Disertation (Ph.D.)--Worcester Polytechnic Institute. / Keywords: cyanopyridine; methylpyridine; pyridine; phototransposition; azaprefulvene Includes bibliographical references (317-321 ).

Si nanoparticles are new prospective optoelectronic materials. Unlike bulk Si cry-stals, Si nanoparticles display intriguing room-temperature photoluminescence. A major challenge in the fabrication of Si nanoparticles is the control of their size distribution. The rare-earth element Er has unique photo emission properties, including low pumping power, and a temperature independent, sharp spectrum. The emission wavelength matches the transmission window of optical fibers used in the telecommunications industry. Therefore, the study of Er-doped Si nanoparticles may have practical significance. The goals of the research described in this dissertation are to investigate vapor phase pyrolysis methods and to characterize the microstructure and associated defects, particles size distributions and photoluminescence efficiencies of doped and undoped Si nanoparticles using analytical transmission electron microscopy, high resolution electron microscopy, and optical spectroscopy. Er-doped and undoped Si nanoparticles were synthesized via vapor-phase pyrolysis of disilane at Texas Christian University. To achieve monodisperse size distributions, a process with fast nucleation and slow growth was employed. Disilane was diluted to 0.48% with helium. A horizontal pyrolysis oven was maintained at a temperature of 1000 °C. The oven length was varied from 1.5 cm to 6.0 cm to investigate the influence of oven length on the properties of the nanoparticles. The Si nanoparticles were collected in ethylene-glycol. The doped and undoped Si nanoparticles have a Si diamond cubic crystal structure. Neither Er precipitation, Er oxides or Er silicides were detected in any of the samples. The Er dopant concentration was about 2 atom% for doped samples from the 3.0 and 6.0 cm ovens as determined by quantitative analysis using X-ray energy dispersive spectroscopy. The average Si nanoparticle size increases from 11.3 to 15.2 nm in the doped samples and from 11.1 to 15.7 nm in the undoped samples as the oven length increases from 1.5 to 6.0 cm. HREM data show that average Si nanocrystallite size varies from 6.4 to 3.3 to 5.9 nm in the doped samples, and from 7.5 to 12.2 nm in the undoped samples as the oven length increases. Room-temperature Er photoluminescence has been detected near 1.54 :m from all doped samples. Saturation of the Er photoluminescence intensity at large emission power and the monotonic decrease of the intensity as a function of the emission wavelength in the doped sample from the 3.0 cm oven suggest that a carrier-mediated energy transfer process occurs in the Er-doped Si nanoparticles. It is the first time to successfully fabricate and investigate Er-doped Si nanoparticles.

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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

京都大学 / 0048 / 新制・課程博士 / 博士(エネルギー科学) / 甲第20097号 / エネ博第344号 / 新制||エネ||69(附属図書館) / 33213 / 京都大学大学院エネルギー科学研究科エネルギー社会・環境科学専攻 / (主査)教授 坂 志朗, 教授 髙野 俊幸, 准教授 河本 晴雄 / 学位規則第4条第1項該当 / Doctor of Energy Science / Kyoto University / DGAM

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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.

Conductive polymers, since from their discovery, have become a prominent area of research and found many useful applications in all fields of our daily life. Examples are light emitting diodes, heat generation, chemical sensors and electro-active membranes. Polymer coated textile substrates give flexible and lightweight materials. One well utilized and thoroughly explored conductive polymer is poly(3,4-ethylenedioxythiophene) also known as PEDOT. Although there are different ways to produce PEDOT one of the most common is the VPP technique. The typical procedure when using VPP is to introduce the monomer vapor to an oxidant coated substrate so that it polymerizes on the surface of the substrate. Throughout this study, the VPP technique has been used to produce PEDOT on different textile fibers. Aim was first of all optimizing the process gaining low electric resistance, i. e. high conductivity, of produced coated fibers but also multilayer coatings of fibers. Outcome indicates some parameters not having a clear influence over the results while others had a more distinct impact. A noteworthy result was obtained by coating a substrate, namely lyocell fiber, multiple times with layers deposited directly on each other. This decreased the resistance from 5.1 (± 1.6) kΩ/10 cm to 1.0 (± 0.1) kΩ/10 cm, for one layer and multiple layers respectively. Adding 15 wt. % of the copolymer PEG-PPG-PEG to the oxidant solution decreased the resistance from 6.8 (± 1.2) kΩ/10 cm to 3.9 (± 0.8) kΩ/10 cm. Final conclusion is that among the ways, to improve conductivity for PEDOT coated fibers, applied in this study are best results obtained by multi-layer coating.

Doctor of Philosophy / Department of Chemical Engineering / James H. Edgar / The semiconductor boron phosphide (BP) has many outstanding features making it attractive for developing various electronic devices, including neutron detectors. In order to improve the efficiency of these devices, BP must have high crystal quality along with the best possible electrical properties. This research is focused on growing high quality crystalline BP films on a variety of superior substrates like AIN, 4H-SiC, 3C-SiC and ZrB₂ by chemical vapor deposition. In particular, the influence of various parameters such as temperature, reactant flow rates, and substrate type and its crystalline orientation on the properties of BP films were studied in detail. Twin-free BP films were produced by depositing on off-axis 4H-SiC(0001) substrate tilted 4° toward [1-100] and crystal symmetry matched zincblende 3C-SiC. BP crystalline quality improved at higher deposition temperature (1200°C) when deposited on AlN, 4H-SiC, whereas increased strain in 3C-SiC and increased boron segregation in ZrB₂ at higher temperatures limited the best deposition temperature to below 1200°C. In addition, higher flow ratios of PH₃ to B₂H₆ resulted in smoother films and improved quality of BP on all substrates. The FWHM of the Raman peak (6.1 cm⁻¹), XRD BP(111) peak FWHM (0.18°) and peak ratios of BP(111)/(200) = 5157 and BP(111)/(220) = 7226 measured on AlN/sapphire were the best values reported in the literature for BP epitaxial films. The undoped films on AlN/sapphire were n-type with a highest electron mobility of 37.8 cm²/V·s and a lowest carrier concentration of 3.15x1018 cm⁻ᶟ. Raman imaging had lower values of FWHM (4.8 cm⁻¹) and a standard deviation (0.56 cm⁻¹) for BP films on AlN/sapphire compared to 4H-SiC, 3C-SiC substrates. X-ray diffraction and Raman spectroscopy revealed residual tensile strain in BP on 4H-SiC, 3C-SiC, ZrB₂/4H-SiC, bulk AlN substrates while compressive strain was evident on AlN/sapphire and bulk ZrB₂ substrates. Among the substrates studied, AlN/sapphire proved to be the best choice for BP epitaxy, even though it did not eliminate rotational twinning in BP. The substrates investigated in this work were found to be viable for BP epitaxy and show promising potential for further enhancement of BP properties.