Neste trabalho estudamos as propriedades eletrônicas e as estabilidades estruturais do cristal de ZrO2 e dos defeitos de vacância de oxigênio e impureza substitucional de cério. As investigações foram efetuadas através de simulações computacionais baseadas em métodos de primeiros princípios dentro do formalismo da teoria do funcional da densidade e utilizando o método APW + lo (Aumengted Plane Waves plus local orbitals), implementado no código computacional WIEN2k, dentro do esquema de supercélula, com relaxações atômicas tratadas de modo apropriado. A zircônia apresenta 3 fases estruturais, dependendo da temperatura. Sua fase mais estável é a monoclínica e, a altas temperaturas, ela apresenta as fases tetragonal e cúbica, sendo estas duas últimas as mais importantes para aplicações tecnológicas. Ela pode ser estabilizada em uma condição metaestável em uma estrutura quase cúbica quando crescida na forma de pós nanocristalinos, com tamanhos menores que um certo tamanho crítico. Outra maneira de se estabilizar as estruturas cúbica e tetragonal, a temperatura ambiente, é através da adição de dopantes, entre eles o cério. Nesses casos, estão sempre presentes vacâncias de oxigênio. Neste trabalho, para o cristal puro de ZrO2, foram calculadas as propriedades das estruturas cristalinas cúbica e tetragonal, constatando-se que a estrutura quase cúbica, proposta em várias investigações relatadas na literatura, pode ser interpretada como uma estrutura tetragonal de corpo centrado, com pequenos deslocamentos dos átomos de oxigênio na direção k . Destes resultados, propomos que nas análises dos dados experimentais obtidos por difração de raios-X e EXAFS (Extended X-ray Absorption Fine Structure) sejam utilizadas simulações onde a estrutura tetragonal de corpo centrado seja considerada como uma possível estrutura para o cristal. Dos estudos da vacância de oxigênio, obtivemos que sua presença quebra a simetria local do sistema e faz com que existam três diferentes distâncias entre um átomo de Zr e os átomos primeiros vizinhos de oxigênio, podendo, também, explicar resultados experimentais de difração de raios-X e EXAFS. Para o centro de impureza substitucional de Ce no sítio do átomo de Zr, nossos resultados apresentam uma possível explicação de porque as impurezas de Ce, em diferentes concentrações, estabilizam o ZrO2 nas estruturas tetragonal e cúbica. / In this investigation we studied the electronic properties and the structural stabilities of zirconia (ZrO2), as well as oxygen vacancy and Ce substitutional impurity. The investigations were carried by computational simulations using ab initio methods, based on the density functional theory and the APW + lo (Aumengted Plane Waves plus local orbitals) method, as implemented in the WIEN2k code, considering the supercell approach and atomic relaxations. Concerning the ZrO2 bulk, the tetragonal (quasi-cubic) phase is not thermodynamically stable at room temperature, but it can be retained in a metastable condition in nanocrystalline powders with crystallite sizes smaller than a certain critical size, or throught addition of dopants, for example cerium. In this cases, oxygen vacancies are always present. In this work we have obtained the properties of the cubic and tetragonal phases of ZrO2. From the results, we propose that the quasi-cubic structure presented in many articles can be understood as a body centered tetragonal structure, with small oxygen atoms displacement perpendicular to the k direction. Those results suggest that the analysis of the X-ray and EXAFS (Extended X-ray Absorption Fine Structure) data should include in the crystallographic model the body-center tetragonal structure. The results of the structural and electronic properties of the oxygen vacancy suggest that its presence could explain the different models of the Zr first neighbor oxygen shell. For the Ce substitutional impurity, our results present a possible explanation why these impurities, in several concentrations, are able to stabilize the ZrO2 in the tetragonal and cubic phases.

No presente trabalho, foram investigadas propriedades de absorção óptica e termoluminescência para sete variedades de quartzo natural brasileiro (Azul, com enxofre, leitoso, rosa, verde, vermelho e preto). Para efeitos comparativos, empregou-se o quartzo hialino e o sintético, ambos na fase alfa. Ametista e citrino não foram estudados devido ao número grande de relatos na literatura destes materiais. A difração de raios-X mostrou que todas as variedades de quartzo estudadas possuem a mesma estrutura padrão de quartzo. A composição das amostras obtidas por Fluorescência de Raios-X e Espectroscopia de Massas com Plasma (ICP-MS), revelam a presença de Al2O3 e Na2O em todas as variedades além de concentrações de Ca, Zn, Zr e Ba. Os picos TL nas curvas de emissão são discrepantes das curvas usualmente encontradas na literatura, com picos em 1100C, 2200C e 3250C. Apenas o pico em 1100C é comum a todas as amostras. Em relação à forma das curvas de emissão também existe discrepância. O comportamento da intensidade TL em função da dose, para picos em 2200C e 3250C é singular para cada amostra, de forma que o comportamento linear-supralinear-sublinear é observado apenas nos picos em 2200C para amostras de quartzo azul e hialino. O pico em 3250C, apresenta em praticamente todas as amostras, um terceiro estágio de crescimento com a dose. Admiti-se que o segundo estágio, que é da supralinearidade, é causado pela criação de novas vacâncias de oxigênio pela radiação, o segundo estágio é seguido de outro não-linear. Aqui se propõe um modelo em que a radiação cria novas vacâncias, dentro do grupo de tetraedros SiO4, do qual se formou a vacância de oxigênio. O germânio, no presente trabalho, possui concentrações baixíssimas em amostras como o quartzo leitoso e quartzo com enxofre, de maneira que não apresenta correlação com o pico de 110°C, conforme descrito na literatura, pois ambas amostras apresentam intensos picos nesta região de temperatura. Estudos de absorção óptica revelam a existência de bandas de absorção em 620, 450 e 350nm. Conforme a literatura, estas bandas são causadas pela presença do alumínio, pois crescem rapidamente com a radiação, causando a transição do quartzo hialino para quartzo fumê. Ao se comparar com amostra de quartzo artificial, com concentrações de alumínio, próximas as do hialino, a amostra não apresentou as três bandas mencionadas anteriormente, de maneira que se pode concluir que o alumínio não é o responsável por elas. Conclui-se que, as sete variedades de quartzo do presente trabalho, apresentam propriedades TL e de AO muito singulares para cada variedade, ao contrário do que se espera ao analisar os difratogramas das amostras. / Thermoluminescence and optical absorption properties of seven varieties of natural Brazilian quartz, namely, blue, sulphurous, milky, pink, green, red and black quartzs, have been investigated. For comparasion measurements were carried out also on natural alpha and synthetic quartz. Since gemological amethyst and citrine have been studied by several authors, they were not included in this work. The X Ray diffraction analysis has shown that all seven varieties of quartz have a same crystal structure of a standard sample. X Ray fluorescence and Plasma Mass Spectrometry (ICP-MS) analysis reveal Al2O3 and Na2O in all the quartz in fairly large amount, wich are essential in TL emission. Ca, Zn, Ba and Zr are also found in all the quartz samples, however several previous studies of silicate minerals indicated that they do not participate in the physical properties investigated. It is commonly known that a natural alpha quartz presents in its glow curve, 110, 220 and 325°C (sometimes replaced by 375°C) peaks. Except for 110°C peak, the two others are found is some variety but not in others. No explanation was found yet. The shape of glow curves also vary considerably from one variety to others. A striking result was obtained concerning TL response as function of radiation dose of 220°C (245°C in black quartz) and 325°C peaks. The linearsupralinear- sublinear, commonly observed in alkali halides, oxides, sulphates, etc. crystals are not observed in quartz samples except for 220°C peak in blue quartz and hyaline quartz. If linear and supralinear behavior are called first and second stage, the third stage in many of them is not sublinear, rather it keeps growing. In some cases, the first and second stages are strongly supralinear, sulphurous such as in quartz and pink quartz . In alkali halide crystal, for instance, the second stage is due to anion vacancy generated by radiation. In quartz it is due to generation of oxygen vacancy. For the third stage it is proposed that the radiation creates new oxygen vacancy in the group of SiO4 tetrahedron generating oxygen vacancy for the second stage. In the literature, one finds Ge being responsible for production of 110°C peak. The ICP-MS measurements has shown that Ge is found in all the varieties seven quartz, except in sulphurous one, but in less that 2 ppm concentration. Furthermore it was found that the 110°C peak intensity, in these quartz, has no correlation to Ge concentration, the 110°C peak has a huge intensity. Therefore, it is proposed that the oxygen removed from its normal site ends up in an intersticial position as neutral oxygen. The irradiation liberating e-h pairs enable intersticial oxygen to capture electron and became O- centre. This is the source of 110°C peak. The optical absorption spectra of alpha quartz, particularly of heavily irradiated one, show bands at 620, 450 and 350nm. They were attributed to aluminum. Similar result was found in alpha quartz, but the synthetic one with a comparable concentration of aluminum as in the natural alpha quartz did not present such bands, even after irradiation to 20 to 25kGy gamma rays. It was concluded that 620, 450 and 350nm bands are not due to aluminum. It was not found the impurities responsible for there bands. In conclusion, the seven varieties investigated, present quite different behaviour. Compared to that of the usual nature alpha quartz.

by Ranganathan Venugopal. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2001. / Includes bibliographical references (p. 150-165). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Mode of access: World Wide Web. / Abstracts in English and Chinese.

Il est bien connu que divers solides amorphes ont de nombreuses propriétés universelles. L'une d'entre elles est la variation de la conductivité thermique en fonction de la température. Cependant, le mécanisme microscopique du transfert de chaleur dans le domaine de température supérieure à 20 K est encore mal compris. Simulations numériques récentes du silicium et de la silice amorphes montrent que les modes de vibration dans la gamme de fréquences correspondante (au-dessus de plusieurs THz) sont délocalisés. En même temps ils sont complètement différents des phonons acoustiques de basse fréquence, dits « diffusions ».Dans ce travail, nous présentons un modèle stable de matrice aléatoire d'un solide amorphe. Dans ce modèle, on peut faire varier le degré de désordre allant du cristal parfait jusqu'au milieu mou extrêmement désordonné sans rigidité macroscopique. Nous montrons que les solides amorphes réels sont proches du deuxième cas limite, et que les diffusions occupent la partie dominante du spectre de vibration. La fréquence de transition entre les phonons acoustiques et diffusons est déterminée par le critère Ioffe-Regel. Fait intéressant, cette fréquence de transition coïncide pratiquement avec la position du pic Boson. Nous montrons également que la diffusivité et la densité d'états de vibration de diffusons sont pratiquement constantes en fonction de la fréquence. Par conséquent, la conductivité thermique est une fonction linéaire de la température dans le domaine allant à des températures relativement élevées, puis elle sature. Cette conclusion est en accord avec de nombreuses données expérimentales. En outre, nous considérons un modèle numérique de matériaux de type de silicium amorphe et étudions le rôle du désordre pour les vibrations longitudinales et transverses. Nous montrons aussi que la théorie des matrices aléatoires peut être appliquée avec succès pour estimer la densité d'états vibrationnels des systèmes granulaires bloqués. / It is well known that various amorphous solids have many universal properties. One of them is the temperature dependence of the thermal conductivity. However, the microscopic mechanism of the heat transfer above 20 K is still poorly understood. Recent numerical simulations of amorphous silicon and silica show that vibrational modes in the corresponding frequency range (above several THz) are delocalized, however they are completely different from low-frequency acoustic phonons, called “diffusons”.In this work we present a stable random matrix model of an amorphous solid. In this model one can vary the strength of disorder going from a perfect crystal to extremely disordered soft medium without macroscopic rigidity. We show that real amorphous solids are close to the second limiting case, and that diffusons occupy the dominant part of the vibrational spectrum. The crossover frequency between acoustic phonons and diffusons is determined by the Ioffe-Regel criterion. Interestingly, this crossover frequency practically coincides with the Boson peak position. We also show that, as a function of frequency, the diffusivity and the vibrational density of states of diffusons are practically constant. As a result, the thermal conductivity is a linear function of temperature up to rather high temperatures and then saturates. This conclusion is in agreement with numerous experimental data.Further, we consider a numerical model of amorphous silicon-like materials and investigate the role of disorder for longitudinal and transverse vibrations. We also show that the random matrix theory can be successfully applied to estimate the vibrational density of states of granular jammed systems.

Neste trabalho estudamos as propriedades eletrônicas e as estabilidades estruturais do cristal de ZrO2 e dos defeitos de vacância de oxigênio e impureza substitucional de cério. As investigações foram efetuadas através de simulações computacionais baseadas em métodos de primeiros princípios dentro do formalismo da teoria do funcional da densidade e utilizando o método APW + lo (Aumengted Plane Waves plus local orbitals), implementado no código computacional WIEN2k, dentro do esquema de supercélula, com relaxações atômicas tratadas de modo apropriado. A zircônia apresenta 3 fases estruturais, dependendo da temperatura. Sua fase mais estável é a monoclínica e, a altas temperaturas, ela apresenta as fases tetragonal e cúbica, sendo estas duas últimas as mais importantes para aplicações tecnológicas. Ela pode ser estabilizada em uma condição metaestável em uma estrutura quase cúbica quando crescida na forma de pós nanocristalinos, com tamanhos menores que um certo tamanho crítico. Outra maneira de se estabilizar as estruturas cúbica e tetragonal, a temperatura ambiente, é através da adição de dopantes, entre eles o cério. Nesses casos, estão sempre presentes vacâncias de oxigênio. Neste trabalho, para o cristal puro de ZrO2, foram calculadas as propriedades das estruturas cristalinas cúbica e tetragonal, constatando-se que a estrutura quase cúbica, proposta em várias investigações relatadas na literatura, pode ser interpretada como uma estrutura tetragonal de corpo centrado, com pequenos deslocamentos dos átomos de oxigênio na direção k . Destes resultados, propomos que nas análises dos dados experimentais obtidos por difração de raios-X e EXAFS (Extended X-ray Absorption Fine Structure) sejam utilizadas simulações onde a estrutura tetragonal de corpo centrado seja considerada como uma possível estrutura para o cristal. Dos estudos da vacância de oxigênio, obtivemos que sua presença quebra a simetria local do sistema e faz com que existam três diferentes distâncias entre um átomo de Zr e os átomos primeiros vizinhos de oxigênio, podendo, também, explicar resultados experimentais de difração de raios-X e EXAFS. Para o centro de impureza substitucional de Ce no sítio do átomo de Zr, nossos resultados apresentam uma possível explicação de porque as impurezas de Ce, em diferentes concentrações, estabilizam o ZrO2 nas estruturas tetragonal e cúbica. / In this investigation we studied the electronic properties and the structural stabilities of zirconia (ZrO2), as well as oxygen vacancy and Ce substitutional impurity. The investigations were carried by computational simulations using ab initio methods, based on the density functional theory and the APW + lo (Aumengted Plane Waves plus local orbitals) method, as implemented in the WIEN2k code, considering the supercell approach and atomic relaxations. Concerning the ZrO2 bulk, the tetragonal (quasi-cubic) phase is not thermodynamically stable at room temperature, but it can be retained in a metastable condition in nanocrystalline powders with crystallite sizes smaller than a certain critical size, or throught addition of dopants, for example cerium. In this cases, oxygen vacancies are always present. In this work we have obtained the properties of the cubic and tetragonal phases of ZrO2. From the results, we propose that the quasi-cubic structure presented in many articles can be understood as a body centered tetragonal structure, with small oxygen atoms displacement perpendicular to the k direction. Those results suggest that the analysis of the X-ray and EXAFS (Extended X-ray Absorption Fine Structure) data should include in the crystallographic model the body-center tetragonal structure. The results of the structural and electronic properties of the oxygen vacancy suggest that its presence could explain the different models of the Zr first neighbor oxygen shell. For the Ce substitutional impurity, our results present a possible explanation why these impurities, in several concentrations, are able to stabilize the ZrO2 in the tetragonal and cubic phases.

No description available.

Measurements of atomic parity violation provide important cross-tests of the standard model of electroweak interactions by probing these interactions in the domain of low energies. The effects of parity nonconservation in atoms, both dependent and not dependent on nuclear spin, have been successfully measured in experiments. The existence of permanent electric dipole moment (EDM) of a quantum particle requires that fundamental parity (P) and time-reversal (T) symmetries are violated. By the CPT theorem, this would mean violation of the combined CP (charge conjugation-parity) symmetry as well. Studies of T and CP violation in nature provide valuable information for theories of baryogenesis, and for understanding of fundamental interactions in general. Recently, a new wave of experiments has been initiated to measure the effects of P and T violation in solid state materials. The possibility to substantially increase the experimental sensitivity lies in the larger number of particles compared to the atomic experiments and in the specific collective effects in solids. The downside is the typically larger level of systematics. In the present work, the following effects due to violation of T and P at fundamental level in solids are considered: (a) effects due to the nuclear weak charge (violation of P) in rare-earth trifluorides, a possibility exists to measure the Weinberg angle with high precision; (b) effects due to the nuclear anapole moment (nuclear spin-dependent violation of P) in praseodymium and thulium garnets, the NMR-type experiments can possibly be used to measure nuclear anapole moments of Pr and Tm; (c) effects due to the electron EDM in gadolinium garnets, increase of the experimental sensitivity to the electron EDM of several orders of magnitude is possible; (d) effects due to the nuclear Schiff moment of 207Pb in ferroelectric lead-titanate; this possibility looks particularly promising, offering a potential 10 orders of magnitude increase of sensitivity to the nuclear Schiff moment, which puts the standard model prediction for this value within experimental reach. Also discussed are several other possibilities for experimental observation of these effects and the impact of some possible systematic effects on the proposed measurements.

New transparent p- and n-type semiconductors and luminescent materials have been prepared and characterized. Synthesis, structures, optical and electrical properties of new chalcogenide fluoride p-type transparent semiconductors MCuQF (M=Ba, Sr; Q=S, Se, Te) are described. Band-gap tuning and improvement in conductivity through p-type doping are demonstrated in the family. The new Ag sulfide fluoride BaAgSF has been prepared, and its optical and electrical properties have been examined. Phase stabilization as well as optical and electrical properties of the p-type conductors BaCu₂S₂ and BaCu₂Se₂ are considered. New n-type transparent conducting films of W-doped In₂O₃ and W-doped zinc indium oxide (ZIO) have been prepared by pulsed laser deposition, and their electrical properties have been examined. Results on new transparent thin-film transistors containing SnO₂ or ZIO are also presented. Strong near-infrared luminescence of BaSnO3 is described, and the emission brightness is correlated to the crystallite size of assembled nanoparticles. Syntheses, structures, and optical properties of (La,Y)Sc₃(BO₃)₄:Eu³⁺, (Ba,Sr)Sc₂(BO₃)₄:Eu²⁺, and LuAl₃(BO₃)₄:Ln³⁺ (Ln=Eu, Tb, Ce) have been considered with emphasis on relations between structures and optical properties. Finally, the synthesis and luminescence properties of new potential X-ray phosphors Lu₂O₂S:Ln³⁺ (Ln=Eu, Tb) are summarized. / Graduation date: 2005

Colloidal self assembly is an efficient method for making 3-D ordered nanostructures suitable for materials such as photonic crystals and macroscopic solids for catalysis and sensor applications. Colloidal crystals grown by convective methods exhibit defects on two different scales. Macro defects such as cracks and void bands originate from the dynamics of meniscus motion during colloidal crystal growth while micro defects like vacancies, dislocation and stacking faults are indigenous to the colloidal crystalline structure. This paper analyses the crystallography and energetics of the microscopic defects from the point of view of classical thermodynamics and discusses the strategy for the control of the macroscopic defects through optimization of the liquid-vapor interface. / Singapore-MIT Alliance (SMA)

Graduation date: 1992