Ce manuscrit de thèse présente une étude expérimentale des propriétés optiques, électroniques et structurales du diamant fortement dopé au bore. Ce semi-conducteur à large bande interdite peut être synthétisé par dépôt chimique en phase vapeur assisté par plasma micro-onde (MPCVD). Il est intrinsèquement isolant mais devient métallique, voire supraconducteur conventionnel par dopage de type p. Ce travail s'articule autour de trois grands axes :Le premier concerne le développement de l'ellipsométrie spectroscopique pour la caractérisation de couches de diamant monocristallin. Dans un premier temps, des modèles optiques ont été développés afin de déduire les épaisseurs, résistivités et concentrations de porteurs de plusieurs séries d'échantillons mesurés ex situ. Ces valeurs ont été confrontées à celles obtenues par le biais de mesures SIMS (Spectroscopie par Emission d'ion Secondaires) et de transport électronique. Une masse effective optique des porteurs a pu ainsi être évaluée. Dans un second temps, cette technique a été mise en oeuvre in situ sur le réacteur. L'influence de la température et de la géométrie de la chambre de réaction a été évaluée et des suivis de croissance en temps réel sont présentés.Le second axe porte sur la synthèse des échantillons et l'optimisation des paramètres de croissance. Dans cette partie, nous révélons la présence d'un transitoire dans l'incorporation du bore conduisant à une inhomogénéité de dopage des échantillons. Une augmentation de l'incorporation du bore avec le débit a également été observée pour la première fois. Enfin, la détérioration de la qualité cristalline du diamant, au delà d'une concentration critique d'atomes de bore, est identifiée et discutée.Le troisième et dernier axe de ces travaux de recherche, est dédié à l'investigation des propriétés électroniques du diamant fortement dopé par magnéto-transport de 300K à 50 mK. Dans un premier temps, l'importance de la mésa-structuration de croix de Hall lors des mesures de transport est mise en évidence. L'utilisation d'une géométrie « maîtrisée », permet en effet de limiter les courants parasites dus à l'inhomogénéité de dopage des couches. Nous avons ainsi pu construire un diagramme de phase différent de celui qui avait été rapporté dans la littérature. Une phase métallique et non supraconductrice a été mise en évidence pour la première fois. Une étude de la transition métal-isolant est présentée, et les exposants critiques issus de sa modélisation sont discutés. L'étude de l'état supraconducteur enfin, nous a permis d'aboutir à une nouvelle dépendance de la température de transition (Tc) avec le dopage. Cette dernière est comparée aux calculs ab initio de la littérature. Aucune réduction de la Tc avec l'épaisseur n'a en revanche été observée dans la gamme des couches synthétisées à savoir de 10 nm à 2 µm. / This PhD thesis reports on an experimental study of optical, electronic and structural properties of heavily boron-doped diamond. This wide bandgap semiconductor can be synthesized by Plasma Enhanced Chemical Vapor (MPCVD). Diamond is an insulator that may turn metallic and even superconductor (conventional) upon p-type doping.This work can be divided into three main parts :The first one involves the development of spectroscopic ellipsometry for characterizing single crystal diamond epilayers. First, optical models have been developed to derive the thickness, resistivity and carrier concentrations of several sets of samples measured ex situ. These values were then compared to those obtained through SIMS profiles (Secondary Ion Mass Spectroscopy) and transport measurements. As a result, an optical effective mass of carriers was determined. Second, this technique has been implemented to be set up in situ on the reactor. The influence of the temperature and the geometry of the growth chamber has been evaluated, and real time growth monitoring was achieved.The second part is related to the sample synthesis and optimization of growth parameters. In this section, we reveal the presence of a transient regime in the boron incorporation leading to a doping inhomogeneity. An increase of boron incorporation with the gas flow was also observed for the first time. Finally, the deterioration of the crystalline structure of diamond, above a critical dopant concentration, was identified and discussed.The third axis of this research is dedicated to the investigation of the electronic properties of heavily doped diamond by magneto-transport from 300K to 50 mK. First, the importance of the Hall bar mesa patterning for transport measurements is stressed. The use of a “controlled” geometry limited parasitic currents associated with doping inhomogeneities. Thus we could construct a new phase diagram, differing from previous reports in the literature. A metallic and non-superconducting layer has been unveiled for the first time. A study of the metal-insulator transition is reported and the critical exponents deduced from its modelling are discussed. Finally, the study of the superconducting state revealed a new dependence of the transition temperature (Tc) on doping which is compared with ab initio calculations. However, not any significant reduction of Tc was observed when the layer thickness dropped from 2 µm to 10 nm.

No description available.

Orientador: Prof. Dr. Marcos Roberto da Silva Tavares / Dissertação (mestrado) - Universidade Federal do ABC, Programa de Pós-Graduação em Física, 2015.

Ce travail présente les principaux résultats obtenus avec une large gamme de dispositifs SOI avancés, candidats très prometteurs pour les futurs générations de transistors MOSFETs. Leurs propriétés électriques ont été analysées par des mesures systématiques, agrémentées par des modèles analytiques et/ou des simulations numériques. Nous avons également proposé une utilisation originale de dispositifs FinFETs fabriqués sur ONO enterré en fonctionnalisant le ONO à des fins d'application mémoire non volatile, volatile et unifiées. Après une introduction sur l'état de l'art des dispositifs avancés en technologie SOI, le deuxième chapitre a été consacré à la caractérisation détaillée des propriétés de dispositifs SOI planaires ultra- mince (épaisseur en dessous de 7 nm) et multi-grille. Nous avons montré l’excellent contrôle électrostatique par la grille dans les transistors très courts ainsi que des effets intéressants de transport et de couplage. Une approche similaire a été utilisée pour étudier et comparer des dispositifs FinFETs à double grille et triple grille. Nous avons démontré que la configuration FinFET double grille améliore le couplage avec la grille arrière, phénomène important pour des applications à tension de seuil multiple. Nous avons proposé des modèles originaux expliquant l'effet de couplage 3D et le comportement de la mobilité dans des TFTs nanocristallin ZnO. Nos résultats ont souligné les similitudes et les différences entre les transistors SOI et à base de ZnO. Des mesures à basse température et de nouvelles méthodes d'extraction ont permis d'établir que la mobilité dans le ZnO et la qualité de l'interface ZnO/SiO2 sont remarquables. Cet état de fait ouvre des perspectives intéressantes pour l'utilisation de ce type de matériaux aux applications innovantes de l'électronique flexible. Dans le troisième chapitre, nous nous sommes concentrés sur le comportement de la mobilité dans les dispositifs SOI planaires et FinFET en effectuant des mesures de magnétorésistance à basse température. Nous avons mis en évidence expérimentalement un comportement de mobilité inhabituel (multi-branche) obtenu lorsque deux ou plusieurs canaux coexistent et interagissent. Un autre résultat original concerne l’existence et l’interprétation de la magnétorésistance géométrique dans les FinFETs.L'utilisation de FinFETs fabriqués sur ONO enterré en tant que mémoire non volatile flash a été proposée dans le quatrième chapitre. Deux mécanismes d'injection de charge ont été étudiés systématiquement. En plus de la démonstration de la pertinence de ce type mémoire en termes de performances (rétention, marge de détection), nous avons mis en évidence un comportement inattendu : l’amélioration de la marge de détection pour des dispositifs à canaux courts. Notre concept innovant de FinFlash sur ONO enterré présente plusieurs avantages: (i) opération double-bit et (ii) séparation de la grille de stockage et de l'interface de lecture augmentant la fiabilité et autorisant une miniaturisation plus poussée que des Finflash conventionnels avec grille ONO.Dans le dernier chapitre, nous avons exploré le concept de mémoire unifiée, en combinant les opérations non volatiles et 1T-DRAM par le biais des FinFETs sur ONO enterré. Comme escompté pour les mémoires dites unifiées, le courant transitoire en mode 1T-DRAM dépend des charges non volatiles stockées dans le ONO. D'autre part, nous avons montré que les charges piégées dans le nitrure ne sont pas perturbées par les opérations de programmation et lecture de la 1T-DRAM. Les performances de cette mémoire unifiée multi-bits sont prometteuses et pourront être considérablement améliorées par optimisation technologique de ce dispositif. / The evolution of electronic systems and portable devices requires innovation in both circuit design and transistor architecture. During last fifty years, the main issue in MOS transistor has been the gate length scaling down. The reduction of power consumption together with the co-integration of different functions is a more recent avenue. In bulk-Si planar technology, device shrinking seems to arrive at the end due to the multiplication of parasitic effects. The relay has been taken by novel SOI-like device architectures. In this perspective, this manuscript presents the main achievements of our work obtained with a variety of advanced fully depleted SOI MOSFETs, which are very promising candidates for next generation MOSFETs. Their electrical properties have been analyzed by systematic measurements and clarified by analytical models and/or simulations. Ultimately, appropriate applications have been proposed based on their beneficial features.In the first chapter, we briefly addressed the short-channel effects and the diverse technologies to improve device performance. The second chapter was dedicated to the detailed characterization and interesting properties of SOI devices. We have demonstrated excellent gate control and high performance in ultra-thin FD SOI MOSFET. The SCEs are efficiently suppressed by decreasing the body thickness below 7 nm. We have investigated the transport and electrostatic properties as well as the coupling mechanisms. The strong impact of body thickness and temperature range has been outlined. A similar approach was used to investigate and compare vertical double-gate and triple-gate FinFETs. DG FinFETs show enhanced coupling to back-gate bias which is applicable and suitable for dynamic threshold voltage tuning. We have proposed original models explaining the 3D coupling effect in FinFETs and the mobility behavior in ZnO TFTs. Our results pointed on the similarities and differences in SOI and ZnO transistors. According to our low-temperature measurements and new promoted extraction methods, the mobility in ZnO and the quality of ZnO/SiO2 interface are respectable, enabling innovating applications in flexible, transparent and power electronics. In the third chapter, we focused on the mobility behavior in planar SOI and FinFET devices by performing low-temperature magnetoresistance measurements. Unusual mobility curve with multi-branch aspect were obtained when two or more channels coexist and interplay. Another original result in the existence of the geometrical magnetoresistance in triple-gate and even double-gate FinFETs.The operation of a flash memory in FinFETs with ONO buried layer was explored in the forth chapter. Two charge injection mechanisms were proposed and systematically investigated. We have discussed the role of device geometry and temperature. Our novel ONO FinFlash concept has several distinct advantages: double-bit operation, separation of storage medium and reading interface, reliability and scalability. In the final chapter, we explored the avenue of unified memory, by combining nonvolatile and 1T-DRAM operations in a single transistor. The key result is that the transient current, relevant for 1T-DRAM operation, depends on the nonvolatile charges stored in the nitride buried layer. On the other hand, the trapped charges are not disturbed by the 1T-DRAM operation. Our experimental data offers the proof-of-concept for such advanced memory. The performance of the unified/multi-bit memory is already decent but will greatly improve in the coming years by processing dedicated devices.

L'émergence des énergies renouvelables a entraîné le développement de nouvelles technologies pour la distribution de l'énergie sur de longues distances. Ces dernières sont basées sur le transport via de hautes tensions continues (HVDC) pour éviter les pertes capacitives. Ce réseau de distribution est interconnecté via des Postes Sous Enveloppes Métalliques (PSEM), dont l'isolation est composée de gaz sous pression (SF6) et d'isolants solides (résine époxy), qui doivent résister sous HVDC. Dans ces dispositifs, le champ électrique n'est plus déterminé par la permittivité relative des matériaux, mais par leurs résistivités et les phénomènes d'accumulation de charges. Dans le cas d'un isolant solide présentant une interface avec un gaz, des électrons ou des ions vont être susceptibles de se déplacer suivant les lignes de champ électrique et charger la surface de l'isolant solide. Le comportement des propriétés des isolants (solides et gazeux) constitue un enjeu majeur dans le développement de PSEM HVDC, notamment dans la compréhension des mécanismes d'accumulation et relaxation des charges.Dans ce travail de thèse, la caractérisation de l'isolant solide a d'abord été étudiée, basée sur des mesures de courants faibles bruits. Il est ainsi possible de mesurer le courant de fuite dans le volume et sur la surface des échantillons, dans une enceinte sous pression, à haut champ électrique et pour différentes températures. Ces mesures ont mis en évidence que les résistivités de volume et de surface sont fortement impactées par l'augmentation de la température et la teneur en eau des échantillons. Il a également été montré que la résistivité de surface a un comportement non-linéaire en fonction du champ électrique. Un modèle numérique a été développé pour simuler les résultats obtenus, et implémenter les propriétés de surface de l'isolant solide.Les propriétés isolantes du gaz ont également été étudiées pour différentes géométries de champ électrique, dans le but d'estimer la contribution du courant passant à travers le gaz, sur l'accumulation de charge en surface de l'isolant solide. Des courants non négligeables sont mesurés dans le gaz (~pA-nA). Pour déterminer les mécanismes responsables de la présence de tels courants, il a été caractérisé selon plusieurs paramètres (la rugosité de la surface de l'électrode, la nature du matériau, le champ électrique, la température et l'humidité relative). Cela a mis en évidence que les variations de courants dépendent du conditionnement du dispositif, et sont donc fortement influencés par l'humidité relative adsorbée sur les surfaces du dispositif (électrodes et cuves). En présence d'un système sec, de faibles courants sont mesurés (~pA), et augmentent en fonction de la température. A l'inverse, dans le cas d'un système humide, le courant diminue avec l'augmentation de la température. Ces résultats, combinés à l'influence de la rugosité de l'électrode, suggèrent fortement un mécanisme d'injection de charge à la surface de l'électrode, favorisé en présence d'eau adsorbée.Enfin, les résultats obtenus pour les deux isolants solides et gazeux sont utilisés pour élaborer un modèle numérique ayant une forme proche de celle de l'application industrielle, et permettent d'observer la modification de la distribution du champ électrique en présence de la concentration en eau et du gradient de température. Une estimation du courant circulant au travers des isolants est donc possible.En conclusion, ce travail donne les variations des résistivités de volume et de surface dans une résine époxy en fonction de la température et du champ électrique. Il met également en évidence la forte influence de l'humidité relative et de la température sur les mécanismes d'injection de charges qui contribuent au courant mesuré à travers le gaz. Cette caractérisation approfondie permet de développer une simulation qui prédit les variations de la distribution du champ électrique au sein d'un PSEM sous tension continue. / The emergence of renewable energy leads to a development of new technologies for energy distribution across long distances. The latter will be based on High Voltage Direct Current (HVDC) to avoid capacitance losses. This network is interconnected using Gas Insulated Substation (GIS), which insulation is composed of pressurized gas (SF6) and solid insulators (epoxy resin), which have to withstand HVDC. The electric field is not anymore determined by permittivity of materials, but by resistivities and charge accumulation. In the case of an insulator with an interface with gas, electrons or ions will move across electric field lines and will charge the surface of the solid insulator. The behavior of insulator's properties (gas and solid) constitutes a major challenge for the development of HVDC GIS, to understand the charge relaxation/accumulation mechanisms.In this work, the characterization of solid insulator has first been investigated, based on a low-noise current measurement method. It is thus possible to measure the leakage current through samples and onto their surface, in a pressurized gas, at high electric field and for different temperatures. Those measurements permit to evidence that both volume and surface resistivities are strongly impacted by the increase of temperature and water concentration. It has also been shown that surface resistivity has a non-linear behavior with electric field. A numerical model was developed, to simulate experimental results, showing that the surface properties of the insulator can be implemented.Furthermore, the insulating properties of the gas were also investigated through different electric field geometry (coaxial and uniform), in order to estimate the contribution of current through gas on the charge accumulated on solid insulators. It has been found that a non-negligible current passes through the gas (~pA to nA). To determine the mechanisms responsible for such currents, the latter has been characterized depending on several parameters (electrode surface roughness, material nature, electric field, temperature and relative humidity). It revealed that the variations of currents are strongly impacted by the conditioning of the device and thus by the relative humidity adsorbed on electrodes and enclosure surfaces. In presence of a dry system (dry gas and device) low current were measured (~pA), which increases with temperature. On the contrary, in case of a “wet” system (humid gas and device) the current decreases with increasing temperature. Those results combined with the influence of the electrode roughness, strongly suggest a mechanism of charge injection at the electrode surface, enhanced by water adsorption.Finally, the results obtained for both solid and gaseous insulations are used to develop a numerical model with a shape close to the industrial application, and observe the modification of electric field distribution in presence of water concentration and temperature gradient. An estimation of current flowing through the insulator and gas is thus possible in case of uniform and gradient temperature.In conclusion, this work gives the variations of both volume and surface resistivities in an epoxy resin with temperature and electric field. It also evidences the major influence of relative humidity and temperature on charge injection mechanisms which contribute to the current measured through gas. The extensive characterization performed, enables to develop a simulation which predicts the variations of electric field distribution within an HVDC GIS.

Submitted by Luciana Ferreira (lucgeral@gmail.com) on 2018-01-29T12:59:29Z No. of bitstreams: 2 Dissertação - Flávio de Lima Vieira - 2017.pdf: 3009793 bytes, checksum: f2afe605bb678159dc5e79283554d32b (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2018-01-29T12:59:56Z (GMT) No. of bitstreams: 2 Dissertação - Flávio de Lima Vieira - 2017.pdf: 3009793 bytes, checksum: f2afe605bb678159dc5e79283554d32b (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2018-01-29T12:59:56Z (GMT). No. of bitstreams: 2 Dissertação - Flávio de Lima Vieira - 2017.pdf: 3009793 bytes, checksum: f2afe605bb678159dc5e79283554d32b (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2017-08-31 / This research aims to evaluate the tecniques for disposal of waste obtained from electrical insulators. These pieces are one of the supplies widely used for electric power generation, and become a waste due to their replacement for new ones after maintenance and expansion works, in places like substations, generating units, distribution networks, transmission lines and its own production process. In Brazil, it is possible to acumulate waste from these insulators in courtyards and waste areas, besides wastelands, impairing the environment. Thus, it is known that an alternative for treatment is needed and the lack of knowledge and techical safe forces the development of reasearches about this subject, what are still in the beggining. So, this study proposes the evaluation of potential use of such a porcelain in concrete, through the replacement of conventional aggregates and cement. The research was conducted with a careful characterization of the waste in different maximum dimension sizes, with physicochemical and mineralogical analysis obtained from X-Ray diffration and images from scanning eletronic microscopy, for example. Besides, tests of alkali-aggregate reaction were perfomed in order to assess the chemical stability of the waste in mortar. Regarding to viscoelastic and mechanical properties, the compressive strength, modulus of elasticity, water absorption, and abrasion/erosion were performed. The experimental program considered eleven different mixes of pumped concrete, take into account the following replacement rates: 8% replacement of cement; 50% and 100% replacement of fine aggregate; and 45% and 100% replacement of coarse aggregate. Some mixes were done with both replacement of fine and coarse aggregate. The investigation of mechanical strength, deformation and durability, in conditions aforementioned, demonstrates that concrete with replacement was statistically similar to concrete without any replacement by waste, resulting a suitable concrete with porcelain waste content. The efficiency of compressive strength ranged from 0,087 MPa/kg to 0,107 MPa/kg and the modulus of elasticity reached values up to 38 GPa, indicating expressive results for these properties. Lastly, in research is possible to observe the conclusions about reological characteristics of all concrete and the influence of these replacement on cement content. / A presente pesquisa aborda a temática da destinação do resíduo dos isoladores elétricos proveniente da cadeia geradora de energia elétrica, como as relacionadas às manutenções e ampliações das subestações, unidades geradoras, redes de distribuição, linhas de transmissão e do próprio processo de produção do isolador. No Brasil esta cadeia acumula progressivamente resíduos em pátios e áreas de descarte, e às vezes esses materiais são lançados por terceiros em locais como terrenos baldios, impactando no meio ambiente. Nesse contexto, uma alternativa seria sua utilização para outros fins, os quais, por falta de conhecimento e segurança técnica, ainda se encontram em fases iniciais de estudo. Diante disso, a presente pesquisa propõe a investigação do potencial de uso destas porcelanas no concreto, em substituição aos agregados convencionais e também ao cimento. Para tanto, conduziu-se incialmente uma caracterização minuciosa do resíduo nas suas diversas dimensões, por meio de análises químicas, físicas e mineralógicas utilizando diferentes métodos, como a difração de raios X e imagens por microscópico eletrônico de varredura, por exemplo. Na sequência foram realizados testes para verificar a estabilidade química do resíduo em argamassa para o desencadeamento de reações álcalis-agregado. Em relação à sua incorporação no concreto, foram realizados ensaios para aferição da resistência à compressão, módulo de elasticidade, absorção de água, abrasão e erosão. As análises foram realizadas em onze concretos estruturais bombeáveis com diferentes teores de substituição, que contemplaram adição de 8% em substituição ao cimento, no agregado miúdo com 50% e 100% de substituição, no agregado graúdo com 45% e 100%, e em algumas composições com substituições simultâneas no miúdo e graúdo. De posse dos resultados, foi traçado um perfil de resistência mecânica, deformabilidade e durabilidade que apresentaram para algumas substituições valores estatisticamente iguais ao concreto sem resíduo, tornando factível a utilização do concreto com porcelana. Eficiências para resistência à compressão variando de 0,087 MPa/kg a 0,107 MPa/kg, módulo de elasticidade com valores de até 38 GPa, são números significativos para as propriedades. Análises da reologia do concreto e impactos no consumo de cimento são aspectos também observados e discutidos no decorrer do trabalho.

Orientador: Bernardo Laks / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin / Made available in DSpace on 2018-08-12T11:04:39Z (GMT). No. of bitstreams: 1 Marcal_Nei_D.pdf: 86929566 bytes, checksum: 04c8aa7c4176175d973ff0990de45bad (MD5) Previous issue date: 2008 / Resumo: Antes da década de 70, todos os materiais poliméricos eram considerados como isolantes e suas aplicações tecnológicas levavam em conta esta característica. De lá para cá, uma nova classe desses materiais, os polímeros conjugados, determinaram uma nova forma de aplicação de sistemas poliméricos baseados em suas propriedades elétricas e de ótica não-linear. Um maior estímulo surgiu a partir do experimento de Mac Diarmid, Heeger e Shirakawa [1] que, expondo o Poliacetileno a agentes oxidantes, demonstraram ser possível obter um sistema no estado metálico. Atualmente encontramos filmes de Poliacetileno com condutividade elétrica da ordem do cobre (105 S/cm). O Poliacetileno, quando no regime metálico, i.e., sob alta dopagem, apresenta algumas características de metal comum: alta condutividade elétrica (cresce 13 ordens de grandeza), susceptibilidade de Pauli finita e absorção no infravermelho. Já outras propriedades como a presença de modos vibracionais localizados no infravermelho e o não comportamento da condutividade com o inverso da temperatura evidenciam ser este um material não usual. Estes polímeros conjugados que apresentam uma extensiva delocalização de elétrons são considerados semicondutores orgânicos com gap de energia relativamente pequeno, da ordem de 1,5 a 2,0 eV. O comportamento semicondutor e as propriedades decorrentes entre os elétrons e a luz têm originado a construção de vários dispositivos semicondutores e optoeletrônicos [2, 7, 3]. Problemas técnicos como estabilidade ao ambiente, processabilidade e solubilidade destes materiais provocaram a produção de uma nova classe de materiais poliméricos que foi obtida por polimerização eletroquímica [57, 58, 59] cuja estrutura molecular trata-se de sistemas que introduzem grupos vinilas (V) entre anéis de tiofeno (T). Experimentos de voltametria cíclica, espectroscopia de absorção ótica e ressonância eletrônica de spin indicam que esses sistemas possuem potencial de ionização e gap de energia menores que o apresentado pelo Politiofeno. Estudos com oligômeros de tiofeno (T) com vinilenos (V) sugerem a possibilidade de escolha desse material como alternativa ao politiofeno. O objetivo deste trabalho foi investigar teoricamente a influência do grupo vinila (V) sobre as propriedades eletrônicas nestes polímeros, reproduzir os resultados experimentais e determinar qual proporção de vinilenos (V) e tiofenos (T) que provoque o menor gap de energia de forma que quando sobre dopagem possibilite uma transição isolante metal. Desta maneira, primeiramente, determinamos as geometrias dos sistemas de interesse utilizando métodos semi-empíricos. Posteriormente investigamos a estrutura eletrônica dos polímeros de tiofeno (T) com vinilenos (V), sendo que estes polímeros foram estudados para o caso neutro e na presença de defeitos conformacionais do tipo pólaron e bipólaron. Finalizamos o estudo investigando as absorções ópticas UV-vis dos sistemas de interesse através de cálculos semi-empíricos utilizando o código ZINDO/S. / Abstract: Before the 1970s, all polymeric materials were considered insulators; therefore their technological applications would take this trait into account. Since then, a new development on these materials, the conjugated polymers, determined new applications for polymeric systems based in their electrical and nonlinear optical properties. Greater interest arose from the experiment by Mac Diarmid, Heeger and Shirakawa [1] who, by using polyacetylene and oxidizing agents, showed that it is possible to obtain a system in the metallic state. Nowadays it is possible to find polyacetylene films with electrical conductivity of the order of copper (10-5 S/cm). Polyacetylene, when in its metallic behavior, i.e., under high dopage, presents some characteristics of real metal: high electrical conductivity (increased by 13 orders of magnitude), finite Pauli susceptibility and infrared absorption. On the other hand, other properties such as the presence of vibrational modes localized on infrared and the odd behavior of conductivity versus the inverse of temperature make clear that this is a unusual material. These conjugated polymers, presenting an extensive delocalization of electrons, are considered organic semiconductors with relatively low energy gap, of the order of 1.5 to 2.0 eV. The semiconductive behavior and the resulting properties of the interaction between electrons and light have been the drive for the manufacturing of several semiconductor and optoelectronic devices [2, 7, 3]. Technical problems, such as environmental stability, processability and solubility of these materials, gave rise to the production of a new kind of polymeric materials that were obtained by electrochemical polymerization [57, 58, 59], in which the molecular structure is a system that introduces vinylene groups (V) between tiophene rings (T). Experiments involving cyclic voltametry, optical absorption spectrometry and spin electronic ressonance indicate that these systems have ionization potential and energy gap smaller than those presented by Polythiophene. Studies with thiopene oligomers (T) with vinylene (V) suggest this material can be chosen as an alternative to Polytiophene. The goal of this work is to theoretically investigate the in uence of the vinyle group (V) on the electronic properties on these polymers, reproduce experimental results and determine what is the vinylene (V) to thiophene (T) rate that causes the smallest energy gap, such that doping will produce a insulator-metal transition. Therefore, we first determine the target systems' geometry using semi-empirical methods. Then we investigate the electronic structure of the tiophene (T) and vinylene (V) polymers both for neutral systems and in the presence of conformational defects of polaron and bipolaron types. We nalized the study by investigating the UV-vis optical absorption of the target systems through semi-empirical calculations using ZINDO/S code. / Doutorado / Estrutura Eletronica de Atomos e Moleculas ; Teoria / Doutor em Ciências

A novel insulating cross-arm (ICA) has been developed for new and existing overhead transmission lines of up to 400 kV. The cross-arm consists of four insulating members, end fittings, field grading devices and a nose connection for the attachment of the conductor. The two main structural elements of the assembly have a unique non-cylindrical geometry which gives them improved mechanical characteristics compared to conventional overhead line insulators. The profile for the compression insulator has been designed. After examining six profile variations, it was determined that the lateral orientation which would give the best performance would be with the flat face of the core facing upwards and tilted by 6o. Using the results obtained from performing flashover tests on a conventional 145 kV insulator, the elevation angle for the compression insulator was set to 6o. The dimensions of the compression insulator were calculated based on the assumption that the ICA would be used to uprate an OHL with L3 towers from 275 kV to 400 kV. The optimal insulator profile was determined to be an alternating profile with three different shed sizes, an arcing distance of 3083 mm and a creepage distance of 12470 mm. Electric field grading devices for the ICA were designed. For the LV end, a grading device resembling a ring which follows the general shape of the cross-section of the insulator was designed. For the HV end, an iterative process yielded two designs. First, the ‘butterfly’ grading device was a unibody piece of cast aluminium for all four ICA members. FEA simulations and tests in the laboratory showed that it could effectively control the electric field at voltages of up to 132 kV. The design was patented and the device was used on six cross-arms installed on a live line in Scotland in August 2013. Second, the ‘M-W’ grading device, was a solution made out of four components for managing the field at voltages of up to 400 kV. The device was designed to be easy to install and service, easy and cheap to manufacture and to have minimal visual impact. The compression insulator and the cross-arm assembly were subjected to a multitude of tests adapted from international standards and the Technical Specifications of National Grid. The performed tests aimed to test the electrical characteristics of the cross-arm and the quality of the materials and manufacturing process of the compression insulator. All of the tests were completed successfully except from the corona extinction test for which the appropriate equipment was not available at the time. Two trials were commissioned to examine how the cross-arm performs in a service-like environment. The snow and ice accretion patterns recorded at the mechanical trial site were used for optimising the profile of the compression insulator. The results after a year of continuous monitoring of leakage current and weather conditions at the live trial site showed that there were humidity and visibility thresholds, above 93% for the former and below 400 m for the latter, which increased the average leakage current by 15% on the tension insulators and by 20% on the compression insulators. It was found that when the longitudinal axis of the cross-arm was perpendicular to the weather the leakage current was higher because more of its surface was exposed. The performance of the novel compression insulators was found to be as good as that of the industry standard tension insulators, reaffirming the potency of the design. Finally, on-site observations showed that the ‘butterfly’ grading device could not effectively manage the electric field on the cross-arm at 400 kV, confirming the results of the FEA simulations and testing.

No description available.

Metal-insulator-metal (MIM) capacitors are used for analog, RF, and DRAM applications in ICs. The International Technology Roadmap for Semiconductors (ITRS) specifies continuing increase in capacitance density (> 7 fF/ m2), lower leakage current density (< 10 8 A/cm2), very low effective oxide thickness (EOT < 1 nm, for DRAM applications), and better capacitance density-voltage (C-V) linearity ( < 100 ppm/V2, for analog/RF applications). In addition, the maximum fabrication/processing temper-ature should not be greater than 400 0C, in order to be compatible with the thermal budget of back-end fabrication steps. Low dielectric constants of conventional SiO2 and Si3N4 capacitors limit the capacitance densities of these devices. Although scaling down of dielectric thickness increases the capacitance density, it results in large leakage current density and poor C-V linearity. In this work, the effects of high-k materials (Eu2O3, Gd2O3, TiO2) on the device performance of MIM capacitors are studied. The performance of multi-dielectric stack, and doped-dielectric stack devices are also investigated. The effects of anneal temperature, anneal ambient, anneal mode, and dielectric thickness on device performance are evaluated. C-V, current density-voltage (J-V), and reliability measurements are performed to benchmark the electrical performance, and this is correlated to the structural and material properties of the films through ellipsometry, scanning electron microscopy (SEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) measurements. High-performance MIM capacitors are fabricated by using (RF sputtered) Eu2O3 dielectric. The fabricated devices are subjected to different anneal conditions, to study their device performance. Forming gas (FG) and argon (Ar) annealed devices are shown to have higher capacitance densities (7 fF/ m2jF G), lower leakage current densities (3.2 10 8 A/cm2jAr at -1 V), and higher , compared to oxygen (O2) annealed de-vices ( 100kHz = 193 ppm/V2jO2). The electrical characterization results are correlated with the surface chemical states of the films through XPS measurements. The annealing ambient is shown to alter the surface chemical states, which, in turn, modulate the electrical characteristics. High-density MIM capacitors are fabricated by using (RF sputtered) Gd2O3, and Gd2O3-Eu2O3 stacked dielectrics. The fabricated Gd2O3 capacitors are also subjected to different anneal conditions, to study their device performance. Although Gd2O3 capacitors provide high capacitance density (15 fF/ m2), they suffer from high leakage current density, high , and poor reliability. Therefore, stacked dielectrics of Gd2O3 and Eu2O3 (Gd2O3/Eu2O3 and Eu2O3/Gd2O3) are fabricated to reduce leakage current density, improve , and improve reliability, with only a marginal reduction in capacitance density, compared to Gd2O3 capacitors. Density of defects and barrier/trap heights are extracted for the fabricated capacitors, and correlated with the device characteristics. High-performance MIM capacitors with bilayer dielectric stacks of (ALD-deposited) TiO2-ZrO2, and Si-doped ZrO2 are characterized. Devices with (ALD-deposited) TiO2/ ZrO2/TiO2 (TZT) and AlO-doped TZT stacks are also characterized. The influence of doping on the device performance is studied. The surface chemical states of the deposited films are analyzed by high-resolution XPS. The structural analysis of the samples is performed by XRD measurements, and this is correlated to the electrical characteristics of the devices. Reliability measurements are performed to study the effects of constant voltage and current stress on device performance. High capacitance density (> 45 fF/ m2), low leakage current density (< 5 10 8 A/cm2 at -1 V, for most devices), and sub-nm EOT are achieved. These parameters exceed the ITRS specifications for DRAM storage capacitors.