Orientador: Carlos Kenichi Suzuki / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecanica / Made available in DSpace on 2018-08-14T07:35:33Z (GMT). No. of bitstreams: 1 Santos_JulianaSantiagodos_D.pdf: 5083498 bytes, checksum: a60b455d6e9c947ecbd7491e564b8f10 (MD5) Previous issue date: 2009 / Resumo: Neste trabalho estudou-se o efeito da variação dos parâmetros do processo VAD (Vaporphase Axial Deposition) sobre as propriedades estruturais e ópticas da sílica vítrea visando o desenvolvimento de um material de alto desempenho óptico empregado no sistema óptico de equipamentos litográficos. As propriedades estruturais das preformas foram caracterizadas por microscopia eletrônica de varredura (MEV), espalhamento de raios-X a baixo ângulo (SAXS) e espectroscopia de absorção de estrutura fina de raios-X (XAFS). Absorção de raios-X (ARX) e tratamento de imagem digital foram utilizados para a obtenção da distribuição radial da densidade e da densidade média da sílica porosa, respectivamente. As propriedades ópticas foram determinadas por interferometria, espectroscopia óptica, espectrometria de polarização, espectroscopia Raman, espectroscopia no infravermelho e espectrofotometria de absorção óptica. Como principal resultado, obteve-se sílica vítrea com homogeneidade radial da estrutura, ?n = 3 ppm, birrefringência = 2 nm/cm e transmitância de 87 % em ? = 400 nm quando consolidada em atmosfera de He podendo superar 90 % quando consolidadas em vácuo. Este desempenho óptico foi obtido em até 95 % do diâmetro da preforma sem a necessidade de etapas adicionais, como o recozimento e a extração da região do diâmetro externo da preforma (geralmente a parte heterogênea) através de corte, reduzindo significativamente o tempo e custo de fabricação da sílica. / Abstract: This research reports the study of the effect of processing parameters of VAD (Vapor-phase Axial Deposition) method on structural and optical properties of silica glass aiming the development of an optically homogeneous material for use on lithographic equipments. The structural properties were characterized by the scanning electron microscopy (SEM), small-angle X-ray scattering (SAXS), and X-ray absorption fine structure (XAFS). X-ray absorption (XRA) and digital image processing were used to obtain the density radial distribution and average density of silica soot, respectively. The optical properties were determined by interferometry, optical spectroscopy, polarization spectrometry, Raman spectroscopy, infrared spectroscopy, and optical absorption spectrophotometry. As a main result, silica glass was produced with structural radial homogeneity, ?n = 3 ppm, birefringence = 2 nm/cm, and transmittance of 87 % at ? = 400 nm when it was consolidated with He atmosphere and higher than 90 % in vacuum. This optical performance was obtained in 95 % of preform diameter without additional steps, such as annealing and cutting of preform outer diameter region (usually the heterogeneous part) which significantly reduces the time and cost of silica fabrication. / Doutorado / Materiais e Processos de Fabricação / Doutor em Engenharia Mecânica

Orientador: Carlos Kenichi Suzuki / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecanica / Made available in DSpace on 2018-08-04T03:08:00Z (GMT). No. of bitstreams: 1 Santos_JulianaSantiagodos_M.pdf: 5007909 bytes, checksum: 812aaee54d3a8b29c20786e4372c3da5 (MD5) Previous issue date: 2005 / Resumo: No Laboratório Ciclo Integrado do Quartzo (LIQC), FEM, UNICAMP, está em andamento o desenvolvimento do processo VAD ("Vapor-phase Axial Deposition") para a fabricação de preformas para fibras ópticas de alta qualidade. Para isto, os parâmetros do processo de fabricação devem ser cuidadosamente controlados, incluindo o perfil de índice de refração, determinado pelo perfil de dopagem de germânio e responsável pelas características de transmissão de dados pela fibra óptica. Neste trabalho estudou-se o efeito da variação dos parâmetros de fabricação de preformas VAD principalmente, da geometria da preforma no perfil de dopagem de germânio, que foi obtido através da caracterização de amostras de preformas consolidadas por espectrometria de fluorescência de raios-X. Também foram apresentados uma metodologia e um sistema de automação em LabVIEW para a quantificação do perfil da superfície de deposição da preforma e determinação do perfil de dopagem de germânio em tempo real. Este estudo possibilitou a fabricação de preformas com perfil de dopagem com formato parabólico e triangular. Além disso, a implantação do sistema de automação permitiu determinar o tipo de fibra a ser produzida no início da deposição da preforma como também, reproduzir o perfil de dopagem, que é essencial para a viabilização comercial do processo VAD / Abstract: Fabrication of preforms for special optical fiber using VAD, "Vapor-phase Axial Deposition" tecnique has been in progress at the LIQC, UNlCAMP/FEM. ln this method, the processing parameters must be accurately controlled, particularly the refractive index profile determined by the germanium doping profile, which controls de data transmission characteristics in optical fiber. ln the present research, a study of VAD deposition parameters on the germanium doping profile of nanostructured preform was conducted. The quantitative analysis of germanium concentration was performed by X-ray fluorescence spectrometry. An automation system using LabVIEW was developed for data acquisition and analysis ofthe deposition surface profile of the preform and on-line determination of the germanium doping profile. As a result, the present development allowed the manufacture of various types of doping profile, such as parabolic and triangular shapes. Moreover, the determination of the type of fiber to be producedand its uniformity control during the process, as well as the reproduction of a specific doping profile were made possible using this system. Applications for industrial use becomes strategic / Mestrado / Engenharia de Materiais / Mestre em Engenharia Mecânica

Orientador: Carlos Kenichi Suzuki / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecanica / Made available in DSpace on 2018-08-04T09:09:03Z (GMT). No. of bitstreams: 1 Gusken_Edmilton_D.pdf: 6952554 bytes, checksum: 8821d17728533a1b9ab6e2f57e4b4f51 (MD5) Previous issue date: 2005 / Resumo: A emissão do érbio na região de comprimentos de onda usada em comunicações ópticas tem despertado grande interesse tecnológico, especialmente quando este é incorporado à matriz de sílica. Entretanto, a dificuldade maior está na sua inserção em concentrações elevadas e de forma homogênea, e mesmo na atualidade, o mecanismo de dopagem da sílica com érbio ainda não é totalmente conhecido. Nesta pesquisa, foi desenvolvido um esforço concentrado no trabalho de entender e controlar a nanoporosidade da sílica através de diversos parâmetros de fabricação usando a técnica de deposição axial fase vapor, e também por tratamento térmico posterior à deposição. Duas metodologias de dopagem do érbio foram utilizadas: (i) imersão da preforma de sílica nanoestruturada em solução de c1oretode érbio em etanol; e (ii) deposição simultânea da solução de érbio aspergido com nanopartículas de sílica sintetizados em chama de Hz/Oz. A utilização da primeira metodologia de dopagem, juntamente com os resultados de estudo de caracterização, tiveram como principal mérito o entendimento do mecanismo de incorporação do érbio em nível nanoestrutural. A segunda metodologia demonstrou a alta eficiência e economia do método com a incorporação de alguns milhares de ppm's atômico de érbio com a correspondente resposta fotoluminescente / Abstract: A special property of erbium to emit light in the wavelength used for optical communications has aroused great technological interest, particularly for erbium doped fiber and devices. However, the key point of this technology is to get high concentration and homogeneouserbium doping into silica structure. Even now, the doping mechanism of erbium in silica glass is still not well known. A research work to study and to control the nanoporosity in silica glass has presently been developed by using various processing parameters of vapor phase axial deposition technique. Post-deposition heat treatment to control the distribution of nanoporosity has also been applied. Two methods to dope erbium have been developed: (i) immersion of nanostructured silica preform into a solution of erbium chloride and ethanol, and (ii) simultaneousdeposition of silica nanopartic1es and vaporized erbium chloride in Hz/Oz flame. The merit of the first doping methodology was to understand the doping mechanism in nanostructurallevel. And the result of the second technique demonstrated a new procedure to obtain highIy efficient and low cost erbium doped silica preform containing a concentration of few thousands atomic ppm with corresponding photoluminescence response / Doutorado / Materiais e Processos de Fabricação / Doutor em Engenharia Mecânica

Doctor of Philosophy / Department of Chemistry / Daniel A. Higgins / This dissertation describes the application of wide-field single-molecule fluorescence microscopy techniques to investigations of DNA-surface interactions on chemically graded organosilane surfaces. The adsorption and desorption behaviors of double-stranded (ds) plasmid DNA along the amino-trimethoxysilane and octyl-trichlorosilane gradients were explored as a function of solution pH, solution ionic strength and surface properties. The results provide an improved fundamental understanding of DNA interactions with different surfaces and are certain to aid in the development and advancement of DNA-based biological and biomedical devices. Three distinct experiments were performed in completion of the work for this dissertation. In the first study, total internal reflection fluorescence (TIRF) microscopy was employed to study DNA interactions with aminosilane gradient surfaces under relatively acidic and basic environments. Electrical potentials were applied to assist DNA adsorption and desorption. The single-molecule data clearly showed that DNA capture and release was achieved on the monolayer and submonolayer coated regions of the aminosilane gradient surface under relatively basic pH conditions, with the help of an electrical potential. Meanwhile, DNA adsorption was found to be quasi-reversible on the multilayers at the high aminosilane end of the gradient in the relatively acidic solution. The results of these studies demonstrate the importance of manipulating the electrostatic interactions of DNA with charged surfaces in order to achieve DNA capture and release. The fundamental knowledge of the DNA-surface interactions gained in these studies will be helpful in diverse fields ranging from the layer-by-layer assembly of polyelectrolyte-based thin films to the selective electronic sensing of charged biomolecules. In the second study, the local dielectric properties of the least polar environments in dsDNA were assessed by using the solvatochromic dye, nile red, as a polarity-sensitive probe. TIRF spectroscopic imaging methods were employed in these studies. Although the dielectric constant within the least polar regions of dsDNA was previously predicted by theoretical and computational methods, no experimental measurements of its value had been reported to date. The results provide important knowledge of the factors governing the polarity of DNA microenvironments to which intercalators bind, and provide vital experimental support for the values determined in computational studies. In the third study, TIRF microscopy and single molecule tracking methods were employed to study DNA interactions with an opposed two-component C8-silane and aminosilane gradient surface as a function of solution pH. The mobility of surface-adsorbed DNA molecules was explored and quantified in these studies. The preliminary results further demonstrated the importance of electrostatic interactions over hydrophobic interactions in governing the adsorption of DNA to surfaces. The mobility of surface-adsorbed DNA was found to be largely independent of position along the two-component gradient. These studies were originally undertaken as a route to observation of cooperative effects that are believed to govern DNA-surface binding. Unfortunately, no clear evidence of cooperative effects was observed at the mixed regions of the two-component gradient surface.

Orientador: Carlos Kenichi Suzuki / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecânica / Made available in DSpace on 2018-08-19T09:14:43Z (GMT). No. of bitstreams: 1 Shimahara_AlbertoYassushi_M.pdf: 5253309 bytes, checksum: ba0303e6e0217876246733070863f5fc (MD5) Previous issue date: 2002 / Resumo: Neste trabalho estudou-se a morfologia e o tamanho dos agregados de sílica em preforma porosa preparadas pelo processo VAD por MEV em conjunto com um software analisador de imagens e suas relações com os parâmetros de deposição. As observações revelam que o tamanho dos agregados variam entre 0,06 à 0,30 ?m sendo influenciados principalmente pela temperatura, que é fortemente influenciada pela distância alvo/maçarico e pela razão H2/O2 empregado. No centro da preforma a dimensão média dos agregados é maior e se reduz ao longo do raio da preforma porosa, na qual ocorre uma tendência a uma distribuição bimodal na região externa da preforma e mono modal na direção central da preforma influenciada pelo movimento de rotação do alvo. Para distâncias alvo/maçarico pequenas nota-se que os agregados se pré-sinterizam, devido à alta temperatura da chama e para distâncias longas os agregados tendem a se aglomerar ligados fragilmente entre si, devido a pouca ação da chama sobre a superfície de deposição / Abstract: In this work we studied the morphology and size of silica aggregates in porous preform prepared by VAD with SEM in conjunction with a Image Analyzer software and the relations with the deposition parameters. The observations reveal that the size of aggregates vary between 0.06 to 0.30 ?m being mainly influenced by temperature, which is strongly influenced by the distance of the target/blowtorch and reason H2/O2. In the center of the preform the average size of aggregates is greater and reduces along the radius of the porous preform, which is a trend to a bimodal distribution in the outer region of the preform and mono-modal in central direction of preform influenced by the of rotation of the target. To small distances target/blowtorch; note that the aggregates are melted due to the high temperature of flame and for long distances the aggregates are weekly connected among themselves, because the small flame action over the surface / Mestrado / Materiais e Processos de Fabricação / Mestre em Engenharia Mecânica

Im Rahmen der Arbeit wurde eine neuartige Variante der Hochtemperatur-Gasphasenepitaxie (HTVPE) für die Herstellung von GaN entwickelt, die eine hohe Flexibilität und bessere Kontrolle des Züchtungsprozesses ermöglicht. Für die Realisierung des Konzeptes wurde eine Züchtungsanlage für die HTVPE entworfen und aufgebaut. Des Weiteren wurde ein numerisches Modell des Wärme- und Stofftransports entwickelt und für die Untersuchungen der Transportphänomene im HTVPE-Reaktor sowie für die Weiterentwicklung des Züchtungsreaktors verwendet. Die systematischen Züchtungsexperimente zeigten eine gute Übereinstimmung mit den Simulationsergebnissen und lieferten ein besseres Verständnis der HTVPE und ihres Anwendungspotentials. Die versbesserte Prozesskontrolle ermöglichte die erstmalige Anwendung der Niedertemperatur-Nukleation für die heteroepitaktische Abscheidung von GaN auf Saphir mit der HTVPE. Weiterhin wurden Wachstumsraten über 80 µm/h erreicht und das Potential der HTVPE für die Herstellung von GaN-Volumenschichten demonstriert.

Im Rahmen der Arbeit wurde eine neuartige Variante der Hochtemperatur-Gasphasenepitaxie (HTVPE) für die Herstellung von GaN entwickelt, die eine hohe Flexibilität und bessere Kontrolle des Züchtungsprozesses ermöglicht. Für die Realisierung des Konzeptes wurde eine Züchtungsanlage für die HTVPE entworfen und aufgebaut. Des Weiteren wurde ein numerisches Modell des Wärme- und Stofftransports entwickelt und für die Untersuchungen der Transportphänomene im HTVPE-Reaktor sowie für die Weiterentwicklung des Züchtungsreaktors verwendet. Die systematischen Züchtungsexperimente zeigten eine gute Übereinstimmung mit den Simulationsergebnissen und lieferten ein besseres Verständnis der HTVPE und ihres Anwendungspotentials. Die versbesserte Prozesskontrolle ermöglichte die erstmalige Anwendung der Niedertemperatur-Nukleation für die heteroepitaktische Abscheidung von GaN auf Saphir mit der HTVPE. Weiterhin wurden Wachstumsraten über 80 µm/h erreicht und das Potential der HTVPE für die Herstellung von GaN-Volumenschichten demonstriert.

Metallic bronze-Co-Ag alloys ranging from1-90 µm have been discovered in bomb and lava vesicles from the mafic volcanoes of Kilauea in Hawaii and Vesuvius, Stromboli and Etna in Italy. It is inferred that the metals for these alloys were transported (in part) as chloride complexes, and that the metal ratios in the alloys may be a function of S/Cl. Alloy compositions in each system are extremely heterogeneous with Co concentrations from 1% to 94%, Cu from 2% to 89%, Sn from 1% to 22% and Ag from 0.5% to 42%. Maximum abundances (in wt%) of other trace or minor elements are, Fe (3.0), Zn (0.11), As (0.50), Pd (0.05), Pt (0.05), Au (0.05), Hg (0.10) and Pb (.13) Spot analyses and element maps of alloy grains reveal that three major exsolved components exist. They are bronze, Co, and Ag. Kilauean alloys are dominantly Cu-Sn (bronze) with little Co and Ag while a systematic decrease in the bronze component and an increase in Co occurs in grains from Stromboli to Etna to Vesuvius. Element maps show a covariance of Cu and Sn while Co and Ag concentrations vary independently. Element maps of the alloys also reveal that chlorides are occasionally present in the same vesicles as the alloys. Sulphur content of the metal alloys rarely exceed about 0.4 wt%. Electron back-scatter diffraction (EBSD) was employed for lattice characterization of the exsolved phases and shows a FCC structure for the Cu-Sn section of the alloys. Cu-Sn alloys high in Sn are successfully indexed using the Cu6Sn5 pattern (hexagonal), even though the Sn:Cu ratio of our alloys is considerably lower than 5:6. Cu-Sn alloys containing significant subequal amounts of Co and Fe (≈5 wt% each) indexes as body-centered cubic (BCC). The presence of alloys suggests metal transport as complexes in a vapor phase before being reduced to native metals. Our current model for the origin of the alloys suggests that the metals are transported to vesicles as chlorides and then deposited as sulfides and/or native metals. Oxidation and removal of most of the S then occurs. This data suggests that in some circumstances Cu-Sn-Co and Ag are readily partitioned into escaping magmatic volatiles during quenching of mafic magma. Further examination into vesicle-hosted alloys may confirm that the ratio of Cu, Ag, Au, Zn, and Pb in vesicles reflects the ratio of available metals present in the magma and in subsequent ore deposits.

In dieser Arbeit wurde die atomare Struktur von Si(100)- und Ge(100)-Oberflächen untersucht, die mit metallorganischer chemischer Gasphasenabscheidung (MOCVD) für anschließende Heteroepitaxie von III-V-Halbleitern präpariert wurden. An der III-V/IV Grenzfläche werden atomare Doppelstufen auf der Substratoberfläche benötigt, um Antiphasenunordnung in den III-V-Schichten zu vermeiden. Die MOCVD-Prozessgasumgebung beeinflusst die Domänen- und Stufenbildung der Si- und Ge(100)-Oberfläche sehr stark. Deswegen wurden in situ Reflexions-Anisotropie-Spektroskopie (RAS) und Ultrahochvakuum-(UHV)-basierte oberflächensensitive Messmethoden verwendet, um die verschiedenen Oberflächen zu charakterisieren. In situ RAS ermöglicht die Identifizierung der Oberflächenstruktur und somit Kontrolle über die Oberflächenpräparation, insbesondere der Domänenbildung auf Si- und Ge(100). Beide Oberflächen wechselwirken stark mit dem H2-Prozessgas, was zu Monohydrid-Bedeckung während der Präparation führt und sogar zu Si-Abtrag während Präparation unter hohem H2-Druck. Die Erzeugung von Leerstellen auf den Terrassen bewirkt eine kinetisch bedingte Oberflächenstruktur, basierend auf Diffusion von Leerstellen und Atomen. Dadurch kommt es zu ungewöhnlichen DA-Doppelstufen auf verkippten Si(100)-Substraten während auf exakten Substraten ein schichtweiser Abtrag stattfindet. Unter niedrigem H2-Druck bildet sich eine energetisch bedingte Domänen- und Stufenstruktur. Während das H2-Prozessgas keinen direkten Einfluss auf die Stufen- und Domänenbildung von verkippten Ge(100)-Oberflächen zeigt, ist der Einfluss von Gruppe-V-Elemente entscheidend. Die As-terminierten Ge(100)-Oberflächen bilden eindomänige Oberflächen unterschiedlicher Dimerorientierung und Stufenstruktur abhängig von Temperatur und As-Quelle. Angebot von P an Ge(100)-Oberflächen durch Heizen in Tertiärbutylphosphin führt zu einer ungeordneten, P-terminierten Ge(100)-Oberfläche, die instabiler als die Ge(100):As-Oberfläche ist. / In this work, the atomic surface structure of Si(100) and Ge(100) surfaces prepared in metalorganic chemical vapor phase deposition (MOCVD) ambient was studied with regard to subsequent heteroepitaxy of III-V semiconductors. At the III-V/IV interface, double-layer steps on the substrate surface are required to avoid anti-phase disorder in the epitaxial film. The MOCVD process gas ambient strongly influences the domain and step formation of Si and Ge(100) surfaces. Therefore, in situ reflection anisotropy spectroscopy (RAS) and ultra-high vacuum-based (UHV) surface sensitive methods were applied to investigate the different surfaces. In situ RAS enabled identification of the surface structure and the crucial process steps, leading to complete control of Si and Ge(100) surface preparation. Both surfaces strongly interact with H2 process gas which leads to monohydride termination of the surfaces during preparation and Si removal during processing in high H2 pressure ambient. The generation of vacancies on the terraces induces a kinetically driven surface structure based on diffusion of vacancies and Si atoms leading to an energetically unexpected step structure on vicinal Si(100) substrates with DA-type double-layer steps, whereas Si layer-by-layer removal occurs on substrates with large terraces. Processing in low H2 pressure ambient leads to an energetically driven step and domain structure. In contrast, H2-annealed vicinal Ge(100) surfaces show no direct influence of the H2 ambient on the step structure. At the Ge(100) surface, group-V elements strongly influence step and domain formation. Ge(100):As surfaces form single domain surfaces with different majority domain and significantly different step structures depending on temperature and As source, respectively. In contrast, exposure to P by annealing in tertiarybutylphosphine leads to a very disordered P-terminated vicinal Ge(100) surface which is less stable compared to the Ge(100):As surfaces.