Low-temperature magnetic force microscopy was used to study the phase diagram of a La1/3Pr1/3Ca1/3MnO3 thin film grown on a (110) NdGaO3 (NGO) substrate by pulsed laser deposition. Traditionally, one can observe the phase change at the nanoscale level as the sample is cooled from room temperature through the transition temperature to liquid nitrogen temperatures, but in this case a fixed voltage ranging from 0 V to 31 V was applied before each cooling cycle. From in and ex situ transport measurements, it is observed that the temperature of the peak of the transition increases with applied field; however, the MFM images show that the magnetic transition begins at a lower temperature with the same increase in field. Thus, this dissertation shows that a new voltage control exists for the phase transition in certain manganites. / text

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[pt] Apesar do constante avanço do envelhecimento populacional brasileiro, a sociedade tende a desestimular a participação da população envelhecida nos processos sócio-econômicos e culturais de produção e nos processos de decisão e integração da sociedade. Esta pesquisa pretende contribuir a integração da população envelhecida sugerindo recomendações que adaptem os terminais de auto-atendimento bancários às suas características físicas, cognitivas e culturais. A pesquisa foi realizada com pessoas idosas com o objetivo de avaliar e compreender a maneira como elas interagem com os terminais. Os métodos utilizados foram: dois questionários, uma análise de similares, análise de leitura das opções no menu do sistema dos terminais de auto- atendimento bancários e uma análise de hierarquização de etapas do sistema. A partir dos resultados, foi possível propor recomendações que podem adequar algumas das funcionalidades dos terminais de auto-atendimento bancários às capacidades e habilidades de interação da população envelhecida. / [en] Despite of the constant advances of the Brazilian population aging, the society tends to discourage the participation of the elderly population in the socioeconomic and cultural processes of production and in the processes of decision and integration of the society. This research intends to contribute with the integration of the elderly population suggesting recommendations that adapt the automated teller machine (ATM) to their Physical , cognitive and cultural characteristics . The research was accomplished with aged people with the objective to evaluate and understand the way they interact with the terminals (ATM). The used methods were: two questionnaires, an analysis of similarities, an reading analysis of options in the menu of the automated teller machine systems and an analysis of hierarchization of stages of the system. Starting from the results, it was possible to propose recommendations that can adapt some of the functionalities of the automated teller machine to the capacities and abilities of interaction of the elderly population.

Ce travail est une contribution à l'étude des excitations de basse énergie des manganites Pr(1-x)Ca(x)MnO(3) (0 ≤ x ≤ 1) par la mesure de la réflectivité entre 0.01 et 2.2 eV en fonction de la température de 4 à 300 K. Les propriétés de ces systèmes d'électrons fortement corrélés sont gouvernées par des interactions en compétition qui induisent un diagramme de phase riche et complexe.<br />Nous interprétons quantitativement la forme et l'évolution des spectres de conductivité optique tirés de la réflectivité, en fonction de (x,T) en utilisant un modèle minimal constitué de deux excitations polaroniques et interbandes dues à l'effet Jahn - Teller. Dans les phases FI et AFI-A, nous relions l'évolution en température du poids spectral de l'excitation JT à l'aimantation par un modèle de double échange. Dans les composés à ordre de charge, nous observons dessous de TCO une augmentation des énergies des transitions optiques que nous attribuons à un renforcement progressif du couplage électron – phonon.

Ce rapport d'habilitation présente une synthèse des activités de recherche que j'ai menées ces huit dernières années. J'ai distingué d'une part les recherches concernant la spectroscopie rovibrationnelle dans un état électronique singulet (Partie III) et d'autre part celles concernant la spectroscopie rovibronique dans un état électronique dégénéré (Partie IV).

Du point de vue théorique, un formalisme tensoriel adapté à l'étude des molécules ou ions octaédriques possédant un moment angulaire demi-entier a été développé pour la première fois. Nous avons utilisé ici la méthode des représentations projectives, plus cohérente que celle des groupes doubles. Un jeu complet de coefficients et de formules de couplage, ainsi que les programmes de calcul correspondants ont été mis au point. Ceci a tout d'abord permis l'écriture d'un modèle simple décrivant la structure électronique des hexafluorures colorés. Ensuite, un certain nombre d'applications de ce formalisme à l'étude des couplages rovibroniques pour les molécules de type XY6 dans un état électronique quatre fois dégénéré ont été examinées, en particulier concernant les opérateurs associés à l'effet Jahn-Teller dynamique. Du point de vue expérimental, nous nous sommes intéressés à IrF6, dont nous avons pu maîtriser les processus de synthèse, de purification et de conservation. Une première étude à basse résolution (absorption et diffusion Raman spontanée) a été réalisée sur cette molécule. Nous avons ensuite mis en place deux dispositifs spectroscopiques à haute résolution dans le visible (absorption saturée - testée sur une cuve à iode - et simple absorption avec multiples passages). Ceux-ci utilisent notamment un laser à colorant. Ils doivent maintenant permettre la spectroscopie de la bande visible de IrF6, afin d'en résoudre pour la première fois la structure fine rotationnelle.

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The nonlinear optical properties of semiconductor heterostructures, such as GaAsAl/GaAs alloys, are studied with analytic and numerical methods on the basis of quantum mechanics. Particularly, second and third-order nonlinear optical properties of quantum wells described by the various types of confining potentials are considered within the density matrix formalism. We consider a P&ouml / schl-Teller type potential which has been rarely considered in this area. It has a tunable asymmetry parameter, making it a good candidate to investigate the effect of the asymmetry on the nonlinear optical properties. The calculated nonlinear quantities include nonlinear absorption coefficient, second-harmonic generation, optical rectification, third-harmonic generation and the intensity-dependent refractive index. The effects of the DC electric field on the corresponding nonlinearities are also studied. The results are in good agreement with the results obtained in other types of quantum wells, such as square and parabolic quantum wells. The effects of the Coulomb interaction among the electrons on the nonlinear intersubband absorption are considered within the rotating wave approximation. The result is applied to a Si-delta-doped, square quantum well in which the Coulomb interaction among the electrons are relatively important, since there has been no work on the nonlinear absorption spectrum of the Si-delta-doped quantum well. The results are found to be new and interesting, especially when a DC electric field is included in the calculations.

This dissertation reports on the synthesis, structural and thermal characterization and electrical and thermal transport properties of a variety of strongly correlated spinels. General structure property relationships for electrical and thermal transport are discussed. However, the relationship between thermopower and features of the crystal structure such as spin, crystal field, anti-site disorder, and structural distortions are explored in depth. The experimental findings are reported in the context of improving existing oxide thermoelectric materials, screening for new materials or using thermopower as a unique characterization tool to determine the cation distribution in spinels. The need for improved n-type oxide thermoelectric materials has led researchers to consider mixed valence \((+3/+4)\) manganese oxides. Contrary to previous findings we report herein that the \(LiMn_2O_4\) compound reaches the relatively large n-type thermopower of \(-73 \mu V/K\) which is three times larger than the value observed in other manganese oxides, \(-25 \mu V/K\). The cause of this increase in thermopower is shown to be the absence of a Jahn-Teller distortion on the \(Mn^{3+}\) ions in \(LiMn_2O_4\). By avoiding this structural distortion the orbital degeneracy is doubled and the Koshibae et al.’s modified Heikes formula predicts a thermopower of \(-79 \mu V/K\) in good agreement with the experiment. Altering the \(Mn^{3+/4+}\) ratio via aliovalent doping did not affect the thermopower and is a second evidence of universal charge transport first reported by Kobayashi et al. The role of anti-site disorder was further examined in \(Fe_xMn_{1-x}NiCrO_4\) x=0, ½, ¾, 1 spinels but the effect on thermopower was inconclusive due to the presence of impurity phases. Next, the thermopower as a function of temperature in \(Co_3O_4\) was investigated as a means whereby the Wu and Mason’s 30 year old model for using thermopower to calculate cation distribution in spinels could be revisited. We report evidence that Wu and Mason’s original model using the standard Heikes formula and considering octahedral sites alone leads to a stoichiometrically inconsistent result at high temperatures. Alternate models are evaluated considering Koshibae et al.’s modified Heikes formula and accounting for tetrahedral site contributions. Furthermore, the effect of a possible spin state transition is considered. / Engineering and Applied Sciences

The deposition of amorphous silica from aqueous solution on to rutile particles has been studied with the aim of elucidating the nature of the silica-titania interactions occurring and of following the progressive build up of the silica coating. The coating process, which involves the addition of an aqueous sodium silicate solution to an aqueous dispersion of titanium dioxide, has been investigated by performing a series of controlled preparations and using the technique of microelectrophoresis. Prepared silica-coated rutile samples ranging from partial to full silica coatings have been characterized using transmission electron microscopy, microelectrophoresis and nitrogen, argon and water sorption. Nitrogen and argon adsorption isotherms have been analysed using the equation of Brunauer, Emmett and Teller (BET). Differential energies of adsorption of nitrogen and argon have been determined calorimetrically. Water sorption isotherms have been analysed using the BET equation and the Frenkel - Halsey - Hill (FHH) equation. It has been shown that uniform silica coatings can be produced if adsorption of monomeric silica is followed by polymerization of silica at the solid/liquid interface. Surface cations on rutile may be hydroxylated or co-ordinately bound to water molecules and it appears that monomeric silica adsorbs preferentially by replacing ligand water molecules. Rutile particles with silica coatings thicker than approximately 2.5nm exhibit characteristics typical of silica and not of the base rutile. Silica coatings deposited at pH 10 contain narrow channels which are accessible to water molecules but not to nitrogen or argon. Neutralization to pH 7 reduces the volume in the coating accessible to water molecules.