abstract: Point of Load (PoL) converters are important components to the power distribution system in computer power supplies as well as automotive, space, nuclear, and medical electronics. These converters often require high output current capability, low form factor, and high conversion ratios (step-down) without sacrificing converter efficiency. This work presents hybrid silicon/gallium nitride (CMOS/GaN) power converter architectures as a solution for high-current, small form-factor PoL converters. The presented topologies use discrete GaN power devices and CMOS integrated drivers and controller loop. The presented power converters operate in the tens of MHz range to reduce the form factor by reducing the size of the off-chip passive inductor and capacitor. Higher conversion ratio is achieved through a fast control loop and the use of GaN power devices that exhibit low parasitic gate capacitance and minimize pulse swallowing. This work compares three discrete buck power converter architectures: single-stage, multi-phase with 2 phases, and stacked-interleaved, using components-off-the-shelf (COTS). Each of the implemented power converters achieves over 80% peak efficiency with switching speeds up-to 10MHz for high conversion ratio from 24V input to 5V output and maximum load current of 10A. The performance of the three architectures is compared in open loop and closed loop configurations with respect to efficiency, output voltage ripple, and power stage form factor. Additionally, this work presents an integrated CMOS gate driver solution in CMOS 0.35um technology. The CMOS integrated circuit (IC) includes the gate driver and the closed loop controller for directly driving a single-stage GaN architecture. The designed IC efficiently drives the GaN devices up to 20MHz switching speeds. The presented controller technique uses voltage mode control with an innovative cascode driver architecture to allow a 3.3V CMOS devices to effectively drive GaN devices that require 5V gate signal swing. Furthermore, the designed power converter is expected to operate under 400MRad of total dose, thus enabling its use in high-radiation environments for the large hadron collider at CERN and nuclear facilities. / Dissertation/Thesis / Masters Thesis Electrical Engineering 2018

L’avenir des nouvelles caméras embarquées pour l’astrophysique spatiale semble passer par unaccroissement du nombre de pixels et un fonctionnement à très basse température (en dessous de 0,1 K).Avec cette évolution, le nombre important de fils en sortie du détecteur refroidi représente souvent lacharge thermique prédominante sur la source froide (cryostat).Dans ce contexte, l’isolation thermique entre les différents circuits de détection est un point crucial pources caméras. Une brique technologique innovante a été développée pour apporter une solution présentantune excellente conduction électrique couplée à une grande isolation thermique. Cette innovation,protégée par un brevet, permet de résoudre cet apparent paradoxe. La solution proposée consiste enl’empilement d’un grand nombre de couches minces de matériaux supraconducteurs dans lesinterconnexions.La résistance thermique à chaque interface est dépendante des propriétés élastiques des matériaux,de la qualité des interfaces et de la température à laquelle le système fonctionne. A très basse température,le modèle AMM, couplé aux mesures des caractéristiques des matériaux composants la multicouche,permettent une estimation théorique de la résistance thermique pour une interface. Les mesures effectuéesavec les liaisons supraconductrices à forte résistivité thermique concordent avec les estimationsthéoriques. Nous avons ainsi pu mesurer des résistances thermiques de l’ordre de 3,3.105 K/W à 200 mKpour une multicouche composée d’une succession (62 interfaces) de couches minces de nitrure de titaneet de niobium sur une surface de 16 mm2. Dans les conditions d’utilisation prévues pour une camérarayons X de 4000 pixels microcalorimétriques, l’utilisation de cette brique technologique devrait assurerune charge thermique sur la source froide (à 50 mK) très inférieure au μW pour plus de 8000 pointsde contact. Ce dispositif pourra être utilisé à l’avenir dans nombre de projets cryogéniques, lorsqu’une excellenteisolation thermique associée à une excellente conduction électrique sera recherchée. / Future of the next camera onboard space observatories implies a major enhancement in number of pixelsand a very low operative temperature (below 0.1 K). In this evolution, the large number of output wiresfrom the cool detector is often responsible of the most important thermal load onto the cold bath(cryostat).In this context, the thermal insulation between the different detection circuits is the bottleneck for thesecameras. An innovative technological component, protected by a patent, has been developed to tackle thisproblem. This device has both an excellent electrical resistivity and a very high thermal resistivity.The proposed solution is a stack of thin superconducting layers at electrical interconnections.The thermal resistance at each interface relies on the elastic properties of the materials used, the quality ofthe interfaces and temperature. The AMM model used in conjunction with the measured materialcharacteristics allows a theorical estimation of the thermal resistance per interface. The measurementsundertaken with superconducting connections with very high thermal resistivity are very well describedby this AMM model. We have measured thermal resistances as high as 3.3 105 K/W @ 200 mKfor a multilayer of 62 interfaces built with titaniun nitride and niobium alternatively on a 16 mm2 array.In the conditions foreseen for a 4000 micro-calorimeters camera operating at 50 mK in X-rays,this multilayer technique should allow a thermal load onto the cold bath that is much lower that 1 mWfor more than 8000 contacts.

Ce travail de thèse a porté sur la synthèse de boîtes quantiques (BQs) de semi-conducteurs nitrures orientés (11-22) ou (0001) par épitaxie par jets moléculaires à plasma d'azote, pour des applications aux capteurs chimiques pour la détection du niveau de pH, d'hydrogène ou des hydrocarbures dans des environnements gazeux ou liquides. Dans la première partie de ce manuscrit, je décri la synthèse des couches bidimensionnelles semi-polaires (11-22) : des couches binaires (AlN, GaN, and InN) et des ternaires (AlGaN et InGaN), qui sont requises pour le contact de référence dans les transducteurs et aussi pour établir une connaissance de base pour comprendre la transition dès la croissance bidimensionnelle à la croissance tridimensionnel des BQs. Un résultat particulièrement relevant est l'étude de la cinétique de croissance et l'incorporation de l'indium dans les couches d'InGaN(11-22). De même que pour InGaN polaire (0001), les conditions optimales de croissance pour l'orientation cristallographique semi-polaire correspondent à la stabilisation de 2 ML d'In sur la surface, en excellent accord avec des calculs théoriques. Les limites de la fenêtre de croissance en termes de température du substrat et de flux d'In sont les mêmes pour les matériaux semi-polaire et polaires. Cependant, j'ai constaté une inhibition de l'incorporation de l'In dans les couches semi-polaires, même pour une température en dessous du seuil de la ségrégation pour l'InGaN polaire. Dans une deuxième étape, j'ai fabriqué des super-réseaux de BQs de GaN/AlN et InGaN/GaN, à la fois dans l'orientation polaire et semi-polaire. Les mesures de photoluminescence et de photoluminescence en temps résolu confirment la réduction du champ électrique interne dans les boîtes semi-polaires. D'autre part, les BQs semi-polaires à base d'InGaN doit relever le défi de l'incorporation d'In dans cette orientation cristallographique. Pour surmonter ce problème, l'influence de la température de croissance sur les propriétés des boîtes quantiques InGaN polaires et semi-polaires a été étudiée, en considérant la croissance à haute température (TS = 650–510 °C, où la désorption d'In est active) et à basse température (TS = 460–440 °C, où la désorption d'In est négligeable). J'ai démontré que les conditions de croissance à faible TS ne sont pas compatibles avec le plan polaire, tandis qu'ils fournissent un environnement favorable au plan semi-polaire pour améliorer l'efficacité quantique interne de nanostructures InGaN. Enfin, j'ai synthétisé un certain nombre de transducteurs à BQs de GaN/AlN et InGaN/GaN selon les axes de croissance polaire et semi-polaire. Dans chaque cas, les conditions de croissance pour atteindre la fourchette spectrale ciblée (420-450 nm d'émission à avec une couche contact transparente pour des longueurs d'onde plus courtes que 325 nm) ont été identifiés. L'influence d'un champ électrique externe sur la luminescence des transducteurs ont confirmé que la meilleure performance (plus grande variation de la luminescence en fonction de la polarisation) a été fournie par des structures à base de BQs d'InGaN/GaN. Avec ces données, les spécifications des transducteurs opto-chimiques ont été fixées : 5 perides de BQs d'InGaN/GaN sur une couche contact d'Al0.35Ga0.65N:Si). Puis, j'ai synthétisé un certain nombre de ces transducteurs afin d'obtenir un aperçu sur la reproductibilité, limites et les étapes critiques du processus de fabrication. En utilisant ces échantillons, nous avons réalisé un système capteur intégré qui a été utile pour le suivi de la valeur du pH de l'eau. / This thesis work has focused on the synthesis of (In)GaN-based quantum dot (QD) structures by plasma-assisted molecular-beam epitaxy (PAMBE), deposited in both polar (0001) and semipolar (11-22) crystallographic orientations, for application as optical transducers for chemical sensors for detection of pH levels, and hydrogen or hydrocarbon concentrations in gas or liquid environments. In the first part of this work, I describe the synthesis of semipolar-oriented two-dimensional layers: binary alloys (AlN, GaN and InN) and ternary alloys (AlGaN and InGaN), which are required for the reference contact of the transducers and set the basic know-how to understand the transition from two-dimensional growth to three-dimensional QD nanostructures. It is particularly relevant the study of indium kinetics and indium incorporation during the PAMBE growth of InGaN(11-22) layers. Similarly to (0001)-oriented InGaN, optimum growth conditions for this semipolar crystallographic orientation correspond to the stabilization of 2 ML of In on the growing InGaN surface, in excellent agreement with first-principles calculations. The limits of the growth window in terms of substrate temperature and In flux lie at same values for polar and semipolar materials. However, I observe an inhibition of the In incorporation in semipolar layers even for substrate temperatures below the segregation threshold for polar InGaN. In a second stage, I report the successful fabrication of superlattices (SLs) of GaN/AlN and InGaN/GaN QDs, both in polar and semipolar orientations. Photoluminescence and time-resolved photoluminescence confirmed the reduction of the internal electric field in the semipolar GaN/AlN QDs in comparison with polar structures. On the other hand, semipolar InGaN QDs must face the challenge of In incorporation in this crystallographic orientation. To overcome this problem, the influence of the growth temperature on the properties of the polar and semipolar InGaN QDs has been studied, considering growth at high temperature (TS = 650–510 °C, where In desorption is active) and at low temperature (TS = 460–440 °C, where In desorption is negligible). I demonstrate that low-TS growth conditions are not compatible with polar plane whereas they provide a favorable environment to semipolar plane to enhance the internal quantum efficiency of InGaN nanostructures. Finally, I have synthesized a number of GaN/AlN and InGaN/GaN QD optical transducers, grown in polar and semipolar orientations. In each case, the growth conditions to attain the targeted spectral range (emission at 420-450 nm with buffer transparent for wavelengths shorter than 325 nm) were identified. The influence of an external electric field on the luminescence of the transducers confirmed that the best performance (larger variation of the luminescence as a function of bias) was provided by InGaN/GaN QD structures. With this feedback, the specifications of the targeted opto-chemical transducer structures have been established (5 InGaN/GaN QD layers on Al0.35Ga0.65N:Si). Then, I have synthesized a number of InGaN/GaN opto-chemical transducers in order to get an insight on the reproducibility, limitations and critical steps in the fabrication process. Using these samples, we have achieved an integrated sensor system based on polar InGaN QD SLs, and the system was useful for monitorization of the pH value of water.

Ce travail de thèse porte sur la croissance par épitaxie par jets moléculaires assistée plasma et sur la caractérisation de nanofils (NF) de GaN et d'hétérostructures filaires de GaN/AlN. Dans un premier temps, la morphologie des NFs de GaN (densité, longueur moyenne, diamètre moyen, dispersion de longueurs) est étudiée en fonction des paramètres de croissance. Via la diffraction d'électrons rapides, la morphologie des NFs GaN est corrélée à la dynamique de nucléation de ces derniers. Des expériences de diffraction de rayons X en incidence rasante effectuées à l'ESRF permettent également de clarifier les processus de nucléation des NFs GaN. Nous démontrons ensuite l'utilisation de la diffraction de rayons X résonnante pour déterminer la polarité des NFs GaN. Nous montrons que ces derniers sont de polarité N lorsque fabriqués sur Si nu. Des tests complémentaires de gravure sélective au KOH révèlent que les NFs GaN fabriqués sur un substrat de Si recouvert d'un fin buffer d'AlN ainsi que ceux dont la fabrication est initiée après pré-déposition de Ga sur la surface du Si, sont aussi de polarité N. Concernant les hétérostructures filaires GaN-AlN, la croissance d'AlN autour et sur les nanofils de GaN est étudiée en fonction de divers paramètres de croissance. Le rapport d'aspect des coquilles d'AlN (longueur/épaisseur) est décrit par un modèle géométrique. En utilisant une combinaison de diffraction anomale multi-longueurs d'onde, de microscopie en transmission de haute résolution et des calculs théoriques, l'état de contrainte des coeurs de GaN est analysé en fonction de l'épaisseur de la coquille. Cette contrainte augmente avec l'épaisseur de la coquille tant que l'AlN croît de manière homogène autour des NFs de GaN. Dès lors que la coquille est asymétrique, le système relaxe plastiquement. Nous étudions enfin la possibilité de fabriquer des îlots de GaN dans des NFs AlN. Nous déterminons le rayon critique de NFs AlN au-dessus duquel le GaN déposé subit une transition de forme de 2D à 3D. L'analyse des propriétés optiques de ces nanostructures originales revèle la présence de nombreux états localisés. / This work focuses on the growth by plasma-assisted molecular beam epitaxy and on the characterization of GaN nanowires (NWs) and of GaN/AlN NW heterostructures. We first investigate GaN NW morphology (density, mean length, mean diameter, length dispersion) dependence on the growth parameters. Using reflection high energy electron diffraction, GaN NW morphology is correlated to their nucleation dynamics. In situ grazing-incidence X-ray diffraction experiments performed at the ESRF allow clarifying GaN NW nucleation processes on bare Si(111) and when usinga thin AlN buffer deposited on Si(111). The use of resonant X-ray diffraction for the determination of GaN NW polarity is then successfully demonstrated. GaN NWs grown on bare Si(111) are shown to be N-polar. Additional KOH selective etching tests reveal that both GaN NWs grown using a thin AlN buffer on Si(111) and when pre-depositing Ga on the Si(111) surface are N-polar, too. Regarding GaN-AlN NW heterostructures, the growth of an AlN shell around GaN NWs is studied as a function of various growth parameters. The AlN shell aspect ratio is described by a geometrical model. Using a combination of multiwavelength anomalous diffraction, high resolution transmission microscopy and theoretical calculations, GaN core strain state is investigated as a function of the AlN shell thickness. This strain is shown to increase with the shell thickness as long as AlN grows homogeneously around GaN NWs. When the shell is asymmetric, the system relaxes plastically. Eventually, we study the possibility to fabricate island-like GaN insertions in AlN NWs. We determine the critical AlN NW radius above which GaN undergoes a 2D to 3D shape-transition. Regarding optical properties of these novel structures, the presence of multiple localized states is identified.

Le graphène possède un gaz bidimensionnel de porteurs de charge stable et exposé à l'environnement sans aucune protection. Par conséquent, ses performances électriques sont extrêmement sensibles aux conditions environnementales, notamment aux impuretés chargées et aux corrugations imposées par le substrat sous-jacent. Ces éléments ont une contribution majeure dans la dégradation des propriétés de transport électronique du matériau.L'objectif de cette thèse est d'explorer par diverses techniques des méthodes pour atténuer ces effets par optimisation de son environnement direct.La première méthode consiste à reporter le graphènesur une couche neutre d'un cristal de nitrure de bore hexagonal (BN). Diverses techniques de fabrication d'empilement de Graphène sur BN sont présentées, notamment la croissance directe de graphène sur un cristal de BN exfolié sur un substrat catalytique qui aboutit à la formation d'empilements de structure bien contrôlée. Les échantillons sont mesurés à très basse température. Les effets de localisation faible mesurés par magnéto-transport montrent une amélioration nette des performances notamment de la longueur de cohérence et de la mobilité électronique par rapport à un échantillon de référence constitué du même ruban de graphène déposé sur substrat conventionnel de silicium oxydé.La deuxième technique consiste à isoler le graphène de son support par surgravure de la silice et suspension du graphène sous la forme d'une membrane autosupportée et tenue par ses extrémités. Après avoir introduit des techniques de fabrication spécifiques, les mesures de transport et le couplage à des modes de vibration mécanique sont étudiés température variable. Ces données permettent notamment une mesure du coefficient d'expansion thermique du graphène. / Charge carriers in graphene form stable two-dimensional gases which are fully exposed to the environment. As a consequence, the electrical performance of graphene is strongly affected by surface charged impurities as well as topographic perturbations inherited from the underlying substrate.This thesis addresses several methods to circumvent that issue.The first method consists in embedding graphene in an optimized environment by depositing graphene onto some neutral and crystalline material. Novel 2D insulating materials such as hexagonal boron nitride buffer layer (BN) appears as ideal substrates to get rid of detrimental effect of interfacial charges and corrugation. Several fabrication schemes of Graphene/BN stacks are shown including some direct in-situ growth of graphene on BN crystal using an innovative proximity-driven chemical vapour growth based on BN exfoliation on copper. In order to explore the effects of the improved substrate on the transport properties of graphene, we have performed low temperature magneto-transport studies on these stacks. We present a direct comparison of weak localization signals with those acquired on a graphene/silica reference device. A clear increase of the coherence length is shown on Graphene/BN stacks together with improved electronic mobility and charge neutrality.Removing the substrate and suspending graphene is another approach for optimization of the graphene environment which forms the second topic covered in this thesis. After introducing an improved recipe for preserving the quality of graphene throughout an elaborate fabrication process, we probe the room- and low-temperature performance of the nano-electro-mechanical devices based on doubly clamped suspended graphene ribbons. The obtained data are used for characterizing the thermal expansion of CVD graphene.

Submitted by Vasti Diniz (vastijpa@hotmail.com) on 2017-09-11T13:33:18Z No. of bitstreams: 1 arquivototal.pdf: 2568503 bytes, checksum: df847883585ac25cc1e993ba9c1fcd9f (MD5) / Made available in DSpace on 2017-09-11T13:33:18Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 2568503 bytes, checksum: df847883585ac25cc1e993ba9c1fcd9f (MD5) Previous issue date: 2017-02-24 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / The opening a energy gap in graphene is probably one of the most important and urgent topics in its research currently, since most of the proposed applications for graphene in nanoelectronic devices require the ability to adjust its gap. In materials similar to graphene as BN and BC2N, the tuning of some properties is also indispensable so that they can be used as basic components of future nanoelectronic and spintronic. Graphene nanoribbons are strong candidates in this regard. All these systems have widely tunable properties and there are several theoretical and experimental methods which can be used for this purpose, one of them is to incorporate defects, since these defects have been obtained experimentally in these systems. In this context, using first-principles calculations, based on the density functional theory (DFT), we investigate alterations in the structural, electronic, energetic and magnetic properties due to the inclusion of different types of defects in monolayers and nanoribbons of graphene, BN and hybrid graphene-BC2N. As a result of the controlled inclusion of these defects, a series of new results were observed, as well as the tuning of the structural, electronic, energetic and magnetic properties in these systems. / A abertura de um gap de energia no grafeno é provavelmente um dos temas mais importantes e urgentes em sua pesquisa atualmente, uma vez que, a maioria das aplicações propostas para o grafeno em dispositivos nanoeletrônicos requer a capacidade de ajustar seu gap. Em materiais similares ao grafeno como BN e o BC2N o ajuste de algumas propriedades também é indispensável para que eles possam fazer parte como componentes ativos na nanoeletrônica e spintrônica no futuro. As nanofitas são fortes candidatas nesse sentido. Todos esses sistemas possuem propriedades bastante ajustáveis e existem vários métodos teóricos e experimentais que podem ser usados para este fim, um deles, é a inclusão de defeito, defeitos têm sido obtido experimentalmente nesses sistemas. Neste contexto, usando cálculos de primeiros princípios baseados na teoria do funcional da densidade (DFT), investigamos as mudanças provocadas nas propriedades eletrônicas, energéticas, estruturais e magnéticas devido à inclusão de vários tipos de defeitos em monocamadas e nanofitas de grafeno, BN e híbridas de grafeno-BC2N. Como resultado da inclusão controlada desses defeitos, observamos uma série de novos resultados, bem como o ajuste de várias propriedades para esses sistemas através da inclusão controlada de defeitos.

O desempenho de componentes de engenharia está intimamente ligado a fenômenos de superfície, pois esta funciona como a interface entre o componente e o ambiente que o cerca. A escolha de um material com propriedades superficiais adequadas é fundamental para a sua funcionalidade. Neste trabalho as propriedades físico-químicas, estruturais e mecânicas do filmes de nitreto de silício depositados por magnetron sputtering reativo com uma fonte de radiofreqüência, antes e após tratamento térmico em 18O2, foram analisadas por diferentes métodos, tais como nanodureza, difração de raios X, perfilometria por reação nuclear ressonante, nanoindentação, espectrometria de retroespalhamento Rutherford, espectroscopia de fotoelétrons induzidos por raios X e reflectometria de raios X. Os filmes de Si3N4 depositados são essencialmente amorfos, estequiométricos e livres de contaminantes para vários parâmetros de deposição, com valores de dureza que variam de 16,5 GPa 22 GPa, dependendo principalmente da temperatura de deposição dos filmes. Depois de realizado o tratamento térmico em 18O2 a 1000 °C, a dureza de filmes converge para 21 GPa, independentemente da temperatura de deposição o que é explicado com base na cristalização dos filmes nesta temperatura de tratamento térmico. Além disso, o oxigênio é incorporado apenas 7,5 nm do filme de Si3N4, formando oxinitreto de silício na superfície do filme, indicando uma boa resistência à oxidação em altas temperaturas. Finalmente, a deformação elástica até a fratura H3/E2, que é um bom indicador da resistência ao desgaste do filme, dobra após o tratamento térmico a 1000 °C. Estas observações mostram o grande potencial do nitreto de silício como um revestimento duro para aplicações em altas temperaturas. / Submitted by Marcelo Teixeira (mvteixeira@ucs.br) on 2014-06-03T19:57:31Z No. of bitstreams: 1 Dissertacao Cristiane Marin.pdf: 10200632 bytes, checksum: 55a17a7df0f8900cefa2a80a1fe4c086 (MD5) / Made available in DSpace on 2014-06-03T19:57:31Z (GMT). No. of bitstreams: 1 Dissertacao Cristiane Marin.pdf: 10200632 bytes, checksum: 55a17a7df0f8900cefa2a80a1fe4c086 (MD5) / The performance of engineering components is closely tied to surface phenomena, because it acts as an interface between the component and the environment that surrounds it. The choice of a suitable material with surface properties is critical to its functionality. In this study the physicochemical, structural and mechanical properties of silicon nitride films deposited by radio frequency reactive magnetron sputtering before and after thermal annealing in 18O2 were analyzed using different methods, such as nanohardness, X-ray diffraction, profilometry resonant nuclear reaction, nanoindentation, Rutherford backscattering spectrometry, photoelectron spectroscopy and X-ray induced X-ray reflectometry The Si3N4 films deposited are essentially amorphous, stoichiometric and free of contaminants for various deposition parameters, with hardness values ranging from 16.5 GPa 22 GPa, depending mainly on the deposition temperature of films. After 18O2 annealing at 1000°C, films hardness converged to 21 GPa, independently of the deposition temperature, which is explained on the basis of crystallization of the films at this annealing temperature. Furthermore, oxygen is incorporated only in the 7.5 nm film of Si3N4, forming silicon oxynitride on the surface of the film, indicating good oxidation resistance at high temperature. Finally, the elastic strain to failure H3/E2, which mimics the wear resistance of the film, doubles after the 1000°C annealing. These observations show the great potential of silicon nitride as a hard coating for high temperature applications.

Submitted by Lucas Jorge Affonço (lucas_jorgeaffonco@yahoo.com.br) on 2018-09-25T18:16:47Z No. of bitstreams: 1 Dissertação_POSMAT_LucasJorgeAffonco.pdf: 1122070 bytes, checksum: 3aa8bf900f18ab0cc3c2d9fdbbc0ce2e (MD5) / Rejected by Lucilene Cordeiro da Silva Messias null (lubiblio@bauru.unesp.br), reason: Solicitamos que realize uma nova submissão seguindo as orientações abaixo: 1 - Inserir no corpo do texto uma cópia da ata de defesa, pois é um item obrigatório. Agradecemos a compreensão on 2018-09-26T13:33:08Z (GMT) / Submitted by Lucas Jorge Affonço (lucas_jorgeaffonco@yahoo.com.br) on 2018-09-26T13:39:25Z No. of bitstreams: 1 Dissertação_POSMAT_LucasJorgeAffonco.pdf: 1731555 bytes, checksum: 7c7c9ba43b8b832af33307bef8e74d22 (MD5) / Approved for entry into archive by Lucilene Cordeiro da Silva Messias null (lubiblio@bauru.unesp.br) on 2018-09-26T17:02:25Z (GMT) No. of bitstreams: 1 affonço_lj_me_bauru.pdf: 1731555 bytes, checksum: 7c7c9ba43b8b832af33307bef8e74d22 (MD5) / Made available in DSpace on 2018-09-26T17:02:25Z (GMT). No. of bitstreams: 1 affonço_lj_me_bauru.pdf: 1731555 bytes, checksum: 7c7c9ba43b8b832af33307bef8e74d22 (MD5) Previous issue date: 2018-07-26 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / O nitreto de titâno apresenta uma vasta gama de aplicações. Entre elas destacam-se as aplicações em recobrimento de superfícies que exploram características mecânicas tais como dureza e módulo de elasticidade do material para aplicações em biomateriais. Essas características e suas correlações com a microestrutura são investigadas, nesse trabalho, em função dos parâmetros de deposição de filmes de TiN. Os filmes foram depositados pela técnica de magnetron sputtering reativo em rádio frequência, sobre substratos de titânio, de sílica, de silício e de uma liga de titânio-nióbio. Nas deposições, foi utilizado um alvo de titânio puro e misturas gasosas de argônio e nitrogênio, com diferentes fluxos de nitrogênio. As potências empregadas foram de 240 W e 300 W, com diferentes tempos de deposição. Medidas de taxa de deposição e emissão óptica do plasma auxiliaram na escolha dos parâmetros de deposição. As análises das difrações de raios X mostraram que com o aumento do fluxo de nitrogênio os cristalitos tendem a apresentar uma orientação preferencial com os planos (200) do TiN paralelos à superfície do substrato, além de indicar a presença de strain nos filmes. Medidas de nanoindentação foram realizadas nas amostras, com o intuito de obter a dureza e o módulo de elasticidade dos filmes depositados com diferentes fluxos de nitrogênio. Buscando assim determinar a influência do fluxo sobre as propriedades mecânicas e a microestrutura dos filmes. Verificou-se que a dureza nas amostras depositadas a 10 sccm foi a maior, variando de 10 a 18 GPa de acordo com a profundidade de penetração, sendo essa amostra a que apresentou maior textura de orientação favorecendo os planos (200). O módulo de elasticidade foi maior para a amostra de 8 sccm, em torno de 140 GPa, sendo essa a amostra que apresentou maior strain compressivo. Verificou-se que a técnica de sputtering reativo é versátil para o crescimento dos filmes de nitreto de titânio, e que o fluxo de nitrogênio usado nas deposições é um parâmetro de grande impacto nas características mecânicas e estruturais dos filmes obtidos. / The titanium nitride (TiN) has mechanical properties that are useful in a wide range of applications. In special, it is being investigated to improve the surfaces of bone implants. The mechanical properties of TiN films deposited by reactive magnetron sputtering and their correlations with microstructure will be investigated in this dissertation as a function of the deposition parameters. The films were deposited in titanium, silica, silicon and titanium-niobium substrates. A pure titanium target and a mix of argon and nitrogen gases were used in the depositions. The influence of the variation of the reactive gas fluxes on the mechanical properties and in the microstructure of the films were investigated, for applied powers of 240 W and 300 W at 13.6 MHz. Deposition rate and plasma optical emission measurements helped to control the deposition parameters. X ray diffraction analysis show that all films present compressive strain and, at high nitrogen fluxes, a preferred crystallite orientation of planes (200) parallel to the substrate surface occurs. Nanoidentation measurements were performed, for different nitrogen fluxes, to obtain the hardness and elastic modulus of TiN films. The hardness of films deposited at 10 sccm, varied between 10 and 18 GPa, as a function of the penetration depth, and is higher than the observed in other samples. These films also showed the higher (200) plane texture. The elastic modulus is higher on films deposited at 8 sccm N2 flow (around 140 GPa). These films also showed the higher compressive strain. It was checked that the reactive sputtering is a resourceful technique for titanium nitride deposition, and nitrogen flux present a high impact in the structure and mechanical properties of the deposited films.

De nos jours, les produits chimiques toxiques industriels ne sont pas toujours traités proprement, et leurs contaminants peuvent directement affecter la sécurité de l'eau potable. La photocatalyse, «une technologie verte» est une approche efficace et économique qui joue un rôle important dans la conversion de l'énergie solaire et la dégradation des polluants organiques. Ce manuscrit de thèse rapporte sur le développement des matériaux avancés (basés sur TiO2 et ZnO) susceptibles d'exploiter l'énergie solaire renouvelable pour résoudre les problèmes de pollution environnementale. Une partie de ce travail a été consacrée pour l’amélioration de l’activité photocatalytique du TiO2 sous lumière UV et visible. Par conséquent, les nanofibres composites de rGO/TiO2, BN/TiO2 et BN-Ag/TiO2 ont été élaborées en utilisant la technique d'électrofilage (electrospinning). La deuxième partie porte sur le ZnO, ainsi que les nanotubes multi co-centriques de ZnO/ZnAl2O4 et les nanotubes de ZnO dopés Al2O3 qui ont été synthétisés en combinant les deux techniques : dépôt de couche atomique (ALD) et electrospinning. Les propriétés morphologiques, structurelles et optiques de toutes les nanostructures synthétisées ont été étudiées par différentes techniques de caractérisations. Les résultats ont montré que les propriétés chimiques et physiques ont un effet très important sur les propriétés photocatalytiques des matériaux synthétisés. En outre, il a été constaté que l'effet de dopage conduit à une séparation de charge efficace dans le photocatalyseur, ce qui rend l’activité photocatalytique plus efficace. De plus, le méthyle orange et le bleu de méthylène ont été utilisés comme modèle de référence. Une amélioration significative et une stabilité à long terme de l’activité photocatalytique ont été observées avec les matériaux dopés comparés aux matériaux non-dopés sous lumière UV et visible. Des tests antibactériens contre Escherichia coli ont été également effectués; les résultats indiquent que BN-Ag/TiO2 présente à la fois des propriétés photocatalytiques intéressantes pour la dégradation des composés organiques et pour l'élimination des bactéries. / Nowadays, industrial toxic chemicals are still not properly treated and these contaminants may directly impact the safety of drinking water. Photocatalysis “a green technology” is an effective and economical approach and plays an important role in solar energy conversion and degradation of organic pollutants. This thesis manuscript reports on developing advanced materials (based on TiO2 and ZnO) being capable of exploiting renewable solar energy for solving the environmental pollution problems. A part of this work was dedicated to improve the UV and visible light TiO2 photoresponse. Therefore, rGO/TiO2, BN/TiO2 and BN-Ag/TiO2 composties nanofibers were successfully elaborated using the electrospinning technique. The second part focused on ZnO. Novel structures of ZnO/ZnAl2O4 multi co-centric nanotubes and Al2O3 doped ZnO nanotubes were designed by combining the two techniques of atomic layer deposition (ALD) and electrospinning. The morphological, structural and optical properties of all synthesized nanostructures were investigated by several characterization techniques. The results show that the chemical and physical properties have a high impact on the photocatalytic properties of the synthesized materials. Moreover, it was found that the doping effect lead to a more efficient charge separation in the photocatalyst, which is an advantage for photocatalytic activities. In addition, methyl orange and methylene blue were used as model reference. A significant enhancement and a long-term stability in the photocatalytic activity were observed with the doped materials compared to the non-doped ones under both UV and visible light. Antibacterial tests against Escherichia coli have also been performed; the results indicate that BN-Ag/TiO2 present interesting photocatalytic properties for both organic compound degradation and bacterial removal.

Neste trabalho, foi investigado o comportamento tribológico dos pares cerâmicos aluminanitreto de silício no deslizamento em água e em uma suspensão de sílica coloidal em água (hidrosol). O objetivo foi verificar a possibilidade de atingir um coeficiente de atrito da ordem de unidades de milésimos, aqui chamado de ultra-baixo coeficiente de atrito (UBCA), verificar se a mudança do meio, de água para hidrosol, diminui o running-in do coeficiente de atrito, e verificar o efeito da variação da rugosidade inicial da alumina no comportamento do atrito. Os ensaios foram realizados na configuração de teste esferasobre- disco, no qual a esfera foi de nitreto de silício e o disco de alumina, sob carga normal de 54 N e velocidade de 1 m/s. A água utilizada nos ensaios foi destilada e deionizada, e a sílica coloidal amorfa, hidrofílica, sem porosidade e de tamanho médio de partícula de 12 nm foi a Aerosil® 200, e o hidrosol foi preparado com pH 8,5 num eletrólito de NaCl de 1 mM. A esfera de nitreto de silício, adquirida comercialmente, e a alumina, sinterizada em laboratório, foram caracterizadas quanto a densidade, as fases foram determinadas por difração de raios X, microscopia eletrônica de varedura (MEV) observada em amostras ceramográficas atacadas. Algumas propriedades mecânicas como dureza, módulo de elasticidade e tenacidade à fratura foram determinadas. Duas condições de rugosidade dos discos de alumina foram utilizadas nos ensaios tribológicos, 350 nm e 10 nm RMS. Em todos os ensaios, em água, em hidrosol e independentemente da rugosidade inicial do disco o coeficiente de atrito no regime permanente apresentou pequena dispersão de valores de 0,002 a 0,006, e não foi possível estabelecer diferença entre elas. A menor rugosidade do disco de alumina acarretou menor desgaste e menor período de running-in de coeficiente de atrito, tanto em água quanto em hidrosol. Os ensaios em meio de hidrosol acarretaram menor desgaste das cerâmicas e apresentaram menor running-in de coeficiente de atrito, comparados aos ensaios com água. O disco de alumina apresentou menor desgaste do que a esfera de nitreto de silício, em todas as condições estudadas. Com a análise das perdas volumétricas, da rugosidade final das superfícies desgastadas, das curvas de coeficiente de atrito e das espessuras mínimas de filme lubrificante, calculadas com uso de modelo da literatura, foi possível relacionar a diminuição do desgaste e do running-in de coeficiente de atrito em meio de hidrosol, com a presença da sílica na superfície ou próxima dela. / In this work, the tribological behavior of the alumina-silicon nitride couple was investigated under water and hydrosol (colloidal silica suspensions in water) lubricated sliding. The purposes were to study how an ultra-low friction coefficient can be achieved and to analyze the effects of the environment, lubricant and alumina roughness changes on the friction behavior. Ball-on-disk tests with a normal load of 54 N and a sliding speed of 1 m/s were carried out, using a silicon nitride ball and an alumina disk. The water used as lubricant was distilled and deionized. The silica was amorphous colloidal and hydrophilic, without porous and with a 12 nm medium particle diameter, commercially named Aerosil ® 200. The hydrosol was obtained with a pH value of 8,5 and a 1mM NaCl electrolyte. To estimate the minimum film thickness, formed during the lubricated sliding tests, a theory model was used. The commercial silicon nitride balls and the alumina disks, which were conformed and sintered in laboratory, were characterized by density, X-ray diffraction and scanning electron microscopy measurements. The mechanical properties such as hardness, Young modulus and fracture toughness were determined. The friction coefficient values obtained in the steady state regime showed low standard deviations (0,002 to 0,006) under all conditions. A shorter period of running-in was observed with the lower disk roughness, both in water and hydrosol lubrication. The hydrosol lubricated sliding produced a lower wear and friction running-in comparing with the tests under water lubrication. The alumina disk always showed lower wear than the silicon nitride ball. The volume loss, friction coefficients, worn surfaces roughness and minimum film thickness results suggest that the wear and friction coefficient running-in decrease was caused by the presence of silica on the sliding surfaces or on the near surface regions.