<p> An approximate model has been developed for the p-n-p lateral segmented transistor, and used to characterize the behaviour of the common-emitter dc current gain to the collector segment when the control segment is set to arbitrary voltage levels. The model is a development of the type introduced by Ebers and Moll. </p> <p> The dc current gain is found to be a sensitive function of the control segment voltage, and for changes in this voltage level of the order of± 200mV, it can be made to vary between two limiting values which are dependent on device geometry. A number of applications for this device have been suggested, particularly where an a.g.c. function or controlled current source requirement are needed. </p> <p> An analytic expression has been obtained for the controlled hFE in terms of the control segment voltage and the device parameters, using an approximate analogue for the device geometry. The results have been found to describe the behaviour for a family of p-n-p lateral transistors, having circular geometry with different segment periphery ratios, within the limits of the approximations and experimental errors. </p> / Thesis / Master of Engineering (MEngr)

L'objectif du projet VELSIC a été de démontrer la faisabilité de jonctions p+/n- profondes dans le semiconducteur 4H-SiC, de haute qualité électrique, comprenant une zone p++ réalisée par un procédé original d'épitaxie localisée à basse température (1100 – 1200°C), en configuration VLS (Vapeur - Liquide - Solide). Cette technique innovante de dopage par épitaxie utilise le substrat de SiC mono cristallin comme un germe de croissance sur lequel un empilement enterré de Al - Si est porté à fusion pour constituer un bain liquide, lequel est alimenté en carbone par la phase gazeuse. Cette méthode se positionne comme une alternative avantageuse à l'implantation ionique, actuellement utilisée par tous les fabricants de composants en SiC, mais qui présente des limitations problématiques encore non résolues à ce jour. Les travaux de thèse ont exploré toutes les facettes du processus complet de fabrication de diodes de test, avec une attention particulière portée sur l'optimisation de la gravure de cuvettes dans le substrat SiC. Le cœur des travaux a été concentré sur l'optimisation de l'épitaxie VLS localisée. L'étude a confirmé la nécessité de limiter la vitesse de croissance vers 1 µm/h pour conserver une bonne cristallinité du matériau épitaxié. Elle a également mis en évidence l'action directe du champ électromagnétique radiofréquence sur la phase liquide, conduisant à une très forte influence du diamètre des cuvettes gravées sur l'épaisseur du SiC déposé. Un remplissage quasiment complet des cuvettes de 1 µm de profondeur à très fort dopage p++ a été démontré. À partir des couches VLS optimisées, des démonstrateurs de types diodes p+/n- ont été fabriqués. Sur les meilleurs échantillons, sans passivation ni protection périphérique, des tensions de seuil en régime direct (entre 2,5 et 3 V) ont, pour la première fois, été mesurées, sans recourir à un recuit haute température après épitaxie. Elles correspondent aux valeurs attendues pour une vraie jonction p-n sur 4H-SiC. Des densités de courant de plusieurs kA/cm2 ont également pu être injectées pour des tensions situées autour de 5 - 6 V. En régime de polarisation inverse, aucun claquage n'est observé jusqu'à 400 V et les densités de courant de fuite à faible champ électrique dans la gamme 10-100 nA/cm2 ont été mesurées. Toutes ces avancées si situent au niveau de l'état de l'art pour des composants SiC aussi simples, toutes techniques de dopage confondues / The objective of the VELSIC project has been to demonstrate the feasibility of 1 µm deep p+/n- junctions with high electrical quality in 4H-SiC semiconductor, in which the p++ zone is implemented by an original low-temperature localized epitaxy process ( 1100 - 1200 °C ), performed in the VLS (Vapor - Liquid - Solid) configuration. This innovative epitaxy doping technique uses the monocrystalline SiC substrate as a crystal growth seed. On the substrate (0001-Si) surface, buried patterns of Al - Si stack are fused to form liquid islands which are fed with carbon by C3H8 in the gas phase. This method is investigated as a possible higher performance alternative to the ion implantation process, currently used by all manufacturers of SiC devices, but which still experiences problematic limitations that are yet unresolved to date. Although the main focus of the study has been set on the optimization of localized VLS epitaxy, our works have explored and optimized all the facets of the complete process of test diodes, from the etching of patterns in the SiC substrate up to the electrical I - V characterization of true pn diodes with ohmic contacts on both sides.Our results have confirmed the need to limit the growth rate down to 1 µm/h to maintain good crystallinity of the epitaxial material. It has also highlighted the direct action of the radiofrequency electromagnetic field on the liquid phase, leading to a very strong influence of the diameter of the etched patterns on the thickness of the deposited SiC. A nearly complete filling of the 1 µm deep trenches with very high p++ doping has been demonstrated. Using optimized VLS growth parameters, p+/n- diode demonstrators have been processed and tested. On the best samples, without passivation or peripheral protection, high direct-current threshold voltages, between 2.5 and 3 V, were measured for the first time without any high-temperature annealing after epitaxy. These threshold voltage values correspond to the expected values for a true p-n junction on 4H-SiC. Current densities of several kA/cm2 have also been injected at voltages around 5 - 6 V. Under reverse bias conditions, no breakdown is observed up to 400 V and low leakage current densities at low electric field, in the range 10 - 100 nA/cm2, have been measured. All these advances align with or exceed state-of-the-art results for such simple SiC devices, obtained using any doping technique

Ce travail de thèse a été consacré à l'étude à la fois théorique et expérimentale de la dynamique de l'aimantation assistée par un champ électrique dans un dispositif à base de (Ga,Mn)As. Une couche de (Ga,Mn)As, dont l’anisotropie magnétique est complexe, est un matériau de choix pour la manipulation de l’aimantation par un champ électrique.J’ai présenté une stratégie de retournement précessionnel de l'aimantation qui tire partie de la réduction transitoire de l'anisotropie cubique provoquée par une courte impulsion de champ électrique. A l’aide d’un modèle macrospin, j’ai démontré notamment qu'une impulsion de champ électrique de quelques ns de durée est suffisante pour basculer l'aimantation entre deux positions d'équilibres.L'aspect expérimental est basé sur l'utilisation d'une jonction p-n tout semi-conducteur dont la région dopée p est formée par une couche mince de (Ga,Mn)As. La déplétion des porteurs de charge dans le canal semi-conducteur provoquée par l'application d'un train d'impulsions de tension de courte durée induit une forte diminution du champ d'anisotropie cubique. L'étude expérimentale du renversement de l'aimantation en champ magnétique a conduit à la mise en évidence d'un retournement de l'aimantation via la nucléation et la propagation de parois et d’une distribution large des champs de piégeage. L'inhomogénéité magnétique au sein de la couche de (Ga,Mn)As a empêché l'observation d'une résonance ferromagnétique induite par un champ électrique. Néanmoins, des mesures de retournement avec une ou plusieurs impulsions de tension de grille ont permis de proposer un processus de renversement de l'aimantation induit par un champ électrique. / This work has been devoted to the study of both theoretical and experimental electric field induced magnetization dynamics in a (Ga,Mn)As based device. A layer of (Ga,Mn)As, whose magnetic anisotropy is complex, is of particular interest for magnetization manipulation by electric fields.I proposed a scheme for the precessional switching of the magnetization using cubic anisotropy field reduction triggered by electric field pulse. Using a model macrospin, I demonstrated that a ns-pulse is sufficient to switch the magnetization between two equilibrium positions.An all-semiconductor epitaxial p-n junction based on low-doped (Ga,Mn)As was fabricated. Gating effects triggered by low voltage pulses induced a strong decrease of the cubic anisotropy field. I demonstrated that magnetization reversal is dominated by the nucleation and the propagation of domain walls. The distribution of pinning fields was found to be broad. Due to a magnetic inhomogeneity of the (Ga,Mn)As layer, it was not possible to observe any ferromagnetic resonance induced by an electric field. However, I proposed a magnetization reversal scenario based on single or multiple gate voltage pulses measurements

In recent years there is an increasing awareness of the importance of chiral phosphorus ligands in transition metal organometallic chemistry because of the utility of such complexes in homogeneous catalytic reactions. This thesis deals with synthetic, spectroscopic and X-ray crystallographic studies on ruthenium complexes of chiral and achiral P-N-P type ligands, known as "diphosphazanes", with emphasis on ruthenium carbonyl clusters. Several ruthenium carbonyl clusters have been synthesized and characterized by elemental analyses, ER and NMR (lH, nC and 3lP) spectroscopic data. In several instances, the molecular structures of the clusters have been confirmed by single crystal X-ray diffraction studies. Chapter 1 provides a brief overview of various types of chiral phosphorus ligands and general synthetic routes to diphosphazanes. A brief review of the transition metal chemistry of diphosphazanes and diphosphazane chalcogenides (published since 1994) is presented A review of the literature on the carbonyl clusters of the group-8 transition metals (Fe, Ru, Os) bearing mono- and diphosphines is also included in this chapter The scope and aim of the present investigation is outlined at the end of this chapter. Chapter 2 provides the results obtained in the present investigation and a detailed discussion of the spectroscopic and crystallographic data. The essential feature of the work is summarized at the end of the chapter. Chapter 3 gives a detailed account of the experimental procedure for the synthesis of the compounds and spectroscopic and analytical measurements. The experimental details of X-ray structure determination are also given in this chapter. To save space, the coordinates of the H-atoms and the calculated and observed structure factor tables are not included. In some cases, reference to CCDC deposition number is included. The references of the literature are compiled at the end of the thesis and are indicated in the text by appropriate numbers appearing as superscripts. The compounds synthesized in the present study are represented by bold Arabic numerals and are listed in Appendix I. The abbreviations employed in the thesis conform to those generally used in Chemical Abstracts.

Les nanostructures à base de nitrures d’éléments III suscitent un intérêt croissant, en raison de leurs propriétés singulières et de leurs applications technologiques potentielles, dans les diodes électroluminescentes (LED) notamment. La maîtrise et le contrôle du dopage de ces nanostructures est un enjeu crucial, mais difficile. A ce sujet, cette thèse apporte une contribution nouvelle, en explorant le processus de dopage de type n et p des nanofils (NFs) de GaN crus par épitaxie par jets moléculaires (EJM). En particulier, les propriétés électriques de ces structures ont été caractérisées par une approche multi-technique, à l’échelle du NF unique.Tout d'abord, les propriétés structurales et électriques d'une série de NFs de GaN dopés au Si (type n) ont été étudiées. Des mesures de spectroscopie de rayons X à haute résolution sur des NFs individuels ont mis en évidence une incorporation de Si plus élevée dans les NFs que dans les couches minces épitaxiées, ainsi qu’une migration du Si à la surface du NF pour le fil ayant le niveau de dopage le plus élevé. Des mesures de transport sur des NFs uniques (quatre contacts avec une température allant de 300 K jusqu’à 5 K) ont démontré un contrôle du dopage, avec une résistivité allant de 10^2 à 10^-3 Ω.cm et une concentration de porteurs comprise entre 10^17 et 10^20 cm-3. Des mesures réalisées sur des transistors à effet de champ à NFs uniques non intentionnellement dopés ont démontré qu’ils sont de type n avec une mobilité de porteurs élevée.Parallèlement à cela, les conditions de croissance de NFs de GaN dopés au Mg (p-type) et de jonctions p-n ont été déterminées afin d’obtenir une incorporation significative en Mg. Les propriétés électriques de jonctions p-n axiale à base de NFs de GaN posées sur un substrat de SiO2 et contactés avec de l’oxyde d’indium-étain (ITO) ont été étudiées en utilisant la technique du courant induit par faisceau électronique (EBIC). L’analyse EBIC a permis de localiser la jonction p-n le long du fil et de clairement montrer son bon fonctionnement en polarisation directe ou inverse. L'analyse EBIC a démontré que le GaN de type p est hautement résistif, confirmant ainsi les difficultés à réaliser des mesures de transport sur ce matériau.Cette étude originale a permis de décrire les propriétés électriques et de dopage de ces NFs de GaN à une échelle nanoscopique, facilitant ainsi la fabrication des futurs dispositifs incorporant des nanostructures à base de GaN. / III-nitride nanostructures have been attracting increasing attention due to their peculiar properties and potential device applications as lighting LEDs. The control and evaluation of the doping in the nanostructures is a crucial, yet a challenging issue. This thesis advances the field by exploring the n and p type doping process of GaN nanowires (NWs) grown by molecular beam epitaxy (MBE). In particular, their electrical properties have been revealed through a multi-technique approach at the single NW level.Firstly, the structural and electrical properties of a series of Si-doped (n-type) GaN NWs have been studied. High resolution energy dispersive X-ray spectroscopy measurements on single NWs have illustrated the achievement of a higher Si incorporation in NWs than in epilayers, and Si segregation at the edge of the NW with the highest doping. Furthermore, direct transport measurements (four probes measurements from 300 K down to 5 K) on single NWs have shown a controlled doping with resistivity from 10^2 to 10^-3 Ω.cm, and a carrier concentration from 10^17 to 10^20 cm-3. Field effect transistor measurements have evidenced the n-type nature and a high electron mobility of the non-intentionally doped NWs.Secondly, the growth conditions of Mg-doped (p-type) and axial GaN p-n junction NWs have been determined to achieve significant Mg incorporation. Furthermore, the electrical properties of the axial GaN p-n junction NWs, dispersed on SiO2 and contacted by ITO, have been studied using electron beam induced current (EBIC) technique. EBIC technique revealed the location of the p-n junction and clearly demonstrated its operation under reverse and forward polarization. Moreover, EBIC showed highly resistive p-GaN in accordance with the difficulties to perform direct transport measurements on p-GaN NWs.This original study provides a nanoscale description of the electrical and doping properties of the GaN NWs, facilitating the fabrication of the future GaN nanostructures based devices.

?rea de concentra??o: Produtos e coprodutos. / Submitted by Jos? Henrique Henrique (jose.neves@ufvjm.edu.br) on 2017-10-03T14:42:21Z No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) wayler_silva_santos.pdf: 9149649 bytes, checksum: 7d300a18f29fb2d1bfa9a3ab5c806ad3 (MD5) / Approved for entry into archive by Rodrigo Martins Cruz (rodrigo.cruz@ufvjm.edu.br) on 2017-10-09T14:02:32Z (GMT) No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) wayler_silva_santos.pdf: 9149649 bytes, checksum: 7d300a18f29fb2d1bfa9a3ab5c806ad3 (MD5) / Made available in DSpace on 2017-10-09T14:02:32Z (GMT). No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) wayler_silva_santos.pdf: 9149649 bytes, checksum: 7d300a18f29fb2d1bfa9a3ab5c806ad3 (MD5) Previous issue date: 2017 / Universidade Federal dos Vales do Jequitinhonha e Mucuri (UFVJM) / Funda??o de Amparo ? Pesquisa do Estado de Minas Gerais (FAPEMIG) / A convers?o da energia da radia??o solar em H2(g), combust?vel verde, usando-se c?lulas fotoeletroqu?micas (PEC) ? uma estrat?gia atraente para armazenar energia e minimizar o uso extensivo de combust?veis f?sseis. Neste trabalho, foram fabricados fotoeletrodos por deposi??o spray pyrolysis de um comp?sito de BiVO4/Bi4V2O11 puro ou dopado com W, depositado diretamente sobre um substrato condutor FTO (sigla para fluorine-doped tin oxide) ou sobre uma camada de SnO2 previamente depositada sobre o substrato FTO. Inicialmente, os materiais foram testados na clivagem molecular da ?gua. Verificou?se a forma??o de uma camada de invers?o de buracos induzida pela perovskita ferroel?trica Bi4V2O11 na interface com BiVO4 de tipo?n criando uma jun??o p?n virtual. A fotovoltagem de sa?da elevada da jun??o, em rela??o a uma heterojun??o p?n convencional, que pode ser ainda aumentada alterando-se a polariza??o e dopando-se o material ferroel?trico com tungst?nio, acarreta diminui??o da recombina??o dos pares el?tron?buracos fotogerados na superf?cie e aumenta a fotocorrente em at? 180%. O comportamento de semicondutores de tipo?p e n quando iluminados sugere o uso potencial da heterojun??o como fotoanodo e fotocatodo em uma c?lula PEC (ou photoelectrochemical cell) com dois fotoeletrodos. Este conceito foi comprovado pela conex?o do fotoanodo BiVO4/Bi4V2O11 dopado com 1% em massa de tungst?nio com o fotocatodo BiVO4/Bi4V2O11 n?o dopado. O sistema formado pelo acoplamento fotoanodo-fotocatodo produziu uma fotovoltagem de 1,54 V, e 0,36% de efici?ncia STH (solar-to-hydrogen efficiency). Um fotoeletrodo BiVO4/Bi4V2O11 dopado com 2% em massa de W foi otimizado. Evidenciou-se a forma??o da camada de invers?o de buracos na interface semicondutora no filme mais denso. Este ?ltimo foi testado em diferentes solu??es, obtendo-se elevadas densidades de corrente em NaAc 0,5 mol L-1, ? medida que se adicionou glicerina e vinha?a. Obteve?se a menor resist?ncia na transfer?ncia de cargas na interface eletrodo/eletr?lito 1,16 k? sob ilumina??o, utilizando a solu??o NaAc 0,5 mol L-1 contendo 20 %v/v de vinha?a. Nessas condi??es, a efici?ncia da convers?o de energia foi aumentada em aproximadamente 100%, e dependendo do potencial aplicado a efici?ncia aumentou cerca de 30% em solu??o contendo 10 %v/v de glicerina, com rela??o ? solu??o NaAc 0,5 mol L-1 pura, demonstrando que glicerina e vinha?a atuam como agentes de sacrif?cio eficazes no sequestro de buracos eletr?nicos, para evitar a recombina??o dos pares de el?tron?buraco, no processo de foto?oxida??o acionado por buracos. / Tese (Doutorado) ? Programa de P?s-gradua??o em Biocombust?veis, Universidade Federal dos Vales do Jequitinhonha e Mucuri, 2017. / The conversion of solar energy into green fuel H2(g) using photoelectrochemical cells (PEC) is an attractive strategy for storing energy and minimizing the extensive use of fossil fuels. In this work, photoelectrodes were prepared by pyrolysis spray deposition from a pure or W?doped BiVO4/Bi4V2O11 composite deposited directly onto an FTO (fluorine-doped tin oxide) electron-conductive substrate or onto a SnO2 layer previously deposited on an FTO substrate. Initially, these materials were tested for molecular water cleavage. It was observed a hole inversion layer induced by the ferroelectric perovskite Bi4V2O11 at the interface of the n?type BiVO4; a virtual p?n junction with high output photovoltage in relation to a conventional p?n heterojunction was also created. Altering the polarization and doping the ferroelectric material with tungsten may increase the p-n heterojunction. This polarization also reduces the recombination of the photogenerated electron?hole pairs on the surface, to increase the photocurrent to as much as 180%. This characteristic behavior of the p?type and n?type semiconductors when illuminated suggests the use of such a heterojunction as photoanode and photocatode in a PEC cell with two coupled photoelectrodes. This concept was proved to effectively work, by connecting the photovoltaic BiVO4/Bi4V2O11 doped with 1 mass% of W to the non?doped BiVO4/Bi4V2O11 photocathode, which produced a high photovoltage of 1.54 V, and 0.36% STH (solar-to-hydrogen) efficiency. A BiVO4/Bi4V2O11 photoelectrode doped with 2 mass% tungsten was optimized, evidencing the inversion of the hole layer at the semiconductor interface in the resulting denser film. This film tested in different liquid solutions revealed to produce high current densities in 0.5 mol L-1 sodium acetate (NaAc), if glycerol and vinasse were added. The electric resistance in the charge transfer at the electrode/electrolyte interface was relatively low, or 1.16 k? under illumination using 0.5 mol L-1 NaAc solution containing 20 %v/v vinasse. Adding vinasse meant an increase of the energy conversion efficiency corresponding to approximately 100%, and depending on the applied potential efficiency increased by about 30% in solution containing 10% v/v glycerin, relatively to the pure 0.5 mol L-1 NaAc solution. These results evidence that glycerin and vinasse act as effective sacrificing agents, to sequester holes and avoid the recombination of electron?hole pairs in the photo?oxidation driven by holes.

La réponse d’un détecteur de neutrons varie avec l’énergie du neutron incident. La détermination expérimentale de cette variation se réalise au moyen de champs neutroniques monoénergétiques. Ceux-ci sont produits par l’interaction entre un faisceau d’ions accélérés et une cible fine constituée d’un dépôt réactif sur un support métallique. En utilisant différentes réactions telles que 7Li(p,n), 3H(p,n), 2H(d,n) et 3H(d,n), il est possible de produire des neutrons entre 120 keV et 20 MeV dans la direction du faisceau incident (0°).Pour atteindre des énergies inférieures, il est possible d’augmenter l’angle du point de mesure par rapport à la direction du faisceau d’ions. Cependant, cette méthode présente des problèmes d’homogénéité en énergie et en fluence des neutrons à la surface du détecteur, ainsi qu’une augmentation de la proportion de neutrons diffusés. Une alternative est l’utilisation d’autres réactions nucléaires, notamment la réaction 45Sc(p,n) qui permet de descendre jusqu’à des énergies de 8 keV à 0°.Une étude complète de cette réaction et de sa section efficace a été menée au sein d’une coopération scientifique entre le laboratoire de métrologie et de dosimétrie des neutrons (LMDN) de l’IRSN, deux instituts de métrologie européens, le NPL (National Physical Laboratory, RU) et le PTB (Physikalisch-Technische Bundesanstalt, All), et l’IRMM (Institute for Reference Materials and Measurements, CEE). Parallèlement, d’autres réactions envisageables ont été étudiées : 65Cu(p,n), 51V(p,n), 57Fe(p,n), 49Ti(p,n), 53Cr(p,n) et 37Cl(p,n). Elles ont été comparées en termes d’émission neutronique et d’énergie minimale des neutrons produits. / The response of a neutron detector, defined as the reading of the device per unit of incident fluence or dose, varies with neutron energy. The experimental determination of this variation, i.e. of the response function of this instrument, has to be performed by facilities producing monoenergetic neutron fields. These neutrons are commonly produced by interaction between accelerated ions (proton or deuteron) onto a thin target composed of a reactive layer deposited on a metallic backing. Using the 7Li(p,n), 3H(p,n), 2H(d,n) and 3H(d,n) reactions, monoenergetic neutrons are obtained between 120 keV and 20 MeV in the ion beam direction (0°).To reach lower neutron energies, the angle of the measuring point with respect to the ion beam direction can be increased. However, this method presents several problems of neutron energy and fluence homogeneities over the detector surface, as well as an important increase of the scattered neutron contribution. Another solution is to investigate other nuclear reactions, as 45Sc(p,n) allowing to extend the neutron energy range down to 8 keV at 0°.A complete study of this reaction and its cross section has been undertaken within the framework of a scientific cooperation between the laboratory of neutron metrology and dosimetry (IRSN, France), two European national metrological institutes, the National Physical Laboratory (UK) and the Physikalisch-Technische Bundesanstalt (Germany), and IRMM, the Institute for Reference Materials and Measurements (EC).In parallel, other possible reactions have been investigated: 65Cu(p,n), 51V(p,n), 57Fe(p,n), 49Ti(p,n), 53Cr(p,n) and 37Cl(p,n). They were compared in terms of neutron fluence and minimum energy of the produced neutrons.

Ces travaux se sont consacrés à l’étude de l’intégration du silicium poreux au procédé de fabrication des TRIACs. Ce matériau a pour but d’optimiser les structures actuelles du point de vue de leur périphérie. Son utilisation en tant que terminaison de jonction pourrait ouvrir la voie à une diminution de la taille des puces et donc augmenter la quantité de puces par wafer. Le silicium poreux est intégré aux périphéries des TRIACs par gravure électrochimique dans du silicium faiblement dopé n (30−40 Ω.cm). Pour assurer le bon déroulement de la réaction et ce dans un cadre industriel, la technique d’injection de trous depuis une jonction p+/n est étudiée. L’influence des paramètres d’anodisation dans ces conditions est analysée. Une double couche composée de silicium macroporeux rempli de silicium mésoporeux et surmonté d’une couche de nucléation a été obtenue. Le silicium poreux est localisé dans la périphérie des TRIACs. Des mesures de tenue en tension d’une jonction p/n présentant cette terminaison à base de silicium poreux ont été évaluées et ont montrées des tenues en tension dix fois supérieures à la même structure sans silicium poreux. Toutefois, des perspectives d’amélioration sont proposées car ces résultats restent insuffisants. / The integration of porous silicon to TRIACs process is studied. The aim of this material is to optimize current structures dedicated to electrical insulation of those components namely the periphery. The use of porous silicon as junction termination could allow the increase of the number of die per wafer. Porous silicon is integrated to TRIAC peripheries by electrochemical etching in low doped n type silicon (30−40 Ω.cm). Hole injection from a p+/n junction is studied to determine the performance of the reaction as part of an industrial microelectronic process. The reaction parameters are studied in those conditions. A double layer consisting in a macroporous layer fully filled with mesoporous silicon and surmounted by a nucleation layer, is obtained. Porous silicon formation is limited to TRIAC peripheries. Voltage withstand of a p/n junction with porous silicon termination shows values ten times higher than the same structure without this insulator. Nevertheless, prospects of improvement are suggested because those results are insufficient.

Submitted by Vasti Diniz (vastijpa@hotmail.com) on 2017-09-13T12:17:27Z No. of bitstreams: 1 arquivototal.pdf: 26917769 bytes, checksum: 9ff17103475ce4130305b157369d8448 (MD5) / Made available in DSpace on 2017-09-13T12:17:27Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 26917769 bytes, checksum: 9ff17103475ce4130305b157369d8448 (MD5) Previous issue date: 2015-03-06 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / In the present work, we use first-principles calculations based on density functional theory, as implemented in the SIESTA code, to investigate the changes in the structural and electronic properties of the carbon, BN, and hybrid BxCyNz nanotubes produced by one or two of the following mechanisms: doping with carbon atoms, the application of external electric fields, by flattening of the cross section, the encapsulation of a carbon nanowire or the adsorption of hydrogen atoms (hydrogenation). We start with the study of double-walled boron nitride nanotubes (DWBNNTs), zig-zag and armchair, doped with carbon atoms, with chiral vectors (8,0)@(16,0) and (5,5)@(10,10), respectively. Two types of doping were considered: one C atom substituting a B atom on the inner wall (IW) and one C atom substituting a N atom on the outer wall (OW), which we call of CB[IW]@CN[OW], and the opposite situation results in CN[IW]@CB[OW]. In this sense, we generate a (type-p semiconductor)@(type-n semiconductor) and a (type-n semiconductor)@(type-p semiconductor), where the resulting DWBNNTs can be thought of as p-n junctions. At the same time, we apply an external electric field, with magnitude of 0,3 V/Å, in different directions, namely, perpendicular (Ey), parallel (Ex), and antiparallel (E􀀀x) to the line formed by the dopants. Thus, depending on the direction of the applied field, we observe an increase or decrease in the band gap energy between the defect levels (Eig), and such cases are related to the reverse and direct polarization of the p-n junction, respectively. Afterwards, we study the insertion of a carbon nanowire (CNW) inside a (10.0) zigzag carbon nanotube and inside a (10.0) zig-zag BN nanotube. Such systems were called CNW@SWCNT and CNW@SWBNNT, respectively. We produce the flattening of the nanotubes and verify the behavior of the atomic structure of the nanowire as the flattening of the nanotube increases. From the obtained results, it was possible to conclude that, for both CNW@SWCNT and CNW@SWBNNT, there is a critical distance dc (distance between the parallel planes of the flattened nanotubes (d)), with the value of 3.60 Å, so that we can summarize our findings as follows: in the case d > dc, the carbon nanowire does not undergo any deformation; and in the reverse case (d < dc), the carbon nanowire binds to the wall of the nanotube and undergoes deformations. Regarding the electronic properties, we verify that the encapsulation of the CNW inside the SWCNT and SWBNNT, produces a significant reduction of the band gap energy (Eg) of such systems. Moreover, we observe ABSTRACT viii the creation of Dirac points for some flattening ratios of the nanotubes. Finally, we carry out a study on the adsorption of hydrogen atoms (hydrogenation) on the surface of double-walled boron nitride nanotubes (DWBNNTs) and hybrid nanotubes of boron nitride and carbon (DW(BN)xCyNTs). Due to the fact that the nanotubes have two walls, we consider the following cases: (i) coverages of 2H, 4H, 8H, 12H, and 16H on the inner wall, (ii) coverages of 2H, 4H, 8H, 16H, and 32H on the outer wall, and (iii) coverages of 2H, 4H, 8H, 16H, and 32H on both walls. Curiously, we find that for all hydrogen coverages considered, a strong deformation occurs in the hydrogen regions, causing the cross section of the nanotubes take different polygonal shapes: ellipsoidal, rectangular, hexagonal or octahedral. For coverages of 16H and 32H only on the outer wall, we observe that some hydrogens desorbed from the wall forming isolated H2 molecules without preferential orientation. We verify that, in some cases, the bond angles between the B, N and H or C and H atoms exhibit characteristics of the sp3 hybridization. Regarding the structural stability, we verify that the adsorption of H atoms in DWBNCNTs is more favorable than in DWBNNTs. Moreover, we conclude that is possible to control the band gap energy of the nanotubes through the hydrogen coverage. / No presente trabalho, usamos cálculos de primeiros princípios baseados na Teoria do Funcional da Densidade, como implementado no código SIESTA, para investigarmos as alterações nas propriedades estruturais e eletrônicas de nanotubos de carbono, de BN e híbridos BxCyNz, produzidas por um ou dois dos seguintes mecanismos: dopagem com átomos de carbono, aplicação de campos elétricos externos, pelo achatamento da secção transversal, encapsulamento de um nanofio de carbono ou pela adsorção de átomos de hidrogênio (hidrogenação). Iniciamos com o estudo de nanotubos de nitreto de boro de parede dupla (DWBNNTs), zig-zag e armchair, dopados com átomos de carbono, com vetores quirais (8,0)@(16,0) e (5,5)@(10,10), respectivamente. Duas situações de dopagem foram consideradas: um átomo de C substituindo um átomo de B na parede interna (IW) e um átomo de C substituindo um átomo de N na parede externa (OW) a qual chamamos de CB[IW]@CN[OW], e a situação oposta resulta em CN[IW]@CB[OW]. Neste sentido, construímos um (semicondutor do tipo-p)@(semicondutor do tipo-n) e um (semicondutor do tipo-n)@(semicondutor do tipo-p) onde os DWBNNTs resultantes podem ser pensados como junções p-n. Paralelamente, aplicamos um campo elétrico externo, com magnitude de 0,3 V/Å, em diferentes direções, a saber, perpendicular (Ey), paralelo (Ex) e anti-paralelo (E􀀀x) a linha formada pelos dopantes. Assim, dependendo da direção do campo aplicado, observamos um aumento ou diminuição do gap de energia entre os níveis de defeitos (Eig) e tais casos estão relacionados a polarização reversa e direta da junção p-n, respectivamente. Em seguida, estudamos a inserção de um nanofio de carbono (CNW) no interior de um nanotubo de carbono e de BN, ambos com vetor quiral (10.0). Tais sistemas foram chamados de CNW@SWCNT e CNW@SWBNNT, respectivamente. Nós produzimos o achatamento dos nanotubos e verificamos o comportamento da estrutura atômica do nanofio a medida que o achatamento do nanotubo aumenta. A partir dos resultados obtidos, foi possível concluir que para ambos os CNW@SWCNT e CNW@SWBNNT, existe uma distancia crítica dc (distância entre os planos paralelos dos nanotubos achatados (d)), com um valor de 3.60 Å, de tal forma que nós podemos resumir as nossas descobertas como: no caso de d > dc, o nanofio de carbono não sofre nenhuma deformação; e no caso reverso (d < dc), o nanofio de carbono liga-se a parede do nanotubo e sofre deformações. Em relação as propriedades eletrônicas, verificamos que o encapsulamento do CNW nos SWCNT e SWBNNT, produz uma significativa redução do gap de energia (Eg) de tais sisteRESUMO vi mas. Além disso, observamos a formação de pontos de Dirac para algumas taxas de achatamento dos nanotubos. Por último, nós realizamos um estudo da adsorção de átomos de hidrogênio (hidrogenação) sobre a superfície de um nanotubo de parede dupla de nitreto de boro (DWBNNTs) e um nanotubo híbrido de nitreto de boro e carbono (DW(BN)xCyNTs). Devido ao fato dos nanotubos possuírem duas paredes, consideramos os seguintes casos: (i) coberturas de 2H, 4H, 8H, 12H e 16H na parede interna, (ii) coberturas de 2H, 4H, 8H, 16H e 32H na parede externa e (iii) coberturas de 2H, 4H, 8H, 16H e 32H em ambas as paredes. Curiosamente, verificamos que em todas as coberturas de hidrogênio consideradas, uma forte deformação ocorre nos locais de hidrogênio, fazendo a secção transversal dos nanotubos se transformar em diferentes formas poligonais: elipsoidal, retangular, hexagonal ou octaedral. Para coberturas de 16H e 32H apenas na parede externa, observamos que alguns hidrogênios se dessorveram da parede formando moléculas de H2 isoladas sem orientação preferencial. Verificamos que em alguns casos, os ângulos de ligação entre os átomos de B, N e H ou C e H exibem características da hibridação sp3. Com relação a estabilidade estrutural, verificamos que a adsorção de átomos de H em DWBNCNTs é mais favorável do que em DWBNNTs. Ademais, concluímos que é possível controlar o gap de energia dos nanotubos através da cobertura de hidrogênio.

La première partie de ce manuscrit traite de la synthèse de phosphine-boranes P-stéréogènes énantioenrichis à partir d’un précurseur développé par notre laboratoire : le H-phénylphosphinate d’adamantyle. Grâce au développement d’une séquence monotope, une variété d’oxydes de phosphine P-stéréogènes de haute pureté optique a pu être synthétisée. Ces composés comportant une attache hydroxyle ont ensuite été réduits de façon stéréospécifique en présence de borane pour générer les précurseurs phosphine-boranes correspondants. Lors de cette étape de réduction, l’importance de la fonction hydroxyle a été mise en évidence, et un mécanisme basé sur la formation d’une espèce phosphaboracyclique intermédiaire a été proposé, sur la base de l’isolement d’intermédiaires réactionnels O-borés. Les trois rôles du borane (activation, réduction, protection de la phosphine) ont été clairement identifiés dans ce processus. Dans un second temps, nous avons pu mettre à profit la rétroaddition du groupement hydroxyalkyle en milieu basique lors de l’alkylation stéréospécifique chimiodivergente de phosphure-boranes masqués. Cette rétroaddition a permis de contourner l’instabilité chimique et configurationnelle des phosphures générés in situ, permettant l’accès à des phosphine-boranes fonctionnalisés de manière énantiospécifique. Ces ligands P,N ont été ensuite complexés au palladium et les complexes ont pu être testés comme catalyseurs de couplages C-C énantiosélectifs. Lors de ces couplages, l’angle de morsure du ligand s’est révélé crucial pour la réactivité du système catalytique. / The first part of this manuscript deals with the synthesis of enantioenriched P-stereogenic phosphine-boranes from a chiral precursor developed in our laboratory: H-adamantyl phenylphosphinate. Through the design of a one-pot procedure, the synthesis of a wide array of highly enantioenriched phosphine oxides has been achieved. These hydroxy-functionalised compounds were reduced stereospecifically under borane conditions to yield the corresponding hydroxyalkylphosphine-boranes. During the study of this reaction, the importance of hydroxy group has been highlighted, and a mechanism relying on the formation of transient phosphaboracyclic intermediate could be proposed, on the basis of kinetic observation and isolation of O-borylated intermediates. In this transformation, borane seems to display three roles: activating, reducing and protecting agent. Next, we were able to take advantage of the retroaddition of hydroxyalkyl moiety under basic conditions to develop a new approach for the stereospecific and chemodivergent alkylation of masked secondary phosphine-boranes. This unusual reactivity allowed us to circumvent the relative chemical and configurational instability of such in situ generated phosphido-boranes intermediate, thus enabling the stereospecific synthesis of functionalised tertiary phosphine-boranes. These P-N ligands have been complexed to palladium, and the catalytic activity of these complexes in enantioselective C-C couplings has been studied. During the catalytic process, it appears that the ligand bite angle plays an important role in the catalyst activity.