Binary oxides constitute an outstanding class of functional materials with potential applications in many fields such as catalysis, gas sensing, field emission, solar cells, photodetection, etc. Due to the difference in their physical/chemical properties, different oxides have been explored for different applications. For examples, SnO2, Cr2O3 and ZnO are being explored for gas sensing due to their high adsorption capacity for volatile gases, ZnO, Cu2O etc. are being explored in solar cells because of high adsorption coefficient in UV/visible region and so on. Various techniques are available for synthesis of binary oxides and tuning their properties. Most of the physical or chemical synthesis techniques are expensive, need high cost instruments and produces hazardous chemical waste. We need a simple, cost effective and ecofriendly techniques for the synthesis of binary oxides. In present work, a simple and facile thermal oxidation strategy has been employed for the synthesis of various binary oxides (Cu2O, GeO2 and ZnO). For example, CuO nanorods are obtained when Cu is heated around ~ 500 oC, which then heated in Ar atmosphere to obtain a film of porous Cu2O. Similarly, GeO2 with different morphologies and green-luminescent ZnO are obtained by controlling the reaction parameters. These oxides have then been explored for various applications including white light phosphors, catalysis for the degradation of dyes and non-contact thermometry. Overall, we present a thermal oxidation strategy for the synthesis of various binary oxides and explore potential applications in various fields.

Made available in DSpace on 2016-06-02T20:36:16Z (GMT). No. of bitstreams: 1 2035.pdf: 2216348 bytes, checksum: 3c9eeba4a9f95b09746c4737499e2dde (MD5) Previous issue date: 2008-08-22 / Universidade Federal de Sao Carlos / Some materials can be encapsulated with metals, inorganic solids and biomolecules, in a nanometric scale, to form a nanocomposite which has specific properties that can be open to research and technology works. In the literature, they are represented as core@shell. When silica particles are coated with a luminescent material, as the Eu2O3, the final material will have different properties from the core and the shell material. The silica used as a core in this work is the silica-germania VAD, synthesized by the Vapor-phase Axial Deposition (VAD) technique, which has been given by the PhD. Carlos K. Suzuki from FEM-UNICAMP. The luminescent properties of the Eu3+ ion in the SiO2-GeO2@Eu2O3 material, has been studied to get some information about the environment around this ion during the heat treatment process. The emission spectra of the samples presented the main Eu3+ characteristics 5D0→7FJ ( J= 0,1,2,3, 4) bands. The degradation of the polymeric shell which involves the Eu3+ ions degradation occurs as the temperature increases, causing structural changes around this ion. With its degradation, the Eu3+ ion is incorporated to the silica-germania matrix. The interaction between this ion and the matrix is through Ge-O-Eu linkages, which suppress the Eu3+ luminescence. The same luminescence behavior is observed for the SiO2@Eu2O3 and SiO2@Eu2O3 spherical samples heat treat in the same temperatures. The lifetime curves for these materials when they are excited in its respective maximum of emission and excitation, present a mono-exponential feature and the values are higher than Eu2O3 pure. This material presented some novel optical properties, which makes it in a potential candidate to be used in a photonic area. / Materiais quando encapsulados com metais, sólidos inorgânicos e biomoléculas, em escala nanométrica, formam um nanocompósito com propriedades específicas, que podem ser estendidas para diversas áreas da pesquisa e da tecnologia. Este material, na literatura, é designado como core shell ou core@shell. Quando a sílica é revestida com um material luminescente, como o Eu2O3, este material formado terá propriedades diferentes da sílica que constitui o núcleo e do Eu2O3 que constitui a nanocamada. Neste trabalho, a sílica utilizada no encapsulamento, foi a sílica-cermânia VAD, sintetizada pelo método Deposição por fase de vapor (VAD), que nos foi fornecida pelo Prof. Dr. Carlos K. Suzuki, da FEM - Unicamp. As propriedades luminescentes do íon Eu3+, no material SiO2-GeO2@Eu2O3 obtido, foram estudadas para se obter informações do ambiente em que este íon se encontra durante a calcinação do material. Os espectros de emissão das amostras obtidas apresentaram as bandas referentes às transições 5D0→7FJ (J= 0,1,2,3, 4), características do íon Eu3+. Com o aumento da temperatura, ocorre a degradação da camada polimérica que envolvia o íon Eu3+, causando mudanças estruturais ao seu redor. Com a sua degradação, o Eu3+ é incorporado á matriz de sílica. A interação deste íon com a matriz de sílica-germânia se dá através da formação de ligações Ge-O-Eu, que suprimem sua luminescência. O comportamento da luminescência deste íon foi semelhante ao observado nas amostras de SiO2@Eu2O3 e SiO2@Eu2O3 esférica tratadas nas mesmas temperaturas. As curvas de tempo de vida dos materiais quando excitados em seus respectivos máximos de emissão e excitação, apresentaram um comportamento monoexponencial e os valores são maiores quando comparados com o Eu2O3 puro. Este material apresentou algumas propriedades ópticas interessantes, que o torna um candidato em potencial para ser utilizado na área de fotônica.

Fiber Raman amplification using the transmission line is a promising technology to increase the repeater distance as well as the capacity of the communication systems. Because of the growing importance of fiber Raman amplification, it is desired to predict the magnitude and shape of the Raman gain spectrum from the doping level and refractive index profiles of different fiber designs. This thesis develops a method to predict the Raman gain coefficients and spectra for a pure silica core fiber and two different types of GeO2-doped silica fibers given their index profiles. An essential feature of the model is the inclusion of the variation in Raman gain coefficient over the mode field due to the variation in the Ge concentration across the fiber core. The calculated Raman gain coefficients were compared with measurements of the peak Raman gain on a step-index GeO2-doped fiber and with published measurements from various sources. Agreement between the calculated and measured peak gain for the step-index fiber was excellent. There was qualitative agreement with published measurements but there were significant differences between the calculated and published gain coefficients, which are not understood. Part of the work sought a way of predicting Raman gain coefficients from a standard gain curve given only the fiber type and the effective area. This approach appears promising for moderately-doped fibers with the proper choice of effective area. / Master of Science

Defects in the functional oxides play an important role in electronic devices like metal oxide semiconductor field effect transistors (MOSFETs) and resistive random-access memories (ReRAMs). The continuous scaling of CMOS has brought the Si MOSFET to its physical technology limit and the replacement of Si channel with Ge channel is required. However, the performance of Ge MOSFETs suffers from Ge/oxide interface quality and reliability problems, which originates from the charge traps and defect states in the oxide or at the Ge/oxide interface. The sub-oxide layers composed of GeII states at the Ge/GeO2 interface seems unavoidable with normal passivation methods like hydrogen treatment, which has poor electrical properties and is related to the reliability problem. On the other hand, ReRAM works by formation and rupture of O vacancy conducting filaments, while how this process happens in atomic scale remains unclear. In this thesis, density functional theory is applied to investigate the defect behaviours in oxides to address existing issues in these electronic devices. In chapter 3, the amorphous atomic structure of doped GeO2 and Ge/GeO2 interface networks are investigated to explain the improved MOSFET reliability observed in experiments. The reliability improvement has been attributed to the passivation of valence alternation pair (VAP) type O deficiency defects by doped rare earth metals. In chapter 4, the oxidation mechanism of GeO2 is investigated by transition state simulation of the intrinsic defect diffusion in the network. It is proposed that GeO2 is oxidized from the Ge substrate through lattice O interstitial diffusion, which is different from SiO2 which is oxidized by O2 molecule diffusion. This new mechanism fully explains the strange isotope tracer experimental results in the literature. In chapter 5, the Fermi level pinning effect is explored for metal semiconductor electrical contacts in Ge MOSFETs. It is found that germanides show much weaker Fermi level pinning than normal metal on top of Ge, which is well explained by the interfacial dangling bond states. These results are important to tune Schottky barrier heights (SBHs) for n-type contacts on Ge for use on Ge high mobility substrates in future CMOS devices. In chapter 6, we investigate the surface and subsurface O vacancy defects in three kinds of stable TiO2 surfaces. The low formation energy under O poor conditions and the +2 charge state being the most stable O vacancy are beneficial to the formation and rupture of conducting filament in ReRAM, which makes TiO2 a good candidate for ReRAM materials. In chapter 7, we investigate hydrogen behaviour in amorphous ZnO. It is found that hydrogen exists as hydrogen pairs trapped at oxygen vacancies and forms Zn-H bonds. This is different from that in c-ZnO, where H acts as shallow donors. The O vacancy/2H complex defect has got defect states in the lower gap region, which is proposed to be the origin of the negative bias light induced stress instability.