Abstract SrTiO3 is cubic at room temperature, and retains cubic until the phase transition to tetragonal at 105K (-168oC). It is a wide-band-gap semiconductor having an energy gap Eg ≈ 3.0 eV, when its semiconductivity is greatly improved by doping with donor oxides, e.g.Nb2O5 or heat treatment in low oxygen partial pressures (Po2). Donor oxides in solid solution with SrTiO3 forming substitutional defects create electron or cation vacancies as the principal charge compensation defect. In-gap levels are also modified by the oxygen partial pressure (Po2) adopted in sintering, which generates oxygen vacancies in order to maintain the overall charge neutrality in the ceramic. In this research, donor-doping and Po2 used in sintering are investigated for the in-gap-level modification using the cathodoluminescence (CL) spectrometry equipped with a scanning electron microscope (SEM). Other analytical techniques, e.g. transmission electron microscopy (TEM) will be used for characterizing the defect structure. Preliminary results suggest that the in-gap levels are registered at 3.10 eV and 2.69 eV, representing the intrinsic Eg and a donor-level created by oxygen vacancies, respectively.

The high magnetoresistance is one of the most important properties that led the colossal magnetoresistance (CMR) materials been kept attention, however, because of the low phase transition temperature (Tp) and Curie temperature (TC) limits the application of the materials. The Tp could be influenced by many factors, as for the R1-xAxMnO3(R=rare earth element, A=alkaline metal, 0¡Õx¡Õ1) CMR materials, the selections of elements on R, A, and the ratio of x would make the difference. Besides these factors, when the film was grown on a substrate, the strain effect initiated at the substrate/film interface plays an essential role on the change of Tp and other physic properties. In other hand, the Sr element, existed in the SrTiO3(100) substrate, may also diffuse into the thin films during growth and alter the composition of the film and change its physic properties. In this thesis, we mainly focused on the modifying of the surface of substrates to prevent the diffusion problems. A wet chemical method was applied to modify the top layer of substrates such that the surface layer of the substrate is consisted of Ti-O layer only. By varying the high temperature annealing and etching processes, an optima processing condition was established.

<p>I want delay publication of my dissertation until April 30 2013. Thanks.</p> / <p>Strontium titanate (SrTiO₃) has a wide range of applications in the electronic industry and attracts growing world-widely interest recently because of novel discoveries at its surfaces, interfaces and with selected dopants. The understanding of some of the structural properties of SrTiO₃ and its optical properties have been lagging due to limited characterization techniques available to study single monolayers and dopants in this material.</p> <p>In the present thesis, pure SrTiO₃ single crystals with (2x1) and c(4x2) surface patterns were synthesized and samples (Pr, Al) doped SrTiO₃ were prepared through ion implantation. The atomic and electronic structures of these samples were investigated by various high-resolution imaging and spectroscopic techniques available in an aberration-corrected transmission electron microscope. Particularly, the direct imaging of individual light atoms and vacancies within a bulk material containing heavier elements was demonstrated for the first time via the STEM-annular dark-field (ADF)/annular bright-field (ABF) images. In addition, the first electron energy-loss spectroscopy (EELS) 2-dimensional maps of dopants located in a lattice were obtained. These results provided a solid foundation regarding the mechanism of red light emission in doped SrTiO₃. More importantly, a new experimental approach allowing the effective extraction of weak EELS signals from low-dimensional defects was developed and successfully applied to understand the chemical state and coordination of Ti cations within a single monolayer on a reconstructured SrTiO₃surface and the local defect configurations of injected Pr⁺ and Al⁺ ions within SrTiO₃ single crystals.</p> / Doctor of Philosophy (PhD)

Amostras nanoestruturadas do sistema SrTi1-xMnxO3 (STM) com x = 0%, 0.5%, 1%, 2.5%, 5% e 10% na forma de pó foram sintetizadas através do método dos precursores poliméricos. As propriedades térmicas, estruturais e ópticas das amostras STM calcinadas em diferentes temperaturas foram analisadas a temperatura ambiente através de técnicas de análise térmica, difração de raios-x, espectroscopia de absorção de raios-x e fotoluminescência. Os resultados obtidos através das técnicas de analise térmica mostraram que o íon manganês causa um efeito retardante, aumentando a temperatura onde ocorre o início da cristalização. Os resultados de DRX mostraram que no limite de solubilidade estudado, o íon manganês foi incorporado em solução sólida no sítio B na rede do SrTiO3 (ST), assumindo estados de oxidação entre +3,4 e +3,7, indicando que ocorre a criação de defeitos para compensação de cargas, mantendo a neutralidade elétrica do material. A análise dos espectros de fotoluminescência das amostras STM amorfas mostrou que o aumento da quantidade de manganês até 1% leva a um aumento da intensidade fotoluminescência em relação a amostra SrTiO3. Entretanto, a adição de manganês acima desta quantidade leva a uma diminuição pronunciada da intensidade fotoluminescente. Nas amostras amorfas não foi observada uma variação significativa da ordem local ao redor dos átomos de titânio bem como no estado de oxidação dos átomos de manganês à medida que a quantidade de manganês aumenta. Desta forma, a variação da intensidade fotoluminescente não pôde ser atribuída a estes fatores. O aumento da temperatura de calcinação leva a uma diminuição significativa da intensidade fotoluminescente. Uma análise dos espectros XANES medidos na borda K do titânio destas amostras mostrou que ocorre uma maior ordenação dos átomos de Ti nos octaedros de oxigênio [TiO6] a medida que a temperatura de calcinação aumenta, ou seja, à medida que aumenta o grau de cristalinidade das amostras. / Nanostructured SrTi1-xMnxO3 (STM) powder samples with x = 0%, 0.5%, 1%, 2.5%, 5% and 10% were synthesized by the polymeric precursors method. The thermal, structural and optical properties of STM samples heat-treated at different temperatures were analyzed by thermal analysis, X-ray diffraction, X-ray absorption spectroscopy and photoluminescence techniques. The thermal analysis results have shown that manganese ion causes a retarding effect, increasing the onset of the crystallization temperature. The XRD results showed that manganese ion is incorporated in a solid solution in the B site of the SrTiO3 (ST) network for the range of solubility studied, with oxidation states between +3.4 and +3.7, indicating the creation of charge compensation defects, keeping the materials electrical neutrality. The analysis of the photoluminescence (PL) spectra of the STM amorphous samples showed that the PL intensity increases when the amount of manganese is up to 1%. However, higher manganese concentrations leads to a pronounced decrease of the photoluminescence intensity. The amorphous samples showed no significant change of the local order around the titanium atoms, observed as well as in the oxidation state of the manganese atoms as the amount of manganese increases. Thus, the variation of the photoluminescence intensity cannot be explained by these factors. Increasing the calcination temperature leads to a significant decrease of the photoluminescence intensity. An analysis of the XANES spectra measured at the titanium K edge of these samples showed that as the calcination temperature increases, i. e., as it increases the degree of crystallinity, the ordering of the Ti atoms in the oxygen octahedra TiO6 of the samples increases.

O titanato de estrôncio (SrTiO3) é um óxido de estrutura perovskita e tem sido intensamente estudado para uso em diversas aplicações, entre elas, como suporte catalítico. Entretanto, sua utilização especificamente na reação de deslocamento gás-água ainda é pouco explorada. Esta reação é de interesse para a produção de hidrogênio livre de CO, necessário para aplicações como o abastecimento de células de combustível. Este trabalho de tese teve como objetivo o estudo dos compostos SrTi1-xCuxO3, CuO/SrTiO3 e NiO/SrTiO3 como catalisadores para a reação de deslocamento gás-água, uma vez que, dentre os metais de baixo custo, Cu e Ni são altamente ativos para esta reação. As amostras SrTi1-xCuxO3 foram sintetizadas pelo método dos precursores poliméricos com calcinação em N2 e O2, possibilitando a obtenção de partículas de maior área superficial em comparação com a calcinação convencional em atmosfera ambiente. Para as amostras CuO/SrTiO3 e NiO/SrTiO3, o suporte SrTiO3, foi sintetizado pelo método de sol-precipitação e a impregnação com cobre e níquel foi realizada por via úmida. As técnicas de absorção e difração de raios-X in situ em condições de reação mostraram a estabilidade da estrutura e do estado de oxidação após o tratamento de redução. Imagens de microscopia eletrônica de varredura (MEV) e de transmissão (TEM) em conjunto com a espectroscopia de raios-X de energia dispersiva (EDX) foram utilizadas a fim de estabelecer uma relação entre a atividade catalítica e o teor a dispersão de fase ativa sobre o suporte. Todas as composições estudadas se mostraram ativas entre 250 e 350&deg;C, entretanto, a composição NiO/SrTiO3 com 10% de Ni apresentou o melhor resultado, com uma conversão de CO a 350&deg;C, próxima ao equilíbrio e estável por um período mínimo de10 h. / Strontium titanate (SrTiO3) is an oxide of perovskite structure and has been extensively studied for use in several applications, including as catalytic support. However, its use specifically in the water-gas shift reaction is still little explored. This reaction is of interest for the production of CO-free hydrogen, required for applications such as in fuel cell. This work aimed to study SrTi1-xCuxO3, CuO/SrTiO3 and NiO/SrTiO3 compounds to be applied as catalysts for the water-gas shift reaction, since, among the low-cost metals, Cu and Ni are highly active for this reaction. The SrTi1-xCuxO3 samples were synthesized by the polymeric precursor method with the samples submitted to a N2 and O2 calcination, making possible to obtain particles with a larger surface area compared to conventional calcination in ambient atmosphere. For the CuO/SrTiO3 and NiO/SrTiO3 samples, the SrTiO3 support was synthesized by the sol-precipitation method and the impregnation with copper and nickel on the support was performed by a wet method. The in situ X-ray absorption and diffraction techniques under reaction conditions showed the stability of the structure and the oxidation state after the reduction treatment. Scanning electron microscopy (SEM) and transmission (TEM) images in conjunction with energy dispersive X-ray spectroscopy (EDX) were used in order to establish a relationship between the catalytic activity and the content and dispersion of the active phase on the support. All the compositions studied were active at 250 to 350 &deg;C, however, the NiO/SrTiO3 sample with 10% of Ni presented the best result, with a CO conversion at 350 &deg;C, close to equilibrium and stable for a minimum of 10 h.

O titanato de estrôncio (SrTiO3) é um óxido de estrutura perovskita e tem sido intensamente estudado para uso em diversas aplicações, entre elas, como suporte catalítico. Entretanto, sua utilização especificamente na reação de deslocamento gás-água ainda é pouco explorada. Esta reação é de interesse para a produção de hidrogênio livre de CO, necessário para aplicações como o abastecimento de células de combustível. Este trabalho de tese teve como objetivo o estudo dos compostos SrTi1-xCuxO3, CuO/SrTiO3 e NiO/SrTiO3 como catalisadores para a reação de deslocamento gás-água, uma vez que, dentre os metais de baixo custo, Cu e Ni são altamente ativos para esta reação. As amostras SrTi1-xCuxO3 foram sintetizadas pelo método dos precursores poliméricos com calcinação em N2 e O2, possibilitando a obtenção de partículas de maior área superficial em comparação com a calcinação convencional em atmosfera ambiente. Para as amostras CuO/SrTiO3 e NiO/SrTiO3, o suporte SrTiO3, foi sintetizado pelo método de sol-precipitação e a impregnação com cobre e níquel foi realizada por via úmida. As técnicas de absorção e difração de raios-X in situ em condições de reação mostraram a estabilidade da estrutura e do estado de oxidação após o tratamento de redução. Imagens de microscopia eletrônica de varredura (MEV) e de transmissão (TEM) em conjunto com a espectroscopia de raios-X de energia dispersiva (EDX) foram utilizadas a fim de estabelecer uma relação entre a atividade catalítica e o teor a dispersão de fase ativa sobre o suporte. Todas as composições estudadas se mostraram ativas entre 250 e 350&deg;C, entretanto, a composição NiO/SrTiO3 com 10% de Ni apresentou o melhor resultado, com uma conversão de CO a 350&deg;C, próxima ao equilíbrio e estável por um período mínimo de10 h. / Strontium titanate (SrTiO3) is an oxide of perovskite structure and has been extensively studied for use in several applications, including as catalytic support. However, its use specifically in the water-gas shift reaction is still little explored. This reaction is of interest for the production of CO-free hydrogen, required for applications such as in fuel cell. This work aimed to study SrTi1-xCuxO3, CuO/SrTiO3 and NiO/SrTiO3 compounds to be applied as catalysts for the water-gas shift reaction, since, among the low-cost metals, Cu and Ni are highly active for this reaction. The SrTi1-xCuxO3 samples were synthesized by the polymeric precursor method with the samples submitted to a N2 and O2 calcination, making possible to obtain particles with a larger surface area compared to conventional calcination in ambient atmosphere. For the CuO/SrTiO3 and NiO/SrTiO3 samples, the SrTiO3 support was synthesized by the sol-precipitation method and the impregnation with copper and nickel on the support was performed by a wet method. The in situ X-ray absorption and diffraction techniques under reaction conditions showed the stability of the structure and the oxidation state after the reduction treatment. Scanning electron microscopy (SEM) and transmission (TEM) images in conjunction with energy dispersive X-ray spectroscopy (EDX) were used in order to establish a relationship between the catalytic activity and the content and dispersion of the active phase on the support. All the compositions studied were active at 250 to 350 &deg;C, however, the NiO/SrTiO3 sample with 10% of Ni presented the best result, with a CO conversion at 350 &deg;C, close to equilibrium and stable for a minimum of 10 h.

Amostras nanoestruturadas do sistema SrTi1-xMnxO3 (STM) com x = 0%, 0.5%, 1%, 2.5%, 5% e 10% na forma de pó foram sintetizadas através do método dos precursores poliméricos. As propriedades térmicas, estruturais e ópticas das amostras STM calcinadas em diferentes temperaturas foram analisadas a temperatura ambiente através de técnicas de análise térmica, difração de raios-x, espectroscopia de absorção de raios-x e fotoluminescência. Os resultados obtidos através das técnicas de analise térmica mostraram que o íon manganês causa um efeito retardante, aumentando a temperatura onde ocorre o início da cristalização. Os resultados de DRX mostraram que no limite de solubilidade estudado, o íon manganês foi incorporado em solução sólida no sítio B na rede do SrTiO3 (ST), assumindo estados de oxidação entre +3,4 e +3,7, indicando que ocorre a criação de defeitos para compensação de cargas, mantendo a neutralidade elétrica do material. A análise dos espectros de fotoluminescência das amostras STM amorfas mostrou que o aumento da quantidade de manganês até 1% leva a um aumento da intensidade fotoluminescência em relação a amostra SrTiO3. Entretanto, a adição de manganês acima desta quantidade leva a uma diminuição pronunciada da intensidade fotoluminescente. Nas amostras amorfas não foi observada uma variação significativa da ordem local ao redor dos átomos de titânio bem como no estado de oxidação dos átomos de manganês à medida que a quantidade de manganês aumenta. Desta forma, a variação da intensidade fotoluminescente não pôde ser atribuída a estes fatores. O aumento da temperatura de calcinação leva a uma diminuição significativa da intensidade fotoluminescente. Uma análise dos espectros XANES medidos na borda K do titânio destas amostras mostrou que ocorre uma maior ordenação dos átomos de Ti nos octaedros de oxigênio [TiO6] a medida que a temperatura de calcinação aumenta, ou seja, à medida que aumenta o grau de cristalinidade das amostras. / Nanostructured SrTi1-xMnxO3 (STM) powder samples with x = 0%, 0.5%, 1%, 2.5%, 5% and 10% were synthesized by the polymeric precursors method. The thermal, structural and optical properties of STM samples heat-treated at different temperatures were analyzed by thermal analysis, X-ray diffraction, X-ray absorption spectroscopy and photoluminescence techniques. The thermal analysis results have shown that manganese ion causes a retarding effect, increasing the onset of the crystallization temperature. The XRD results showed that manganese ion is incorporated in a solid solution in the B site of the SrTiO3 (ST) network for the range of solubility studied, with oxidation states between +3.4 and +3.7, indicating the creation of charge compensation defects, keeping the materials electrical neutrality. The analysis of the photoluminescence (PL) spectra of the STM amorphous samples showed that the PL intensity increases when the amount of manganese is up to 1%. However, higher manganese concentrations leads to a pronounced decrease of the photoluminescence intensity. The amorphous samples showed no significant change of the local order around the titanium atoms, observed as well as in the oxidation state of the manganese atoms as the amount of manganese increases. Thus, the variation of the photoluminescence intensity cannot be explained by these factors. Increasing the calcination temperature leads to a significant decrease of the photoluminescence intensity. An analysis of the XANES spectra measured at the titanium K edge of these samples showed that as the calcination temperature increases, i. e., as it increases the degree of crystallinity, the ordering of the Ti atoms in the oxygen octahedra TiO6 of the samples increases.

The electronic structure at interface between two insulators LaAlO3 and SrTiO3 has been investigated by using scanning tunneling microscopy and spectroscopy. The atomic-scale interfacial band structure is also demonstrated in the work with the consideration of the tip-induced band bending effect. Experimental results indicate that the magnitude of the built-in field across LaAlO3 is 0.075¡Ó0.005 V/Å. The band bending on SrTiO3 side at the heterointerface is observed. The band downshift of SrTiO3 side at the interface is 0.1 eV with ~1 nm decay length.

In this work, the interfacial electronic property between N-type LaAlO3/TiO2-SrTiO3 has been investigated by using scanning tunneling microscopy and spectroscopy (STM/S). With the consideration of the tip-induced band bending effect during STM measurements and in conjunction with the three-dimensional theoretically analysis, the schematic band structure of the hetero-structured SrTiO3/LaAlO3 is also revealed. Results indicate that the magnitude of the built-in field on the LaAlO3 is (30¡Ó5) mV/Å. The band bending on SrTiO3 side at the heterointerface is also observed. The band downshift of SrTiO3 side at the interface is 0.31 eV with about 0.8 nm decay length.

Heterogeneous nanostructures such as coaxial nanotubes, nanowires and nanorods have been of growing interest due to their potential for high energy-conversion efficiencies and charge/discharge rates in solar cell, energy storage and fuel cell applications. Their superior properties at nanoscale as well as their high surface area, fast charge transport along large interfacial contact areas, and short charge diffusion lengths have made them attractive components for next generation high efficiency energy-conversion devices. The primary focus of this work was to understand the doping mechanism of TiO2 nanotube exclusively with strontium as an alkaline earth metal to shine light on the relation between the observed enhancement in photocatalytic properties of doped TiO2 nanotubes and its structural and electronic characteristics. The mechanism of Sr incorporation into the TiO2 nanotube structure with the hypothesis of possibility of phase segregation has been explored in low concentrations as a dopant and in very high concentrations by processing of SrTiO3 nanotube arrays. Detailed experimental examination of the bulk and surface of the Sr-doped nanotubes has been performed to understand the effect of dopant on electronic structure and optical properties of the TiO2 nanotubes. Moreover, in order to minimize the polarizations associated with the ionic/electronic charge transport in the electrolyte and anode of solid oxide fuel cells (SOFCs), a new platform is developed using vertically oriented metal oxide nanotube arrays. This novel platform, which is made of coaxial oxide nanotubes on silicon substrates, has the potential to simultaneously lower the operating temperature and production cost leading to significant enhancement in the performance of micro-SOFCs.