according to the implanted material in dental socket after extraction: Control (c), autogenous bone (ab), osteoblastic cells (oc), bioceramic (bc), autogenous bone + osteoblastic cells (ab+oc), autogenous bone + bioceramic (ab+bc), bioceramic + osteoblastic cells (bc+oc), and bioceramic + autogenous bone + osteoblastic cells (bc+oc+ab). The animals were sacrificed at 7, 21 and 42 days post-surgery and tissue samples were processed for light microscopy and scanning electron microscopy. Through an image analysis system the quality of implanted biomaterials and the volume of bone, bioceramic, conjunctive tissue and blood clot was evaluated inside the bone defect. Qualitative results revealed that the grafted bioceramic was biocompatible and intimately bonded with the bone. The use of osteoblastic cells, autogenous bone or bioceramic didnt trigger immunogenic reactions, foreign body or tumor formation. Histometrically, the osteoblast cells carried by bioceramic showed a bone filling 19.0% higher than when not carried. The bioceramic/osteoblastic cells + autogenous bone association promoted, at 7 days, a bone deposition 56.52% more effective around the biomaterial than the grafting of bioceramic alone (1%). It was concluded that the bioceramic in question may be a viable carrier to osteoblastic cells to be grafted on sites of bone reconstruction, and this hybrid compound receives a synergistic effect when associated to autogenous bone, thus being able to accelerate the bone formation especially in the early periods of alveolar repair.

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