Submitted by PPG Engenharia e Tecnologia de Materiais (engenharia.pg.materiais@pucrs.br) on 2018-08-23T14:01:45Z No. of bitstreams: 1 Sandro Fernandes Firmino_TESE.pdf: 4757608 bytes, checksum: 52ddad6a85c21dfa1d36627079848e04 (MD5) / Approved for entry into archive by Sheila Dias (sheila.dias@pucrs.br) on 2018-08-27T11:21:40Z (GMT) No. of bitstreams: 1 Sandro Fernandes Firmino_TESE.pdf: 4757608 bytes, checksum: 52ddad6a85c21dfa1d36627079848e04 (MD5) / Made available in DSpace on 2018-08-27T11:37:10Z (GMT). No. of bitstreams: 1 Sandro Fernandes Firmino_TESE.pdf: 4757608 bytes, checksum: 52ddad6a85c21dfa1d36627079848e04 (MD5) Previous issue date: 2018-08-20 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior - CAPES / This work proposes the development of a low cost protocol for the production of TCNTs based on silver nanowires (AgNWs) on rigid substrates, and the improvement of the deposition technique to obtain a higher layer homogeneous, aiming at the optimization of its optical and electrical properties. For this, silver nanowires with length and diameter control were produced, aiming to evaluate the influence of these parameters on the optical and electrical properties of TCTFs. The effects of thermal annealing on the morphology of AgNWs networks and on the electrical and optical properties of TCTFs were also investigated. Studies were carried out to improve the deposition technique to obtain more homogeneous films and, as a result of this study, a new deposition technique (VMCV - Vertical Controlled Mechanical Vibration) was developed with INPI (National Institute of Intellectual Property). Silver nanowires were synthesized through the polyol process, which uses a polymer (N-vinylpyrrolidone) (PVP) as the coating agent. The prepared solutions of AgNWs were deposited on rigid substrates (glass / silicon) for analysis of topological and chemical surfaces, resulting in a random network of nanowires. The networks of AgNWs were characterized by MEV-FEG, UV-Vis, XPS and DSC-TGA techniques. The effect of thermal annealing on the AgNWs networks was investigated by means of in situ measurements of the evolution of the electrical resistances, through the technique of two tips, on a hot plate with temperature control system. Our best results exhibit an optical transparency (~ 83% at 550 nm) equivalent to commercial metal oxide thin films (indium oxide-oxide, ITO or fluoride oxide and tin oxide, FTO) and sheet resistance of ~ 23 ? / ?. / Este trabalho tem como proposta o desenvolvimento de um protocolo de baixo custo para produ??o de TCTFs (Filmes Finos Condutores Transparentes) ? base de nanofios de prata (AgNWs) sobre substratos r?gidos, e o aperfei?oamento da t?cnica de deposi??o para a obten??o de uma camada homog?nea, visando ? otimiza??o de suas propriedades ?pticas e el?tricas. Para isto, foram produzidos nanofios de prata com controle de comprimento e di?metro, visando avaliar a influ?ncia destes par?metros sobre as propriedades ?pticas e el?tricas dos TCTFs. Tamb?m foram investigados os efeitos do recozimento t?rmico na morfologia das redes de AgNWs e sobre as propriedades el?tricas e ?pticas dos TCTFs. Foram realizados estudos para o aperfei?oamento da t?cnica de deposi??o para a obten??o de filmes homog?neos e, como resultado deste estudo, desenvolveu-se uma nova t?cnica de deposi??o (VMCV- Vibra??o Mec?nica Controlada Vertical) registrada junto ao INPI (Instituto Nacional de Propriedade Intelectual). Os nanofios de prata foram sintetizados atrav?s do processo poliol, que utiliza um pol?mero (N-vinilpirrolidona) (PVP) como o agente de cobertura. As solu??es preparadas de AgNWs foram depositadas sobre substratos r?gidos (vidro/sil?cio) para an?lises de superf?cies topol?gicas e qu?micas, resultando em uma rede aleat?ria de nanofios. As redes de AgNWs foram caracterizadas pelas t?cnicas MEV-FEG, UV-Vis, XPS e DSC-TGA. O efeito do recozimento t?rmico sobre as redes de AgNWs foi investigado por meio de medi??es in situ da evolu??o das resist?ncias el?tricas, atrav?s da t?cnica de duas pontas, sobre uma chapa quente com sistema de controle de temperatura. Nossos melhores resultados exibem uma transpar?ncia ?ptica (~ 83% a 550 nm) equivalente a das pel?culas finas de ?xido de metal comercial (?xido de ?ndio-?xido, ITO ou ?xido de fl?or e ?xido de estanho, FTO) e resist?ncia de folha de ~ 23 ?/?.

Nano scale processing of IC chips has become the prime production technique as the microelectronic industry aims towards scaling down product dimensions while increasing accuracy and performance. Accurate control of temperature and a good monitoring mechanism for thickness of the deposition layers during epitaxial growth are critical parameters influencing a good yield. The two-fold objective of this thesis is to establish the feasibility of an alternative to the current pyrometric and ellipsometric techniques to simultaneously measure temperature and thickness during wafer processing. TAP-NDE is a non-contact, non-invasive, laser-based ultrasound technique that is employed in this study to contemporarily profile the thermal and spatial characteristics of the wafer. The Gabor wavelet transform allows the wave dispersion to be unraveled and the group velocity of individual frequency components to be extracted from the experimentally acquired time waveform. The thesis illustrates the formulation of a theoretical model that is used to identify the frequencies sensitive to temperature and thickness changes. The group velocity of the corresponding frequency components is determined and their corresponding changes with respect to temperature for different thickness are analytically modeled. TAP-NDE is then used to perform an experimental analysis on Silicon wafers of different thickness to determine the maximum possible resolution of TAP-NDE towards temperature sensitivity, and to demonstrate the ability to differentiate between wafers of different deposition layer thickness at temperatures up to 600?C. Temperature resolution is demonstrated for ?10?C resolution and for ?5?C resolution; while thickness differentiation is carried out with wafers carrying 4000? and 8000? of aluminum deposition layer. The experimental group velocities of a set of selected frequency components extracted using the Gabor Wavelet time-frequency analysis as compared to their corresponding theoretical group velocities show satisfactory agreement. As a result of this work, it is seen that TAP-NDE is a suitable tool to identify and characterize thickness and temperature changes simultaneously during thermal annealing that can replace the current need for separate characterization of these two important parameters in semiconductor manufacturing.

Commercial pure terephthalic acid (PTA) manufacturing generates process streams mainly containing acetic acid (HAc) and water. A large financial incentive exists to replace the costly and energy intensive distillation column used to recycle HAc-water mixtures. This work focuses on the development of pervaporation technology to separate HAc-water mixtures using a hollow fiber-based membrane unit. Currently a 250 m outer diameter Matrimid® hollow fiber is used in industry for gas separation. Due to the difference between gas and liquid separations, the fiber performance associated with high flux in pervaporation is limited by a pressure change inside the bore along the axial direction of the fiber. A mathematical model was developed to describe the bore pressure change in pervaporation in this work, which demonstrated that spinning a large bore size fiber was a good solution to minimize the bore pressure change. Spinning technology has been adapted to obtain a large bore size defect-free Matrimid® hollow fiber. In addition to a large bore size, the asymmetric fiber exhibits an intrinsically defect-free selective layer supported on an open porous substrate. This eliminates the post-treatment with a caulking layer and has a special advantage for aggressive liquid separation. A proof of concept was provided by testing both small and large bore size defect-free fibers with a model 20% wt HAc feed in a pervaporation system at 101.5oC. The membrane selectivity (~ 25) and water flux (~ 4.5 kg/m2hr) were increased by about 150% with a diameter (O.D. ~ 500 m) twice as large as the regular fiber. Further, a decrease in the HAc flux was observed with the increased bore size due to the reduction in HAc-induced plasticization. Sub-Tg thermal annealing was used to stabilize the fiber by suppressing HAc-induced plasticization. This improves the polymer discrimination of shape and size for penetrants although no chemical reaction occurs with thermal annealing. The resulting membrane selectivity was increased from 10 to about 95 using a large bore size defect-free annealed fiber with acceptable water flux (~ 1.5 kg/m2hr) for 20% wt HAc concentration feed streams. These improvements make Matrimid® hollow fiber membranes very attractive for future scale-up and commercial development.

Nano scale processing of IC chips has become the prime production technique as the microelectronic industry aims towards scaling down product dimensions while increasing accuracy and performance. Accurate control of temperature and a good monitoring mechanism for thickness of the deposition layers during epitaxial growth are critical parameters influencing a good yield. The two-fold objective of this thesis is to establish the feasibility of an alternative to the current pyrometric and ellipsometric techniques to simultaneously measure temperature and thickness during wafer processing. TAP-NDE is a non-contact, non-invasive, laser-based ultrasound technique that is employed in this study to contemporarily profile the thermal and spatial characteristics of the wafer. The Gabor wavelet transform allows the wave dispersion to be unraveled and the group velocity of individual frequency components to be extracted from the experimentally acquired time waveform. The thesis illustrates the formulation of a theoretical model that is used to identify the frequencies sensitive to temperature and thickness changes. The group velocity of the corresponding frequency components is determined and their corresponding changes with respect to temperature for different thickness are analytically modeled. TAP-NDE is then used to perform an experimental analysis on Silicon wafers of different thickness to determine the maximum possible resolution of TAP-NDE towards temperature sensitivity, and to demonstrate the ability to differentiate between wafers of different deposition layer thickness at temperatures up to 600?C. Temperature resolution is demonstrated for ?10?C resolution and for ?5?C resolution; while thickness differentiation is carried out with wafers carrying 4000? and 8000? of aluminum deposition layer. The experimental group velocities of a set of selected frequency components extracted using the Gabor Wavelet time-frequency analysis as compared to their corresponding theoretical group velocities show satisfactory agreement. As a result of this work, it is seen that TAP-NDE is a suitable tool to identify and characterize thickness and temperature changes simultaneously during thermal annealing that can replace the current need for separate characterization of these two important parameters in semiconductor manufacturing.

O carbeto de silício (SiC) apresenta várias propriedades extremamente interessantes para a fabricação de dispositivos eletrônicos submetidos a condições extremas como alta temperatura (300 a 600 °C), alta frequência e alta potência. Além disso, é o único semicondutor composto que, reagindo com o oxigênio, forma um óxido isolante estável, o SiO2. No entanto, as propriedades elétricas de estruturas de SiO2/SiC são degradadas pela alta concentração de estados eletricamente ativos na interface dielétrico/semicondutor. Tal característica representa uma barreira para a fabricação de dispositivos baseados nesse material. Nesta tese foram comparadas e analisadas as propriedades de estruturas SiO2/4H-SiC obtidas por diferentes processos de oxidação térmica. As estruturas resultantes foram caracterizadas por medidas de corrente-tensão, capacitância-tensão e condutância ac de alta frequência, espectroscopia de fotoelétrons induzidos por raios-X, análise por reação nuclear e microscopia de força atômica. O uso dessas técnicas analíticas visou a correlacionar o comportamento elétrico das estruturas obtidas com suas propriedades físico-químicas como, por exemplo, composição e estrutura química do óxido formado. Os resultados evidenciam diferenças específicas entre os ambientes de oxidação e temperaturas aos quais as amostras foram submetidas, com uma forte distinção entre 4H-SiC tipo-n e tipo-p. Em geral, amostras do substrato tipo-n apresentaram menores quantidades de defeitos na interface SiO2/SiC em comparação com as do tipo-p. Foram identificados comportamentos relacionados a defeitos no óxido, próximos à interface, responsáveis pela captura de portadores majoritários provenientes do semicondutor. Ficou evidente que alguns ambientes e temperaturas de oxidação beneficiam a interface em detrimento da qualidade do filme de óxido e vice-versa. Uma atmosfera de oxidação alternativa, utilizando H2O2 como agente oxidante, foi proposta. Tal processo mostrou-se eficaz na redução da quantidade de estados eletricamente ativos na interface em estruturas tipo-n através da conversão de compostos carbonados em SiO2 no filme dielétrico formado. / Silicon carbide (SiC) presents many advantageous properties for electronic devices designed to work under extreme conditions such as high-temperature (300 ~ 600 °C), high-frequency, and high-power. In addition, the formation of an insulating oxide layer (SiO2) by thermal oxidation is an attractive property for the microelectronics industry. Nevertheless, large densities of interface states at the SiO2/SiC interface degrade electrical properties of the resulting structure. Such states are responsible for undesirable effects which hamper the development of SiC-based devices. In this thesis, the properties of SiO2/4H-SiC structures obtained by distinct oxidation processes where analyzed and compared. The resulting structures where characterized by currentvoltage, high-frequency capacitance-voltage and ac conductance, X-ray photoelectron spectroscopy, nuclear reaction analysis, and atomic force microscopy. Such techniques were employed in order to correlate electrical and physico-chemical properties of the formed structures like composition and chemical bonding of the oxide layer. Results evidence differences among samples prepared under several oxidation atmospheres and temperatures, with a strong distinction among n- and p-type 4H-SiC. Overall, p-type samples presented larger values of interface states densities in comparison with their ntype counterparts. Near-interface traps in the oxide layer, responsible for capture of majority carriers from the semiconductor substrate, were identified. We could evidence that some oxidation conditions improve the bulk properties of the oxide layer, at the same time that they degrade the SiO2/SiC interface quality, and vice versa. An alternative oxidation process using H2O2 as oxidizing agent was proposed. Such process has shown to reduce the amount of electrically active defects at the interface in n-type samples by converting carbonaceous compounds in SiO2 in the formed dielectric layer.

O carbeto de silício (SiC) apresenta várias propriedades extremamente interessantes para a fabricação de dispositivos eletrônicos submetidos a condições extremas como alta temperatura (300 a 600 °C), alta frequência e alta potência. Além disso, é o único semicondutor composto que, reagindo com o oxigênio, forma um óxido isolante estável, o SiO2. No entanto, as propriedades elétricas de estruturas de SiO2/SiC são degradadas pela alta concentração de estados eletricamente ativos na interface dielétrico/semicondutor. Tal característica representa uma barreira para a fabricação de dispositivos baseados nesse material. Nesta tese foram comparadas e analisadas as propriedades de estruturas SiO2/4H-SiC obtidas por diferentes processos de oxidação térmica. As estruturas resultantes foram caracterizadas por medidas de corrente-tensão, capacitância-tensão e condutância ac de alta frequência, espectroscopia de fotoelétrons induzidos por raios-X, análise por reação nuclear e microscopia de força atômica. O uso dessas técnicas analíticas visou a correlacionar o comportamento elétrico das estruturas obtidas com suas propriedades físico-químicas como, por exemplo, composição e estrutura química do óxido formado. Os resultados evidenciam diferenças específicas entre os ambientes de oxidação e temperaturas aos quais as amostras foram submetidas, com uma forte distinção entre 4H-SiC tipo-n e tipo-p. Em geral, amostras do substrato tipo-n apresentaram menores quantidades de defeitos na interface SiO2/SiC em comparação com as do tipo-p. Foram identificados comportamentos relacionados a defeitos no óxido, próximos à interface, responsáveis pela captura de portadores majoritários provenientes do semicondutor. Ficou evidente que alguns ambientes e temperaturas de oxidação beneficiam a interface em detrimento da qualidade do filme de óxido e vice-versa. Uma atmosfera de oxidação alternativa, utilizando H2O2 como agente oxidante, foi proposta. Tal processo mostrou-se eficaz na redução da quantidade de estados eletricamente ativos na interface em estruturas tipo-n através da conversão de compostos carbonados em SiO2 no filme dielétrico formado. / Silicon carbide (SiC) presents many advantageous properties for electronic devices designed to work under extreme conditions such as high-temperature (300 ~ 600 °C), high-frequency, and high-power. In addition, the formation of an insulating oxide layer (SiO2) by thermal oxidation is an attractive property for the microelectronics industry. Nevertheless, large densities of interface states at the SiO2/SiC interface degrade electrical properties of the resulting structure. Such states are responsible for undesirable effects which hamper the development of SiC-based devices. In this thesis, the properties of SiO2/4H-SiC structures obtained by distinct oxidation processes where analyzed and compared. The resulting structures where characterized by currentvoltage, high-frequency capacitance-voltage and ac conductance, X-ray photoelectron spectroscopy, nuclear reaction analysis, and atomic force microscopy. Such techniques were employed in order to correlate electrical and physico-chemical properties of the formed structures like composition and chemical bonding of the oxide layer. Results evidence differences among samples prepared under several oxidation atmospheres and temperatures, with a strong distinction among n- and p-type 4H-SiC. Overall, p-type samples presented larger values of interface states densities in comparison with their ntype counterparts. Near-interface traps in the oxide layer, responsible for capture of majority carriers from the semiconductor substrate, were identified. We could evidence that some oxidation conditions improve the bulk properties of the oxide layer, at the same time that they degrade the SiO2/SiC interface quality, and vice versa. An alternative oxidation process using H2O2 as oxidizing agent was proposed. Such process has shown to reduce the amount of electrically active defects at the interface in n-type samples by converting carbonaceous compounds in SiO2 in the formed dielectric layer.

Cette thèse a pour but d'étudier le dopage par implantation ionique pour la réalisation des différentes zones dopées des cellules solaires en silicium cristallin (émetteur, champ arrière...). L'avantage de l'implantation ionique, par rapport à la diffusion gazeuse, est de pouvoir contrôler le profil des dopants implantés ainsi que de simplifier les procédés de fabrication des cellules. Deux techniques d'implantation ionique ont été utilisées dans ces travaux, l'implantation classique par faisceau d'ions et l'implantation par immersion plasma. Des dopages au phosphore, au bore et à l'arsenic ont été réalisés par cette technique d'implantation avec une activation par recuit thermique. L'importance de la température de recuit, des doses d'implantation et des couches de passivation sur la qualité électrique des jonctions formées a été mise en évidence. Des jonctions à faible courant de saturation ont pu être obtenues pour les différentes sources dopantes. Ces dopages par implantation ont ensuite été appliqués à la réalisation de cellules solaires en silicium sur substrat de type p (avec un émetteur dopé au phosphore) et sur substrat de type n (avec un émetteur dopé au bore et un champ arrière dopé au phosphore). L'utilisation de l'implantation ionique a permis d'atteindre un rendement de 19,1 % sur les cellules de type p soit un gain de 0,6 %abs par rapport au dopage par diffusion gazeuse, ainsi qu'un rendement de 20,2 % sur les cellules de type n. / This study aims at investigating the use of ion implantation doping for the realization of emitters and back surface fields of silicon solar cells. The benefits of using ion implantation instead of high temperature gaseous diffusion are the possibility to precisely control the dopant concentration profiles as well as to simplify the solar cells fabrication process. Beam line ion implantation and plasma immersion ion implantation techniques have been used and compared during this work. Phosphorus, boron and arsenic have been implanted and activated by thermal annealing to form the various doping layers. The influences of the annealing temperature, of the implantation doses and of the passivation layers on the junction electrical quality have been studied. Low emitter saturation current densities were reached for each dopant. The implanted doped regions were then integrated in p-type silicon solar cell structure (including a phosphorus doped emitter) and in n-type PERT bifacial solar cell structure (including a boron doped emitter and a phosphorus doped back surface field). With the use of ion implantation, efficiency of 19,1 % was reached for the p-type solar cells corresponding to an overall gain of 0,6 %abs as compared to the gaseous diffusion doping, while 20,2 % of efficiency were measured on the n-type bifacial silicon solar cells.

Les électrodes transparentes (ET) sont présentes dans de nombreux dispositifs optoélectroniques. Par exemple, on peut les trouver au sein de cellules solaires, d'écrans tactiles, d'OLEDs ou encore de films chauffants transparents. Les propriétés physiques de ces électrodes influencent l'efficacité de ces dispositifs. Les ET sont fabriquées à partir de matériaux transparents conducteurs (TCM) dont le développement a débuté dans les années 1950 notamment avec les oxydes métalliques. Parmi ces oxydes transparents conducteurs (TCO), l'oxyde d'étain-indium (ITO) est celui le plus communément utilisé dans les cellules solaires et les écrans de télévision ou de smartphones. Cependant, de nouvelles exigences telles qu'une réduction des coûts, la flexibilité et la fabrication à faible température et/ou faible coût, ont orienté les recherches vers de nouveaux TCM, notamment à base de nanostructures. Parmi ces matériaux émergents, les réseaux de nanofils métalliques, en particulier de nanofils d'argent, présentent déjà des propriétés optiques et électriques approchant celles de l'ITO, c'est-à-dire une conductivité électrique et une transparence élevées. Ces deux propriétés sont cependant intrinsèquement liées à la densité de nanofils constituant le réseau, et lorsque la conductivité augmente, la transparence diminue. Des traitements post-dépôt existent et permettent d'augmenter la conductivité électrique des ET sans changer la densité du réseau. Plusieurs de ces méthodes d'optimisation ont été étudiées pendant ce travail de thèse, en particulier le recuit thermique, analysé minutieusement afin de comprendre les différents mécanismes de réduction de la conductivité électrique induits par la température. L'examen des effets thermiques a soulevé la question de l'instabilité des nanofils en température, qui est aussi abordée et discutée dans ce document. Le paramètre clé de la densité de nanofils optimale menant au meilleur compromis entre transparence et conductivité a été recherché pour des nanofils de différentes dimensions. La taille des nanofils a en effet un fort impact sur les propriétés du réseau. Ainsi, les propriétés électriques, dans le cadre de la théorie de la percolation, les propriétés optiques comme la transmittance et le facteur de haze, et même l'instabilité thermique ont été reliées aux dimensions des nanofils ainsi qu'à la densité du réseau en utilisant des modèles physiques simples. En ce qui concerne les applications de ces ET émergentes, des études ont été menées sur l'application des réseaux de nanofils d'argent comme film chauffant transparent, et les résultats sont rapportés à la fin de ce document. Les limitations soulevées par cette application, comme les limites de stabilités électrique et thermique ont aussi été abordées. Pour finir, des études préliminaires menées sur de nouvelles applications comme des antennes transparentes ou le blindage électromagnétique transparent utilisant les nanofils d'argent sont présentées. / Transparent electrodes (TE) are used in a variety of optoelectrical devices. Among them, solar cells, flat panel displays, touch screens, OLEDs and transparent heaters can be cited. The physical properties of the TE influence the efficiency of the device as a whole. Such electrodes are fabricated from transparent conducting materials (TCM) that have been undergoing development since the 1950s, initially from metallic oxides. Among these transparent conducting oxides (TCO), indium tin oxide (ITO) is the most commonly used in solar cells, and television or smartphone screens. However requirements such as cost reduction, flexibility and low cost/temperature fabrication techniques have oriented the researches toward emerging TCM, mostly using nanostructures. Among them, metallic nanowire networks, and in particular silver nanowires (AgNW), already present optical and electrical properties approaching those of ITO, i.e. a high electrical conductivity and a high transparency. These two properties are intrinsically linked to the network density, therefore a tradeoff has to be considered knowing that when conductivity increases, transparency decreases. Some post-deposition treatments do exist, allowing an increase of the TE electrical conductivity without changing the network density. Several of these optimization methods have been thoroughly studied during this thesis work, especially thermal annealing. This method have been investigated in details to understand the different thermally-induced mechanisms of conductivity improvement. In addition, the investigation of thermal effects raised the question of thermal instability of the nanowires, which is also addressed and discussed in this document. The key issue of density optimization, allowing the best tradeoff between transparency and conductivity, has been investigated for nanowires with different dimensions. Nanowire size has a strong impact on the network properties. Thus, electrical properties, within the framework of percolation theory, optical properties such as transmittance or haziness, and even thermal instability have been linked to the nanowires' dimensions and the network density by using simple physical models. Regarding the application of these emerging TE, studies were conducted on the application of AgNWs as transparent heaters, and the results are reported at the end of the document. Limitations arising from this application, like thermal and electrical stabilities, have also been addressed. To finish, preliminary studies conducted on new applications such as transparent antennas and transparent electromagnetic shielding using AgNW are presented.

O carbeto de silício (SiC) apresenta várias propriedades extremamente interessantes para a fabricação de dispositivos eletrônicos submetidos a condições extremas como alta temperatura (300 a 600 °C), alta frequência e alta potência. Além disso, é o único semicondutor composto que, reagindo com o oxigênio, forma um óxido isolante estável, o SiO2. No entanto, as propriedades elétricas de estruturas de SiO2/SiC são degradadas pela alta concentração de estados eletricamente ativos na interface dielétrico/semicondutor. Tal característica representa uma barreira para a fabricação de dispositivos baseados nesse material. Nesta tese foram comparadas e analisadas as propriedades de estruturas SiO2/4H-SiC obtidas por diferentes processos de oxidação térmica. As estruturas resultantes foram caracterizadas por medidas de corrente-tensão, capacitância-tensão e condutância ac de alta frequência, espectroscopia de fotoelétrons induzidos por raios-X, análise por reação nuclear e microscopia de força atômica. O uso dessas técnicas analíticas visou a correlacionar o comportamento elétrico das estruturas obtidas com suas propriedades físico-químicas como, por exemplo, composição e estrutura química do óxido formado. Os resultados evidenciam diferenças específicas entre os ambientes de oxidação e temperaturas aos quais as amostras foram submetidas, com uma forte distinção entre 4H-SiC tipo-n e tipo-p. Em geral, amostras do substrato tipo-n apresentaram menores quantidades de defeitos na interface SiO2/SiC em comparação com as do tipo-p. Foram identificados comportamentos relacionados a defeitos no óxido, próximos à interface, responsáveis pela captura de portadores majoritários provenientes do semicondutor. Ficou evidente que alguns ambientes e temperaturas de oxidação beneficiam a interface em detrimento da qualidade do filme de óxido e vice-versa. Uma atmosfera de oxidação alternativa, utilizando H2O2 como agente oxidante, foi proposta. Tal processo mostrou-se eficaz na redução da quantidade de estados eletricamente ativos na interface em estruturas tipo-n através da conversão de compostos carbonados em SiO2 no filme dielétrico formado. / Silicon carbide (SiC) presents many advantageous properties for electronic devices designed to work under extreme conditions such as high-temperature (300 ~ 600 °C), high-frequency, and high-power. In addition, the formation of an insulating oxide layer (SiO2) by thermal oxidation is an attractive property for the microelectronics industry. Nevertheless, large densities of interface states at the SiO2/SiC interface degrade electrical properties of the resulting structure. Such states are responsible for undesirable effects which hamper the development of SiC-based devices. In this thesis, the properties of SiO2/4H-SiC structures obtained by distinct oxidation processes where analyzed and compared. The resulting structures where characterized by currentvoltage, high-frequency capacitance-voltage and ac conductance, X-ray photoelectron spectroscopy, nuclear reaction analysis, and atomic force microscopy. Such techniques were employed in order to correlate electrical and physico-chemical properties of the formed structures like composition and chemical bonding of the oxide layer. Results evidence differences among samples prepared under several oxidation atmospheres and temperatures, with a strong distinction among n- and p-type 4H-SiC. Overall, p-type samples presented larger values of interface states densities in comparison with their ntype counterparts. Near-interface traps in the oxide layer, responsible for capture of majority carriers from the semiconductor substrate, were identified. We could evidence that some oxidation conditions improve the bulk properties of the oxide layer, at the same time that they degrade the SiO2/SiC interface quality, and vice versa. An alternative oxidation process using H2O2 as oxidizing agent was proposed. Such process has shown to reduce the amount of electrically active defects at the interface in n-type samples by converting carbonaceous compounds in SiO2 in the formed dielectric layer.

La sécurité des installations nucléaires est constamment un souci majeur lors de leur exploitation, mais aussi lors de la conception de nouveaux réacteurs. Leurs durées de vie est limitée à cause des changements de comportement mécanique de leurs composants métalliques (principalement la cuve du réacteur mais aussi ses composants internes), qui sont accélérés ou induits par l’irradiation de neutrons. Une prédiction quantitative précise de ces changements, en fonction de la composition des matériaux et des conditions d'irradiation, est par conséquent un objectif de première importance pour la science des matériaux nucléaires. La modélisation est, de nos jours, considérée comme un complément vital aux approches expérimentales, avec l'objectif d’apporter une meilleure compréhension des processus physiques et chimiques qui se produisent dans les matériaux métalliques sous irradiation de neutrons.<p><p>La modélisation des effets de l'irradiation de neutrons dans les aciers est par nature un problème multi-échelle. Le point de départ est la simulation des cascades de collisions atomiques initiées par les neutrons à hautes énergies qui pénètrent dans le matériau, créant ainsi des défauts ponctuels mobiles. Différents modèles physiques, considérant des échelles de temps et de longueur croissantes, doivent être développés afin de convenablement tenir en compte de tous les différents processus qui provoquent des changements de comportement macroscopique, à cause de la présence de ces défauts ponctuels mobiles. En outre, des liens entre les différents modèles doivent être créés, parce que les prédictions de chacun d'entre eux doivent servir de paramètres d'entrée pour les modèles qui travaillent aux échelles supérieures. Dans cette thèse, un tel lien est créé entre le niveau atomique et les modèles à gros-grains, en développant un nouvel algorithme Monte-Carlo cinétique atomistique (MCCA), où le matériau est décrit comme une collection d'atomes occupant des sites cristallographiques réguliers. Le processus simulé est dès lors naturellement décomposé en séries d'évènements élémentaires activés thermiquement, correspondant à la migration des défauts ponctuels (lacunes ou interstitiels) vers des positions de proches voisins, qui sont en permanence en compétition en fonction de leurs fréquences d'occurrences respectives. Ces dernières sont calculées en fonction des énergies de migrations, qui sont elles-mêmes calculées avec peu d'approximations par une méthode qui prend en compte tous les effets de la relaxation statique et des interactions chimiques à longue portée. Le nouvel algorithme MCCA est par conséquent un modèle physique, entièrement basé sur un potentiel inter-atomique approprié qui est utilisé de la manière la plus complète possible, sans définir de paramètres empiriques qui devraient être, par exemple, fittés depuis des données expérimentales. Finalement, l'algorithme est accéléré de plusieurs ordres de grandeur en utilisant des réseaux de neurones artificiels (RNA), entraînés à prédire les énergies de migrations des défauts ponctuels en fonction de leur environnement atomique local.<p><p>Le nouvel algorithme MCCA est utilisé avec succès pour simuler des expériences de recuits (pour lesquels une seule lacune doit être introduite dans la boîte), afin de valider le modèle grâce à une comparaison directe de ses prédictions avec des résultats expérimentaux trouvés dans la littérature. Une comparaison très satisfaisante est accomplie pour deux alliages modèles importants pour la science des matériaux nucléaires. Dans les deux cas, l'évolution avec le temps de recuit du rayon moyen des précipités formés, ainsi que de leur densité, est en très bonne adéquation avec les mesures expérimentales trouvées dans la littérature, contrairement à ce que d'autres auteurs avaient jusqu’à présent réussi. Ensuite, l'algorithme est généralisé avec succès afin de permettre l'introduction d'un grand nombre de lacunes, ce qui est un des deux ingrédients nécessaires pour la simulation des effets de l'irradiation de neutrons dans les métaux. Cet accomplissement permet la simulation de processus longs et complexes, par exemple le calcul de coefficients de diffusions et temps de vies d'amats de cuivre-lacunes, qui sont des paramètres d'entrée nécessaires pour des modèles de simulation à gros-grains. Finalement, des preuves convaincantes sont apportées que l'algorithme MCCA peut être, dans un futur proche, généralisé d'avantage et permettre la prise en compte des interstitiels, ouvrant ainsi la voie vers la simulation de cycles complets d'irradiation.<p> / Doctorat en Sciences / info:eu-repo/semantics/nonPublished