Orientador: Jose Alexandre Diniz / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Eletrica e de Computação / Made available in DSpace on 2018-08-05T17:29:59Z (GMT). No. of bitstreams: 1 Biasotto_Cleber_M.pdf: 4466326 bytes, checksum: 75500d469b99d21f5c40a3214a755168 (MD5) Previous issue date: 2005 / Resumo: Neste trabalho, filmes finos de nitreto (SixNy), oxido (SiOx) e oxinitreto (SiOxNy) de silicio sobre substrato de silicio, obtidos através da deposição química a partir da fase vapor auxiliada por plasma remoto (RPCVD), foram caracterizados e estudados para aplicações em micromáquinas (micromachining) ou sistemas micro-eletro-mecanico (MEMS). Os filmes de nitreto de silicio (SixNy) foram obtidos para aplicação em estruturas suspensas (pontes e membranas) e como mascara de proteção de dispositivos MOS para remoção do substrato, utilizando os processos de corrosão úmida do substrato de silicio pelas faces superior (front-side bulk micromachining) e inferior (back-side bulk micromachining), respectivamente. Os filmes de oxido de silicio (SiOx) foram aplicados como camada sacrificial em processos de obtenção de estruturas suspensas empregando a técnica de remoção de camadas sacrificiais na superfície (surface micromachining). Os filmes de oxinitreto de silicio (SiOxNy) foram obtidos como filmes alternativos para aplicação em estruturas suspensas (pontes e membranas), utilizando os processos de corrosão úmida do substrato de silicio pela face superior (front-side bulk micromachining). A fabricação destas estruturas e primordial para o desenvolvimento de micro-sensores e micro-atuadores. Neste trabalho foram revisadas as técnicas de processamento CVD (Chemical Vapor Deposition), apresentando a justificativa da escolha do reator ECR (Electron Cyclotron Resonance), que utiliza a tecnologia CVD com Plasma Remoto (RPCVD) para as deposições / Abstract: In this work, silicon nitride (SixNy), oxide (SiOx) and oxynitride (SiOxNy) thin films obtained by remote plasma chemical vapor deposition (RPCVD) on silicon substrate were studied and characterized for micromachining or micro electro-mechanical system (MEMS) applications. Silicon nitride films (SixNy) were used in suspended structures (membranes and bridges) and as MOS device protection mask against wet substrate etching, obtained by wet substrate etching processes using the front-side and back-side bulk micromachining techniques, respectively. Silicon oxide films (SiOx) were employed as sacrificial layers to obtain suspended surface structures using the surface micromachining technique. Silicon oxynitride (SiOxNy) films were used as alternative films in suspended structures (membranes and bridges), using the front-side bulk micromachining technique. The fabrication of these structures is primordial for the micro sensor and actuator development. In these work, CVD (Chemical Vapor Deposition) techniques are revised, presenting the choice justification of ECR (Electron Cyclotron Resonance) reactor, which uses RPCVD technology for the depositions / Mestrado / Mestre em Engenharia Elétrica

Conselho Nacional de Desenvolvimento CientÃfico e TecnolÃgico / O avanÃo e o aperfeiÃoamento das tÃcnicas de sÃntese e manipulaÃÃo de materiais sÃo fundamentais para o entendimento de suas propriedades e das possÃveis formas de produÃÃo e utilizaÃÃo. PorÃm, no caso dos nanomateriais, principalmente, cujas extraordinÃrias capacidades sÃo bastante celebradas, problemas como defeitos estruturais, alto custo de obtenÃÃo e dificuldade de produÃÃo em larga escala ainda necessitam ser solucionados. Inserido neste panorama està o grafeno, um nanomaterial cuja morfologia bidimensional, constituÃda por Ãtomos de carbono dispostos de forma hexagonal, à responsÃvel por propriedades sem precedentes que apresentam revolucionÃria relevÃncia, tanto para a pesquisa bÃsica quanto para a pesquisa aplicada. Neste sentido, existem diferentes mÃtodos de sÃntese de grafeno, estando entre os mais vantajosos o mÃtodo de deposiÃÃo quÃmica em fase de vapor (Chemical Vapor Deposition - CVD). Este mÃtodo consiste na quebra das ligaÃÃes das molÃculas de um gÃs submetido a altas temperaturas de modo que os Ãtomos provenientes do gÃs sejam depositados sobre um determinado substrato. Neste trabalho, utilizou-se o mÃtodo CVD para a sÃntese de grafeno sobre substratos de silÃcio oxidado (Si/SiO2) recobertos por filmes de nÃquel (Ni) com, aproximadamente, 500nm de espessura, os quais funcionaram como catalisadores. O gÃs metano (CH4) foi utilizado como a fonte dos Ãtomos de carbono depositados e os processos de sÃntese tiveram diferentes conjuntos de parÃmetros executados. A sÃntese de grafeno pelo mÃtodo CVD teve como objetivo geral verificar os resultados divulgados na literatura e aperfeiÃoÃ-los, relacionando os parÃmetros utilizados nas sÃnteses e as caracterÃsticas dos filmes de Ni catalisadores com aquelas apresentadas pelos filmes de grafeno obtidos nos experimentos. As amostras foram caracterizadas por meio de Microscopia EletrÃnica de Varredura, Microscopia Ãptica e Raman Confocal e Microscopia de ForÃa AtÃmica. Em consistÃncia com os resultados publicados na literatura, observou-se que sÃo sintetizados filmes finos compostos por flakes de material grafÃtico com espessura nÃo uniforme, e que a obtenÃÃo de filmes mais uniformes à fortemente dependente da morfologia do filme catalisador. RegiÃes apresentando espectro Raman caracterÃstico de monocamadas de grafeno e de grafeno de poucas camadas foram maiores quando combinados o tratamento tÃrmico do filme de Ni com o baixo fluxo e menor tempo de exposiÃÃo ao CH4. Verificaram-se, ainda, variaÃÃes nos espectros Raman dos flakes. Estas variaÃÃes apresentaram-se mais intensas, quanto mais reduzido à o nÃmero de camadas de grafeno e incluem o aparecimento da banda D, alÃm do deslocamento dos picos, revelando a influÃncia dos substratos sobre os filmes sintetizados. Esta pesquisa considerou mÃtodos de estimativa do nÃmero de camadas por caracterÃsticas do espectro Raman, divulgados na literatura, aliados à anÃlise da espessura por AFM que mostraram ser possÃvel a sÃntese de monocamadas de grafeno. / The advancement and improvement of synthesis techniques and handling of materials are fundamental to understand their properties and possible forms of production and use. However, in the case of nanomaterials, problems such as structural defects, high cost and difficulty of achieving production on a large scale have yet to be solved. Inserted in this panorama is graphene, a two-dimensional nanomaterial whose morphology, consisting of carbon atoms arranged in hexagonal form, is responsible for unprecedented properties that have revolutionary relevance for both basic and applied research. There are different methods of synthesis of graphene. The method of Chemical Vapor Deposition (CVD) is among the most advantageous ones. This method consists in breaking the bonds of the molecules of a gas subjected to high temperatures so that the atoms from the gas are deposited on a given substrate. In this work, we used the CVD method for the synthesis of graphene on oxidized silicon substrates (Si/SiO2) coated with a 500 nm thick film of nickel (Ni), which served as the catalyst. Methane gas (CH4) was used as the source of the carbon atoms and the synthesis was carried out using different sets of parameters. Experiments were performed, firstly, using parameters es-tablished in the literature and the results were compared with those obtained by other authors. The influence of the synthesis parameters and the characteristics of the films of Ni catalysts on the properties of the graphene films was studied. The samples were characterized using Scanning Electron Microscopy, Confocal Raman and Optical Microscopy, and Atomic Force Microscopy. In agreement with results from the literature, it could be observed that thin films are synthesized and they are composed of graphitic flakes with a non-uniform thickness, which is strongly dependent of the morphology of catalyst film. Larger regions with characteristic Raman spectra of monolayer and few layer graphene could be obtained by combining thermal treatment of Ni film during the sputtering process with low gas flow and time of exposure to CH4 in the CVD experiment. Variations in the Raman spectra of the flakes could be observed, including the emergence of the D-band and the displacement of the peaks. These variations, which reveal the influence of substrates on the synthesized films, were more intense the smaller the number of graphene layers. Next, we combined methods reported in the literature for estimating the number of layers on the basis of the characteristics of the Raman spectra with AFM analysis to obtain the thickness of the graphene layer. The results obtained from our analysis show that monolayer graphene could be successfully synthesized in the experiments.

Neste trabalho é apresentada a simulação, fabricação e caracterização de filtros interferenciais empregando películas dielétricas amorfas depositadas pela técnica de deposição a vapor assistida por plasma (PECVD) sobre substratos de silício e de Corning Glass (7059). Os dispositivos ópticos foram construídos usando-se processos padrões de microeletrônica e consistiram em camadas periódicas com espessura e índice de refração apropriados para produzir picos da atenuação na transmitância da luz na região visível. Simulações numéricas precedentes foram realizadas baseando-se nas características ópticas das películas dielétricas. Para a caracterização dos filtros interferenciais, uma luz monocromática de um laser de He-Ne, foi injetada nos filtros e a luz obtida na saída foi conduzida então a um detector. O filtro depositado sobre Corning Glass (chamado de filtro vertical) e o filtro depositado sobre silício com cavidades (chamado de filtro suspenso) foram montados sobre dispositivos térmicos e angulares de modo a medir suas respostas à variação angular e térmica. Também, o filtro depositado sobre silício (chamado de filtro horizontal) foi montado sobre um dispositivo térmico, a fim de medir sua resposta à temperatura. Quando os filtros são submetidos a uma mudança na temperatura, uma variação do índice de refração devido ao efeito termo-óptico produz um deslocamento nos picos da atenuação, que podem ser previstos por simulações numéricas. Esta característica permite que estes dispositivos sejam usados como sensores termo-ópticos. Por outro lado, quando o filtro vertical e o filtro suspenso são submetidos a variações angulares entre a normal ao plano do filtro e o feixe de laser, uma variação na potência da luz de saída é produzida. Esta característica permite que estes dispositivos sejam usados como sensores angulares. / In this work, we present the simulation, fabrication and characterization of filters employing amorphous dielectric films deposited by Plasma Enhanced Chemical Vapor Deposition (PECVD) technique on crystalline silicon and Corning Glass (7059) substrates. The optical devices were fabricated using standard microelectronic processes and consisted of periodic layers with appropriated thickness and refractive indexes to produce transmittance attenuation peaks in the visible region. For this, previous numerical simulations were realized based in the optical parameters of the dielectric films. For the characterization of the optical interferential filters, a monochromatic light, a He-Ne laser, was projected onto the filters and the transmitted output light was then conducted to a detector. The optical filters were produced on Corning Glass (here called vertical filter) and on silicon substrates. The silicon substrate was etch in KOH solution to form cavities and suspend part of the filter (here called suspended filter). The vertical and suspended filters were mounted on thermo and angular devices that allowed the measurement of the optical power as a function of temperature and angle changes. A second type of filter deposited over a silicon substrate (here called horizontal filter) was mounted on thermoelectric device, in order to control the temperature responses. When the filters are submitted to a change in temperature, a variation of the refractive index is originated in the dielectric film due to the thermo-optic effect (TOE), producing a shift in the attenuation peaks, which can be well predicted by numerical simulations. This characteristic allows these devices to be used as thermo-optic sensors. On the other hand, when the vertical filter and the suspended filter were subjected to an angular shift between the filter\'s normal and the laser, a variation of the output optical power is originated. This characteristic allows these devices to be used as angular sensors.

A miniaturização de uma biocélula a combustível (BC) enzimática de glicose/O2 para aplicação em dispositivos bioeletrônicos implantáveis representa um grande desafio em eletroquímica moderna. Isso porque é preciso desenvolver bioeletrodos com alta atividade bioeletrocatalítica, com enzimas fortemente ligadas a superfície eletródica. Além disso, o próprio processo de micromanipulação é desafiador, uma vez que é desejável obter biocélulas miniaturizadas e com alta densidade de potência. Assim, propõe-se aqui o desenvolvimento de uma BC que atenda os requisitos supracitados. Para isso, desenvolveram-se bioânodos e biocátodos compostos por folhas de grafeno individuais modificadas com as enzimas glicose desidrogenase (GDh) e bilirrubina oxidase (BOx), respectivamente. Eletrodos de grafeno com área de 10-3 cm2 e espessura de 0,9 ± 0,2 nm foram utilizados em um microchip de Si/SiO2. Observou-se que o grafeno transferido para o microchip permanecia com contaminações de cobre, mesmo após a utilização dos métodos químicos tradicionais de remoção desse metal. A presença de cobre é decorrente do processo de fabricação do grafeno, neste caso, a deposição química em fase vapor (CVD). Para remover qualquer resíduo deste metal, submeteu-se o grafeno a um procedimento de remoção eletroquímica de cobre, denominada aqui como e-etching. Uma vez não observada qualquer corrente faradaica residual associada às impurezas, obtiveram-se os bioeletrodos com a GDh e a BOx. Para a imobilização enzimática, utilizou-se a ligação covalente via funcionalização com o ácido 4-aminobenzóico. As curvas de polarização de estado quase-estacionário obtidas com os bioeletrodos em tampão fosfato pH 7,0 revelaram correntes de onset para oxidação de glicose em -0,13 V e redução de oxigênio em 0,45 V. Por fim, os eletrodos foram utilizados em uma BC sem membrana, operando no microchip de Si/SiO2, em eletrólito tampão fosfato saturado com O2 e glicose 8,0 mmol L-1. A BC apresentou um potencial de circuito aberto em 0,55 V, com densidade de potência volumétrica igual a 1,7 W cm-3, o maior valor reportado até os dias de hoje para uma BC. / The miniaturization of a glucose/O2 enzymatic biofuel cell (BFC) for application in implantable bioelectronic devices is a challenge in electrochemistry. For this purpose, the necessity of bioelectrodes development with high biocatalytic activity such as enzymes strongly attached to electrode surfaces is a current trend. Moreover, the micromanipulation procedure itself is a challenge since the obtention of BFCs with high power density is desirable. Then, the present study shows the partial results obtained in the development of a glucose/O2 BFC with the characteristics exemplified. For the later, bioanodes and biocathodes were obtained with single graphene flakes modified with the enzymes glucose dehydrogenase (GDh) and bilirubin oxidase (BOx), respectively. Graphene flakes electrodes with area of about 10-3 cm2 and thickness of 0,9 ± 0,2 nm were used in a Si/SiO2 microchip. It was observed that transferred graphene to the microchip remained with copper/copper oxide contamination even after the use of conventional methodologies for the remotion of the metal from single graphene foils. The presence of the remaining copper is due to the fabrication process of graphene by chemical vapor deposition (CVD). For the remotion of remaining impurities from graphene, the electrochemical remotion of copper from graphene was carried out in acidic media by the so called e-etching procedure. Since no residual faradaic current was observed due to metal/metal oxide impurities in graphene electrodes, the bioelectrodes were obtained with the enzymes GDh and BOx. The covalent functionalisation of graphene with 4-aminobenzoic acid via diazonium coupling reaction was used for the enzymatic immobilization. The quasi-stationary polarization curves obtained with the bioelectrodes in phosphate buffer pH = 7,0 showed onset oxidation current for glucose at -0.13V and reduction of molecular oxygen starting at +0.45V. Finally, the bioelectrodes were used in a membraneless BFC operating in a Si/SiO2 microchip under saturated oxygen and glucose 8 mmol L-1 in the electrolyte media. The BFC showed an open circuit potential at 0.55V and volumetric power density of 1.7 W cm-3, the highest value reported for an enzymatic BFC so far.

This thesis is concerned with the growth, electronic properties and modification of hydrogenated amorphous carbon films of a thickess range of 50-300 nm, which have been deposited using rf plasma-enhanced chemical vapour deposition. These films may be subdivided into two types according to the electrode on which they are grown and the resulting film properties. These are polymer-like amorphous carbon or PAC, and diamond-like amorphous carbon or DAC. PAC possesses a wide optical band gap (2.7 eV), high resistivity (1014 - 10 15 Ocm) and low density of paramagnetic defects (~ 10 17 spins cm-3). The dominant current transport mechanism at room temperature has been observed to be hopping conduction at low electric fields and space-charge-limited current at high electric fields. The addition of nitrogen gas to the plasma to incorporate nitrogen within the film has been shown to move the Fermi level by 1 eV, towards midgap. A mechanism of doping due to the introduction of aromatic nitrogen-containing sites has been postulated. The boron, carbon and nitrogen ion implantation of PAC has resulted in the controllable increase in conductivity from 1015 to 106 O cm as a function of ion dose, from 2 x 1012 to 2 X 1016 ions cm-2. At low ion doses (up to 6 x 1014 ions cm-2) this occurs without any change in band gap; however, at higher doses the band gap collapses as a result of graphitisation. The dependence on the implant ion shows that it is possible to move the Fermi level towards the valence band with the implantation of boron, and towards midgap with the implantation of nitrogen. A hysteresis effect is observed at intermediate ion doses, which is attributed to the trapping of holes resulting in an increase in electron current. Implanting part of the thickness of the film at this ion dose has resulted in rectification, which has not previously been reported for this type of structure in amorphous carbon. DAC has been shown to possess a smaller band gap (0.7 eV), higher density of defects (~ 1020 spins cm-3) and lower resistivity (~ 1013 O cm) than PAC. The room-temperature current transport is governed by band-tail conduction at fields below 105 V cm-1, and the Poole-Frenkel effect at higher fields. The addition of nitrogen of up to 8 at. % has been observed to increase the band gap from 0.7 to 1.0 eV and therefore decrease the magnitude of the Poole-Frenkel conductivity. The Fermi level remains pinned at midgap, however. Therefore, it appears that PAC shows advantages over DAC in terms of future device applications.

Organometal halide perovskite absorbers such as methylammonium lead iodide chloride (CH3NH3PbI3-xClx), have emerged as an exciting new material family for photovoltaics due to its appealing features that include suitable direct bandgap with intense light absorbance, band gap tunability, ultra-fast charge carrier generation, slow electron-hole recombination rates, long electron and hole diffusion lengths, microsecond-long balanced carrier mobilities, and ambipolarity. The standard method of preparing CH3NH3PbI3-xClx perovskite precursors is a tedious process involving multiple synthesis steps and, the chemicals being used (hydroiodic acid and methylamine) are quite expensive. This work describes a novel, single-step, simple, and cost-effective solution approach to prepare CH3NH3PbI3-xClx thin films by the direct reaction of the commercially available CH3NH3Cl (or MACl) and PbI2. A detailed analysis of the structural and optical properties of CH3NH3PbI3-xClx thin films deposited by aerosol assisted chemical vapor deposition is presented. Optimum growth conditions have been identified. It is shown that the deposited thin films are highly crystalline with intense optical absorbance. Charge carrier separation of these thin films can be enhanced by establishing a local internal electric field that can reduce electron-hole recombination resulting in increased photo current. The intrinsic ferroelectricity in nanoparticles of Barium Titanate (BaTiO3 -BTO) embedded in the solar absorber can generate such an internal field. A hybrid structure of CH3NH3PbI3-xClx perovskite and ferroelectric BTO nanocomposite FTO/TiO2/CH3NH3PbI3-xClx: BTO/P3HT/Cu as a new type of photovoltaic device is investigated. Aerosol assisted chemical vapor deposition process that is scalable to large-scale manufacturing was used for the growth of the multilayer structure. TiO2 and P3HT with additives were used as ETL and HTL respectively. The growth process of the solar absorber layer includes the nebulization of a mixture of PbI2 and CH3NH3Cl perovskite precursors and BTO nanoparticles dissolved in DMF, and injection of the aerosol into the growth chamber and subsequent deposition on TiO2. While high percentage of BTO in the film increases the carrier separation, it also leads to reduced carrier generation. A model was developed to guide the optimum BTO nanoparticle concentration in the nanocomposite films. Characterization of perovskite solar cells indicated that ferroelectric polarization of BTO nanoparticles leads to the increase of the width of depletion regions in the perovskite layer hence the photo current was increased by one order of magnitude after poling the devices. The ferroelectric polarization of BTO nanoparticles within the perovskite solar absorber provides a new perspective for tailoring the working mechanism and photovoltaic performance of perovskite solar cells.

Cette thèse porte sur la modélisation des plasmas micro-ondes en mélanges H2/CH4 et H2/CH4/B2H6, utilisés pour le dépôt de diamant intrinsèque et de diamant dopé au bore. L'objectif est d'établir des modèles de cinétique chimique afin de décrire la phase gazeuse et d'appréhender les limitations des modèles physiques nécessaires à l'étude des plasmas H2/CH4 et H2/CH4/B2H6 fonctionnant à haute densité de puissance (haute pression / haute puissance). L'étude repose sur une approche numérique à travers plusieurs modèles physique (1D et 2D) et chimiques qui permet la description physico-chimique de la phase plasma en fonction de nombreux paramètres expérimentaux (pression, puissance, composition du gaz). Une comparaison des résultats numériques a été effectuée systématiquement avec des mesures de densités intégrées radialement réalisées par TDLAS et OES pour les espèces CH4, CH3, C2H2, C2H4, C2H6, B2H6 et B. Cette comparaison a pour objectif la validation des modèles physiques et des schémas cinétiques. Des écarts significatifs entre le modèle et l'expérience ont révélé une limitation intrinsèque à l'utilisation d'une approche ID radiale pour décrire les propriétés du plasma pour les conditions de haute densité de puissance. L'utilisation d'un modèle 2D fluide conçu à partir du logiciel ANSYS Fluent propose une meilleure description des phénomènes de transport mais ne permet pas de prendre en compte les processus électroniques. L'analyse de la composition chimique des plasmas micro-onde H2/CH4, H2/B2/H6 et H2/CH4/ B2H6 a montré une limitation des schémas cinétiques décrivant ces mélanges par une large gamme de conditions opératoires. En particulier les mécanismes C/B de ces modèles ne reproduisent pas la forte influence observée expérimentalement de l'addition de méthane sur le bore atomique. Enfin une étude numérique sur la distribution spatiale des espèces borées à poximité de la surface est confrontée à des résultats expérimentaux sur le dopage de diamant en fonction de différents paramètres du procédé. / This thesis deals with modelling of high power density microware plasmas of H2/CH4 and H2/CH4/B2H6 mixtures used for growing intrinsic and boron-doped diamond films. The aim of this work is to establish chemical kinetic schemes in order to describe the gas phase composition and to manage limitations of physical models of high power density H2/CH4 and H2/CH4/B2H6 plasmas. This investigation relies on a numerical approach using different physical models (ID and 2D) as well as chemical models according to differents experimental parameters (pressures, power, gas composition). Comparisons are carried out with integrated densities of CH4, CH3, C2H2, C2H4, C2H6, B2H6 and B measured by TDLAS and OES in order to validate the models. Significant discrepancies highlight limitation of ID approach for high power density whereas the use of a 2D fluid model (Fluent based) proposes better description of transport phenomena. The chemical analysis of H2/CH4, H2/B2H6 and H2/CH4/B2H6 MW plasmas also shows a limitation of the current kinetic schemes for a wide range of operating conditions. In particular C/B mechanisms do not reproduce the strong influence of methane addition on B. At least, a numerical study of spatial composition of boron species near the substrate is compared to experimental results on doping efficiency.

Group III-Nitrides (GaN, InN & AlN) are considered one of the most important class of semiconducting materials after Si and GaAs. The excellent optical and electrical properties of these nitrides result in numerous applications in lighting, lasers, and high-power/high-frequency devices. Due to the lack of cheap bulk III- Nitride substrates, GaN based devices have been developed on foreign substrates like Si, sapphire and SiC. These technologies have been predominantly developed on the so called Ga-polarity epitaxial stacks with growth in the [0001] direction of GaN. It is this orientation that grows most easily on sapphire by metal organic chemical vapor deposition (MOCVD), the most common combination of substrate and deposition method used thus far. The opposite [000¯1] or N-polar orientation, very different in properties due to the lack of an inversion centre, offers several ad- vantages that could be exploited for better electronic and optoelectronic devices. However, its growth is more challenging and needs better understanding. The aim of the work reported in this dissertation was a systematic investigation of the relation between the various growth parameters which control polarity, surface roughness and mosaicity of GaN on non-miscut sapphire (0001) wafers for power electronics and lighting applications, with emphasis on the realization of N-polar epitaxial layers. GaN is grown on sapphire (0001) in a two-step process, which involves the deposition of a thin low temperature GaN nucleation layer (NL) on surface modified sapphire followed by the growth of high temperature device quality GaN epitaxial layer. The processing technique used is MOCVD. Various processing methods for synthesis of GaN layers are described with particular em- phasis on MOCVD method. The effect of ex situ cleaning followed by an in situ cleaning on the surface morphology of sapphire (0001) wafers is discussed. The characterization tools used in this dissertation for studying the chemical bond nature of nitrided sapphire surface and microstructural evolution (morphological and structural) of GaN layers are described in detail. The effect of nitridation temperature (TN) on structural transformation of non- miscut sapphire (0001) surface has been explored. The structural evolution of nitrided layers at different stages of their process like as grown stage and thermal annealing stage is investigated systematically. The chemical bond environment information of the nitrided layers have been examined by x-ray photoelectron spectroscopy (XPS). It is found that high temperature nitridation (TN ≥ 800oC) results in an Al-N tetrahedral bond environment on sapphire surface. In contrast, low temperature nitridation (TN = 530oC) results in a complex Al-O-N environment on sapphire surfaces. Microstructural evolution of low temperature GaN NLs has been studied at every stage of processing by scanning electron microscopy (SEM) and atomic force microscopy (AFM). Surface roughness evolution and island size distribution of NLs measured from AFM are discussed. It is found that NLs processed on sapphire wafers nitrided at (TN ≥ 800oC) showed strong wurtzite [0002] orientation with sub-nanometre surface roughness. In contrast, NLs processed at (TN = 530oC) showed zinc blende phase in the as grown stage with higher surface roughness, but acquired a greater degree of wurtzite [0002] orientation after thermal annealing prior to high temperature GaN growth. Polarity, surface quality and crystal quality of subsequently grown high temperature GaN epitaxial layers is described in relation to the structure of the trans- formed nitrided layers. Higher nitridation temperatures (TN ≥ 800oC) consistently yield N-polar GaN whereas lower nitridation temperatures (TN = 530oC) yield Ga-polar GaN. It is found that the relative O atom concentration levels in nitrided layers control the density of inversion domains in N-polar GaN. The effect of various growth parameters (NH3 flow rate, growth temperature, NL thickness) on surface morphology and mosaicity of both Ga & N-polar GaN layers is discussed in detail. We report device quality N-polar GaN epitaxial layers on non-miscut sapphire (0001) wafers by careful optimization of growth temperature. It is found that lower growth temperatures (800oC) are favorable for obtaining smooth N- polar GaN layers. In contrast, N-polar GaN layers grown at higher temperatures (1000 to 1080oC) are rough with hexagonal hillocks.

Carbon nanotubes (CNTs) have become one of the most interesting allotropes of carbon due to their intriguing mechanical, electrical, thermal and optical properties. The synthesis and electron emission properties of CNT arrays have been investigated in this work. Vertically aligned CNTs of different densities were synthesized on copper substrate with catalyst dots patterned by nanosphere lithography. The CNTs synthesized with catalyst dots patterned by spheres of 500 nm diameter exhibited the best electron emission properties with the lowest turn-on/threshold electric fields and the highest field enhancement factor. Furthermore, CNTs were treated with NH3 plasma for various durations and the optimum enhancement was obtained for a plasma treatment of 1.0 min. CNT point emitters were also synthesized on a flat-tip or a sharp-tip to understand the effect of emitter geometry on the electron emission. The experimental results show that electron emission can be enhanced by decreasing the screening effect of the electric field by neighboring CNTs. In another part of the dissertation, vertically aligned CNTs were synthesized on stainless steel (SS) substrates with and without chemical etching or catalyst deposition. The density and length of CNTs were determined by synthesis time. For a prolonged growth time, the catalyst activity terminated and the plasma started etching CNTs destructively. CNTs with uniform diameter and length were synthesized on SS substrates subjected to chemical etching for a period of 40 minutes before the growth. The direct contact of CNTs with stainless steel allowed for the better field emission performance of CNTs synthesized on pristine SS as compared to the CNTs synthesized on Ni/Cr coated SS. Finally, fabrication of large arrays of free-standing vertically aligned CNT/SnO2 core-shell structures was explored by using a simple wet-chemical route. The structure of the SnO2 nanoparticles was studied by X-ray diffraction and electron microscopy. Transmission electron microscopy reveals that a uniform layer of SnO2 is conformally coated on every tapered CNT. The strong adhesion of CNTs with SS guaranteed the formation of the core-shell structures of CNTs with SnO2 or other metal oxides, which are expected to have applications in chemical sensors and lithium ion batteries.

Orientadores: Leandro Tiago Manera, Arismar Cerqueira Sodré Júnior / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Elétrica e de Computação / Made available in DSpace on 2018-08-27T14:09:44Z (GMT). No. of bitstreams: 1 NascimentoJunior_AdrianoRicardo_M.pdf: 49523846 bytes, checksum: 938b4d8587e112835bf6e0988731ba04 (MD5) Previous issue date: 2015 / Resumo: Neste trabalho foram fabricados microrressonadores em anel com alto fator de qualidade utilizando filmes de nitreto de silício (SixNy) depositados a baixa temperatura (20 °C) utilizando a técnica de deposição ECR-CVD (Deposição em Fase Vapor por Resonância Ciclotrônica do Elétron). Graças à alta não linearidade do SixNy, tais filmes têm sido recentemente usados para aplicações em óptica não linear como a geração de pentes de frequência na banda C de telecomunicações. Para tais aplicações, o guia de onda do dispositivo deve possuir um ponto de dispersão nula no centro da banda C, necessitando de uma grande área. Infelizmente, filmes espessos de nitreto de silício (>400 nm) possuem um alto stress responsável pela ocorrência de rachaduras catastróficas no filme que reduzem drasticamente a eficiência do dispositivo. Utilizando simulações numéricas, demonstrou-se que para valores de índice de refração (n) maiores que 2, a área do guia de onda com zero dispersão em ? = 1,55 ?m é consideravelmente reduzida, necessitando assim de uma menor espessura de filme. Foi obtido um filme de SixNy rico em Si, com índice de refração igual a 2, alta taxa de deposição, baixa concentração de hidrogênio e uma rugosidade média de somente 0,52 nm (4,2 nm de desvio padrão). Devido à baixa temperatura da técnica de deposição empregada, não foi observado traços de stress no filme, permitindo a obtenção de uma espessura de 730 nm utilizando uma única etapa de deposição. Os microrressonadores ópticos fabricados com raios de 60 e 120 ?m apresentaram um FSR (Free Spectral Range) equidistante em toda a banda C e um fator de qualidade de 7,2x10^3 foi obtido experimentalmente. Tais resultados demonstraram a alta eficiência dos dispositivos fabricados com o filme de SixNy desenvolvido e sua promissora aplicação para óptica não linear na banda C de telecomunicações / Abstract: Silicon nitride (SixNy) films deposited by low-pressure electron cyclotron resonance plasma enhanced chemical vapor deposition (ECR-CVD) at room temperature are proposed for fabrication of microring resonators with high Q-factor. Due to the high silicon nitride nonlinearity, these films recently have also been used for nonlinear optics applications in the telecommunications C-band. For nonlinear applications such as the generation of frequency combs, the waveguide needs a zero dispersion point in the middle of C-band, requesting large waveguide area. Unfortunately, these thick SixNy films (>400 nm) have high stress and suffer from catastrophic cracking, which reduces the device efficiency. Using numerical simulations it was demonstrated that for refractive index (n) values greater than 2, the area of the waveguide with zero dispersion point at ? = 1.55 ?m is greatly reduced. A Si-rich silicon nitride layer with refractive index of 2, high deposition rate, low hydrogen concentration and roughness average of 0.52 nm with standard deviation of 4.2 nm was obtained. Due to the low temperature deposition, no thermal stress was observed in the SixNy film, allowing a thickness of 730 nm obtained with only one deposition step. After experimental measurements, microring resonators having a radius of 60 and 120 ?m, presented an equidistant Free Spectral Range and a Q-factor of 7.2x10^3 was achieved, showing the high efficiency of the device and their promising application in nonlinear effects in the telecommunication C-band / Mestrado / Eletrônica, Microeletrônica e Optoeletrônica / Mestre em Engenharia Elétrica