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Doctor of Philosophy / Department of Chemistry / Takashi Ito / Self-organized nanoporous materials have drawn a lot of attention because the uniform, highly dense, and ordered cylindrical nanopores in these materials provide a unique platform for chemical separations and chemical sensing applications. Here, we explore self-organized nanopores of PS-b-PMMA diblock copolymer thin films and anodic gallium oxide for chemical separations and sensing applications. In the first study, cyclic voltammograms of cytochrome c on recessed nanodisk-array electrodes (RNEs) based on nanoporous films (11, 14 or 24 nm in average pore diameter; 30 nm thick) derived from polystyrene-poly(methylmethacrylate) diblock copolymers were measured. The faradic current of cytochrome c was observed on RNEs, indicating the penetration of cytochrome c (hydrodynamic diameter ≈ 4 nm) through the nanopores to the underlying electrodes. Compared to the 24-nm pores, the diffusion of cytochrome c molecules through the 11- and 14-nm pores suffered significantly larger hindrance. The results reported in this study will provide guidance in designing RNEs for size-based chemical sensing and also for controlled immobilization of biomolecules within nanoporous media for biosensors and bioreactors. In another study, conditions for the formation of self-organized nanopores of a metal oxide film were investigated. Self-organized nanopores aligned perpendicular to the film surface were obtained upon anodization of gallium films in ice-cooled 4 and 6 M aqueous H2SO4 at 10 V and 15 V. The average pore diameter was in the range of 18 ~ 40 nm, and the anodic gallium oxide was ca. 2 µm thick. In addition, anodic formation of self-organized nanopores was demonstrated for a solid gallium monolith incorporated at the end of a glass capillary. Nanoporous anodic oxide monoliths formed from a fusible metal will lead to future development of unique devices for chemical sensing and catalysis. In the final study, surface chemical property of self-organized nanoporous anodic gallium oxide is explored through potentiometric measurements. The nanoporous anodic and barrier layer gallium oxide structures showed slow potentiometric response only at acidic pH (≤ 4), in contrast to metallic gallium substrates that exhibited a positive potentiometric response to H⁺ over the pH range examined (3-10). The potentiometric response at acidic pH probably reflects some chemical processes between gallium oxide and HCl.

abstract: Wide bandgap (WBG) semiconductors GaN (3.4 eV), Ga2O3 (4.8 eV) and AlN (6.2 eV), have gained considerable interests for energy-efficient optoelectronic and electronic applications in solid-state lighting, photovoltaics, power conversion, and so on. They can offer unique device performance compared with traditional semiconductors such as Si. Efficient GaN based light-emitting diodes (LEDs) have increasingly displaced incandescent and fluorescent bulbs as the new major light sources for lighting and display. In addition, due to their large bandgap and high critical electrical field, WBG semiconductors are also ideal candidates for efficient power conversion. In this dissertation, two types of devices are demonstrated: optoelectronic and electronic devices. Commercial polar c-plane LEDs suffer from reduced efficiency with increasing current densities, knowns as “efficiency droop”, while nonpolar/semipolar LEDs exhibit a very low efficiency droop. A modified ABC model with weak phase space filling effects is proposed to explain the low droop performance, providing insights for designing droop-free LEDs. The other emerging optoelectronics is nonpolar/semipolar III-nitride intersubband transition (ISBT) based photodetectors in terahertz and far infrared regime due to the large optical phonon energy and band offset, and the potential of room-temperature operation. ISBT properties are systematically studied for devices with different structures parameters. In terms of electronic devices, vertical GaN p-n diodes and Schottky barrier diodes (SBDs) with high breakdown voltages are homoepitaxially grown on GaN bulk substrates with much reduced defect densities and improved device performance. The advantages of the vertical structure over the lateral structure are multifold: smaller chip area, larger current, less sensitivity to surface states, better scalability, and smaller current dispersion. Three methods are proposed to boost the device performances: thick buffer layer design, hydrogen-plasma based edge termination technique, and multiple drift layer design. In addition, newly emerged Ga2O3 and AlN power electronics may outperform GaN devices. Because of the highly anisotropic crystal structure of Ga2O3, anisotropic electrical properties have been observed in Ga2O3 electronics. The first 1-kV-class AlN SBDs are demonstrated on cost-effective sapphire substrates. Several future topics are also proposed including selective-area doping in GaN power devices, vertical AlN power devices, and (Al,Ga,In)2O3 materials and devices. / Dissertation/Thesis / Doctoral Dissertation Electrical Engineering 2019

Orientador: Prof. Dr. Dalmo Mandelli / Tese (doutorado) - Universidade Federal do ABC. Programa de Pós-Graduação em Ciência e Tecnologia/Química, 2017. / A oxidacao de compostos organicos tem sido muito estudada nas ultimas decadas e e uma das areas de estudo mais atrativas da quimica moderna. Este tipo de reacao leva a obtencao de produtos de grande aplicacao na industria farmaceutica, de plasticos e fragrancias, como alcoois, cetonas e epoxidos. Varios trabalhos tem sido realizados no sentido de se desenvolver novos catalisadores ativos e seletivos, que tambem possuam custo e toxicidade relativamente baixos, com a finalidade de se obter processos que levem a quantidade cada vez menor de subprodutos e residuos de reacao, dentro do contexto da quimica-verde. Este trabalho foi dividido em duas partes, consistindo a primeira de um Planejamento de Experimentos Fracionario (27-4), nos quais foi possivel definir as principais variaveis que afetam a atividade catalitica dos oxidos de aluminio e galio, a saber: pH final, velocidade de resfriamento e solvente. Na segunda parte, estas variaveis foram exploradas em um Planejamento de Experimentos Completo 23. Por meio das analises de Fisissorcao de N2 e Dessorcao Termoprogramada de Amonia, foi possivel correlacionar algumas das propriedades fisico-quimicas dos catalisadores sintetizados com sua atividade catalitica. Com relacao a acidez dos catalisadores, pH e solvente apresentaram-se como as variaveis mais significativas: houve, em media, reducao da acidez em 1,0 mmolNH3 g-1 ao se realizar a sintese em pH 10 ao inves de pH 9 para Al2O3 e 1,1 mmolNH3 g-1 para Ga2O3; a troca de solvente de etilenoglicol por glicerol causou reducao de 0,60 mmolNH3 g-1 para Al2O3, enquanto houve um aumento de 1,2 mmolNH3 g-1 para Ga2O3. Para as propriedades fisicas, o solvente foi a variavel mais importante; os valores de area superficial, variaram entre 265 e 479 m2 g-1 para Al2O3, havendo um aumento medio de 136 m2 g-1 ao se utilizar glicerol, enquanto que os valores obtidos para Ga2O3 ficaram entre 81 e 280 m2 g-1, com efeito de positivo de 95 m2 g-1 ao se substituir etilenoglicol por glicerol. Com relacao as propriedades cataliticas, verificou-se que o uso de glicerol como solvente resultou em aumento medio de 10,1 % nos rendimentos para Al2O3 durante a epoxidacao de cicloocteno; os melhores resultados foram obtidos com rendimento de 53 % apos 6 h de reacao. Por outro lado, todos os oxidos de galio apresentaram rendimentos superiores a 98 % apos 4 h. A adicao dos acidos HNO3 e TFA como co-catalisadores da reacao de epoxidacao de cicloocteno com Al2O3 e Acido Acetico como co-catalisador do Ga2O3 causaram aumento substancial na velocidade inicial, mais que dobrando seu valor ao se utilizar os mesmos; por outro lado, a adicao de bases, como PCA, levaram a reducoes na atividade catalitica dos sistemas. Outros alquenos, como decen-1-eno, e terpenos, incluindo limoneno, ¿¿-pineno, linalol, geraniol e citral foram testados, resultando em rendimentos que variaram entre 19 e 51 % para A2O3 (10 h) e entre 31 e 100 % para Ga2O3 (7 h). / The oxidation of organic compounds has been much studied in recent decades and is one of the most attractive areas of study in modern chemistry. This type of reaction leads to the obtaining of products of great application in the pharmaceutical, plastics and fragrances industry, like alcohols, ketones and epoxides. Several works have been carried out in order to develop new active and selective catalysts, which also have relatively low cost and toxicity, in order to obtain processes that lead to the decreasing amount of by-products and reaction residues within the context of green chemistry. This work was divided in two parts, consisting the first of a Fractional Factorial Designs (27-4), in which it was possible to define the main variables that affect the catalytic activity of aluminum and gallium oxides, namely: final pH, cooling rate and solvent. In the second part, these variables were explored in a Complete Factorial Designs 23. Through the analysis of N2 Fisissorption and Thermoprogrammed Ammonia Desorption, it was possible to correlate some of the physicochemical properties of the catalysts synthesized with their catalytic activity. In relation to the acidity of the catalysts, pH and solvent were the most significant variables: there was, on average, acidity reduction of 1.0 mmolNH3 g-1 when the synthesis was performed at pH 10 instead of pH 9 for Al2O3 and 1.1 mmolNH3 g-1 for Ga2O3; The exchange of ethylene glycol solvent for glycerol caused a reduction of 0.60 mmolNH3 g-1 to Al2O3, while there was an increase of 1.2 mmolNH3 g-1 for Ga2O3. For the physical properties, the solvent was the most important variable; the values of surface area ranged from 265 to 479 m² g-1 for Al2O3, with an average increase of 136 m² g-1 when using glycerol, while Ga2O3 values were between 81 and 280 m² g-1, with positive effect of 95 m² g-1 when ethylene glycol was substituted by glycerol. Regarding the catalytic properties, it was found that the use of glycerol as solvent resulted in an average increase of 10,1 % in the yields for Al2O3 during cyclooctene epoxidation; the best results were obtained with 53% yield after 6 h of reaction. On the other hand, all gallium oxides presented yields higher than 98% after 4 h. The addition of the HNO3 and TFA acids as co-catalysts of the cyclooctene epoxidation reaction with Al2O3 and acetic acid as co-catalyst of Ga2O3 caused a substantial increase in the initial velocity, rather than doubling their values; on the other hand, the addition of bases, such as PCA, led to reductions in the catalytic activity of the systems. Other alkenes, such as dec-1-ene, and terpenes, including limonene, á-pinene, linalool, geraniol and citral were tested, giving yields ranging from 19 to 51 % for A2O3 (10 h) and between 31 and 100 % for Ga2O3 (7 h).

Die vorliegende Arbeit befasst sich mit der Untersuchung von weitbandlückigen Halbleitern mittels Raman-Spektroskopie. Diese wurde vorwiegend unter Verwendung von Licht einer Wellenlänge von 325 nm im ultravioletten Spektralbereich angeregt. Damit konnten zum einen aufgrund eines erhöhten Streuquerschnittes Messungen zur Probencharakterisierung durchgeführt werden, die mit Anregung im sichtbaren Spektralbereich nicht möglich gewesen wären. Zum anderen wurden bei dieser Anregungswellenlänge auftretende Resonanzeffekte untersucht. Dabei werden zwei verschiedene Materialsysteme behandelt: zum einen Kristalle mit Wurtzitstruktur und zum anderen binäre und ternäre Sesquioxide mit Metallionen der III. Hauptgruppe. An den Kristallen mit Wurtzitstruktur wurde die Streuung des Anregungslichts mit Energie oberhalb der Bandlücke an longitudinal-optischen (LO) Phononen untersucht. Die Streuung an einzelnen LO-Phononen wird unter diesen Anregungsbedingungen von einem Prozess dominiert, der eine elastische Streuung beinhaltet, durch die die Impulserhaltung verletzt wird. Es wurde ein Modell aufgestellt, dass zwischen einer elastischen Streuung an der Oberfläche und an Punktdefekten unterscheidet, und mit Hilfe von Experimenten verifiziert. Weiterhin wurde der Einfluss von Ladungsträgern auf die Energie der LO-Phononen untersucht und es wird eine Anwendung dieser Erkenntnisse zur Charakterisierung der Oberfläche von Zinkoxid vorgestellt. An den binären Oxiden des Galliums und Indiums wurden die Energien der Phononenmoden ermittelt und die resonante Verstärkung bei der verwendeten Anregungswellenlänge untersucht. Für das Galliumoxid wurde dabei insbesondere die Anisotropie des Materials berücksichtigt. Für das Indiumoxid wird dargestellt, dass durch die resonante Anregung alle Phononenmoden beobachtet werden können, was insbesondere auch die Bestimmung der Phononenmoden von Dünnschichtproben ermöglicht. Weiterhin waren Mischkristalle des Galliumoxids Untersuchungsgegenstand, in denen das Gallium teilweise durch Indium oder Aluminium ersetzt wurde. Die Phononenenergien wurden in Abhängigkeit der Zusammensetzung ermittelt und der Einfluss von strukturellen Eigenschaften darauf sowie das Auftreten von Phasenübergängen untersucht.

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The focus of this thesis is the investigation of thin-film transistors (TFTs) based on amorphous oxide semiconductors (AOSs) in two circuit applications. To date, circuits implemented with AOS-based TFTs have been primarily enhancement-enhancement inverters, ring oscillators based on these inverters operating at peak frequencies up to ~400 kHz, and two-transistor one-capacitor pixel driving circuits for use with organic light-emitting diodes (OLEDS). The first application investigated herein is AC/DC rectification using two circuit configurations based on staggered bottom-gate TFTs employing indium gallium oxide (IGO) as the active channel layer; a traditional full bridge rectifier with diode-tied transistors and a cross-tied full-wave rectifier are demonstrated, which is analogous to what has been reported previously using p-type organic TFTs. Both circuit configurations are found to operate successfully up to at least 20 MHz; this is believed to be the highest reported operating frequency to date for circuits based on amorphous oxide semiconductors. Output voltages at one megahertz are 9 V and ~10.5 V, respectively, when driven with a differential 7.07 Vrms sine wave. This performance is superior to that of previously reported organic-based rectifiers. The second AOS-based TFT circuit application investigated is an enhancement-depletion (E-D) inverter based on heterogeneous channel materials. Simulation results using models based on a depletion-mode indium zinc oxide (IZO) TFT and an enhancement-mode IGO TFT result in a gain of ~15. Gains of other oxide-based inverters have been limited to less than 2; the large gain of the E-D inverter makes it well suited for digital logic applications. Deposition parameters for the IGO and IZO active layers are optimized to match the models used in simulation by fabricating TFTs on thermally oxidized silicon and patterned via shadow masks. Integrated IGO-based TFTs exhibit a similar turn-on voltage and decreased mobility compared to the shadow masked TFTs. However, the integrated IZO-based TFTs fabricated to date are found to be conductive and exhibit no gate modulation. Due to the conductive nature of the load, the fabricated E-D inverter shows no significant output voltage variation. This discrepancy in performance between the integrated and shadow-masked IZO devices is attributed to processing complications. / Graduation date: 2009