Made available in DSpace on 2014-12-17T15:15:03Z (GMT). No. of bitstreams: 1 SubeniaM.pdf: 7084944 bytes, checksum: 1be8677e14b90365726bca93148b19d2 (MD5) Previous issue date: 2007-06-11 / The physical properties and the excitations spectrum in oxides and semiconductors materials are presented in this work, whose the first part presents a study on the confinement of optical phonons in artificial systems based on III-V nitrides, grown in periodic and quasiperiodic forms. The second part of this work describes the Ab initio calculations which were carried out to obtain the optoeletronic properties of Calcium Oxide (CaO) and Calcium Carbonate (CaCO3) crystals. For periodic and quasi-periodic superlattices, we present some dynamical properties related to confined optical phonons (bulk and surface), obtained through simple theories, such as the dielectric continuous model, and using techniques such as the transfer-matrix method. The localization character of confined optical phonon modes, the magnitude of the bands in the spectrum and the power laws of these structures are presented as functions of the generation number of sequence. The ab initio calculations have been carried out using the CASTEP software (Cambridge Total Sequential Energy Package), and they were based on ultrasoft-like pseudopotentials and Density Functional Theory (DFT). Two di?erent geometry optimizations have been e?ectuated for CaO crystals and CaCO3 polymorphs, according to LDA (local density approximation) and GGA (generalized gradient approximation) approaches, determining several properties, e. g. lattice parameters, bond length, electrons density, energy band structures, electrons density of states, e?ective masses and optical properties, such as dielectric constant, absorption, re?ectivity, conductivity and refractive index. Those results were employed to investigate the confinement of excitons in spherical Si@CaCO3 and CaCO3@SiO2 quantum dots and in calcium carbonate nanoparticles, and were also employed in investigations of the photoluminescence spectra of CaCO3 crystal / As propriedades f?sicas e o espectro de excita??es em materiais ?xidos e semicondutores s?o apresentados neste trabalho, composto primeiramente por um estudo sobre o confinamento de fonons ?pticos em sistemas artificiais baseados em nitretos III-V, crescidos periodicamente e quasi-periodicamente. A segunda parte deste trabalho descreve c?lculos de primeiros princ?pios realizados para a obten??o de propriedades optoeletr?nicas em cristais de ?xido de C?lcio (CaO) e Carbonato de C?lcio (CaCO3). Para as super- redes peri?dicas e quasi-peri?dicas apresentamos aqui algumas propriedades din?micas relacionadas a fonons ?pticos (de volume e de superf?cie) confinados obtidos atrav?s de teorias simples como o modelo do diel?trico cont?nuo e a utiliza??o de t?cnicas como a aproxima??o da matriz transfer?ncia. O car?ter de localiza??o dos modos de fonons ?pticos confinados, a magnitude das bandas no espectro e a lei de escalas dessas estruturas como fun??o do n?mero de gera??o das sequ?ncias substitucionais s?o apresentadas. Os c?lculos ab initio foram realizados utilizando o software CASTEP (Cambridge Sequential Total Energy Package) baseados nos m?todos de pseudopotenciais tipo ultrasoft e na teoria do funcional de densidade (DFT). Foram efetuadas duas diferentes otimiza?c~oes de geometria para os cristais de CaO e para or tr?s polimorfos do CaCO3, segundo as aproxima??es LDA (aproxima??o de densidade local) e GGA (aproxima??o do gradiente generalizado), determinando prorpiedades como par?metros de rede, tamanho das liga??es entre os ?tomos, densidade de el?trons, estrutura de bandas de energia, densidade de estados eletr?nica, massas efetivas dos portadores el?tron e buraco, al?m de propriedades ?pticas como constante diel?trica, absor??o, reflectividade, condutividade e ?ndice de refra??o do cristal. Estes dados ser?o utilizados na realiza??o de estudos sobre o confinamento de excitons em pontos qu?nticos esf?ricos Si@CaCO3 e CaCO3@SiO2 e nanopart?culas ocas de car- bonato de c?lcio, e na investiga??o do espectro de luminesc?ncia do cristal de CaCO3.

The context of this PhD is the reduction of sizes involved in material development and the confinement of heat in modern devices, which are known to lead to the apparition of hot spots. The goal is to investigate heat conduction from micro- to nanoscale wide Joule-heated wires standing on flat layered materials. A particular focus is given to the analysis of phonon heat dissipation when departing from the well-known Fourier diffusive conduction and entering the ballistic regime. The manuscript starts with a summary of the main observed effects on the effective thermal conductivity in nanoscale materials, especially in light of the values of thermallyaveraged phonon mean free paths and the associated Knudsen number. Then the advantages and drawbacks of various measurement techniques are discussed. The analysis of the experimental configuration requires 2D analytical and 3D finite-element method based numerical studies of diffusive heat conduction from a finite source into a medium. Limitations of the 3! method due to wire length, substrate geometry and thin oxide layers are highlighted. The electro-thermal setup developed and the procedure used to deposit the devices on top of the samples are then detailed. A set of well-known materials with mean free path ranging from few nanometers to hundreds of nanometers is characterized with microwires. The thermal conduction properties of multilayer materials are investigated. Heat dissipation from finite sources on top of silicon substrates is then measured as a function of temperature. The mean free path is known to become large when temperature decreases. As a result, this configuration provides clues for understanding heat conduction from ballistic sources. The observed behavior is very different from the one predicted by Fourier’s law and shows a strong reduction of the dissipation. It is found that the results are comparable to earlier measurements involving ridges. They are analyzed with various levels of approximations of predictions using the Boltzmann transport equation. The results obtained may be useful in many fields, in particular for electronics and thermoelectric designs. / Le contexte de ce doctorat est la réduction des tailles impliquées dans le développement des matériaux et le confinement de la chaleur dans les dispositifs modernes, qui sont connus pour conduire à l'apparition de points chauds. L'objectif est d'étudier la conduction de la chaleur à partir de fils chauffés par Joule à l'échelle nanométrique et à l'échelle nanométrique, reposant sur des matériaux à couches planes. Une attention particulière est accordée à l'analyse de la dissipation thermique des phonons en partant de la conduction de Fourier bien connue et en entrant dans le régime balistique. Le manuscrit commence par un résumé des principaux effets observés sur la conductivité thermique effective dans les matériaux à l'échelle nanométrique, en particulier à la lumière des valeurs des voies libres moyennes des phonons et du nombre de Knudsen associé. Ensuite, les avantages et les inconvénients des différentes techniques de mesure sont discutés. L'analyse de la configuration expérimentale nécessite des études numériques 2D basées sur la méthode des éléments finis et des éléments finis de la conduction de chaleur par diffusion à partir d'une source finie dans un milieu. Limitations du 3! méthode en raison de la longueur du fil, de la géométrie du substrat et des couches minces d'oxyde sont mises en évidence. La configuration électro-thermique développée et la procédure utilisée pour déposer les dispositifs sur les échantillons sont ensuite détaillées. Un ensemble de matériaux bien connus avec un chemin libre moyen allant de quelques nanomètres à des centaines de nanomètres est caractérisé par des microfils. Les propriétés de conduction thermique des matériaux multicouches sont étudiées. La dissipation thermique des sources finies sur les substrats de silicium est ensuite mesurée en fonction de la température. Le libre parcours moyen est connu pour devenir important lorsque la température diminue. En conséquence, cette configuration fournit des indices pour comprendre la conduction de la chaleur à partir de sources balistiques. Le comportement observé est très différent de celui prédit par la loi de Fourier et montre une forte réduction de la dissipation. On trouve que les résultats sont comparables à des mesures antérieures impliquant des crêtes. Ils sont analysés avec différents niveaux d'approximations de prédictions en utilisant l'équation de transport de Boltzmann. Les résultats obtenus peuvent être utiles dans de nombreux domaines, en particulier pour les conceptions électroniques et thermoélectriques.