Three of the most important questions concerning hydrogen storage in metals are how much hydrogen can be absorbed, how fast it can be absorbed (or released) and finally how strongly the hydrogen is bonded. In transition metals hydrogen occupies interstitial sites and the absorption as well as desorption of hydrogen can be fast. The enthalpy of the hydride formation is determined by the electronic structure of the absorbing material, which determines the amount of energy released in the hydrogen uptake and the energy needed to release the hydrogen. This thesis concerns the possibility of tuning hydrogen uptake by changing the extension of the absorbing material and the boundary conditions of extremely thin layers. When working with extremely thin layers, it is possible to alter the strain state of the absorbing material, which is used to influence the site occupancy of hydrogen isotopes. Vanadium is chosen as a model system for these studies. V can be grown in the form of thin films as well as superlattices using MgO as a substrate. Special emphasis are on Fe/V(001) and Cr/V(001) superlattices as these can be grown as high quality single crystals on a routine basis. The use of high quality samples ensured well-defined conditions for all the measurements. In these experiments the hydrogen concentration is determined by the light transmittance of the thin films.  By changing the temperature and the pressure of the hydrogen gas, it is possible to determine the thermodynamic properties of hydrogen in the samples, from the obtained concentrations.  Measurements of the electrical resistivity is used to increase the accuracy in the measurements at low concentrations as well as to provide information on ordering at intermediate and high hydrogen concentrations. The thermodynamic properties and the electrical resistivity of VH are strongly affected by the choice of boundary layers. For example, when hydrogen is absorbed in V embedded by Fe, Cr or Mo in the form of superlattices, both the thermodynamic properties and the changes in the resistivity are strongly influenced. The critical temperature and H-H interactions of hydrogen in thin V(001) layers are found to increase with thickness of the thin films and superlattices. The observed finite size effects resemble same scaling with the thickness of the layers as does the magnetic ordering temperature. The results were validated by investigations of isotope effects in the obtained thermodynamic properties. Close to negligible effects are obtained when replacing hydrogen by deuterium, with respect to the thermodynamic properties. These observations are rationalised by an octahedral occupancy in the strained layers, as compared to tetrahedral occupancy in unstrained bulk. The octahedral site occupancy is found to strongly alter the diffusion coefficient of hydrogen in thin V layers.

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We study the electronic band structure of no-common-atom InAs-GaSb superlattice within a nearest-neighbor bond-orbital model. The effect of interfacial asymmetry is also taken into account. This model can reproduce fairly accurate bulk band structures near the center of the Brillouin zone. We find that interfacial asymmetry, which is first included in bond-orbital model, can yield spin splitting. We also find that a negative indirect band gap appears for long period superlattice, due to interfacial asymmetry and band anisotropy of the heavy hole band in GaSb material. This indicates that the semiconductor-semimetal transition, which occurs when the period d reach a critical value dC, does exist in InAs-GaSb superlattice. In our calculation, the critical period dC is about 150 Å.

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Orientador: André Luiz Malvezzi / Banca: Marcio José Martins / Banca: Alexys Bruno Alfonso / O Programa de Pós-Graduação em Ciência e Tecnologia de Materiais, PosMat, tem caráter institucional e integra as atividades de pesquisa em materiais de diversos campi da Unesp / Resumo: Na área de pesquisa em sistemas de elétrons fortemente correlacionados, o modelo das super-redes Hubbard tem sido utilizada para explicar e prever comportamentos de heteroestruturas, como multicamadas magnéticas, que apresentam propriedades diferentes e incomuns, comparadas com as dos sistemas homogêneos análogos, E.G., ordenamentos magnéticos e de carga. Neste contexto, foram estudados nesta dissertação os efeitos da introdução de um novo valor , 'T IND. C', para o parâmetro de hopping de elétron nas interfaces de camadas diferentes da super-rede, ou seja, introduziu-se uma modulação na condução entre as camadas. Variou-se 'T IND. C'entre 0.1T e T, onde T é o parâmetro de hopping entre sítios da mesma camada. Para a lacuna de carga encontramos um comportamento dependente da densidade eletrônica na rede. Em geral, momentos magnéticos locais e a ocupação eletrônica nos sítios, apresentam uma distribuição mais uniforme para 'T IND. C'=0.1T. No entanto, nas densidades onde ocorre um aumento abrupto na lacuna de carga com a diminuição de 'T IND. C', essa uniformidade é mais pronunciada, possivelmente devido a uma comensurabilidade entre a distribuição dos elétrons na cadeia e a estrutura da super-rede. Para as funções de correlação de carga, que foram estudadas através do fator de estrutura, encontramos em alguns casos uma dependência em 'T IND. C' do período do ordenamento correspondente. / Abstract: In the research field of strongly correlated electron systems, the Hubbard superlattice model has been used for explain and predict the behavior of heterostructures, such as magnetic multilayers, whose unusual properties differ from the properties of the analogous homogeneous counterpart. In this context, we have studied here the effects of introducing a new value for the hopping parameter, 'T IND. C', for electrons between different layers, E.G., we introduced a modulation in the electronic conduction between layers. We consider 'T IND. C' in the range 0.1T to T, where T is the hopping parameter for sites inside the layers. For the charge gap, we found a behavior that depends on the electronic density in the lattice. Local magnetic and electronic occupation on sites, generally, show a greater uniformity with decreasing 'T IND. C'. However, for electronic densities where is an abrupt increase in the charge gap for decreasing 'T IND. C', this uniformity is enhanced, probably due to a commensurability between the electronic distribution in the chain and the underlying superlattice structure. For the charge correlation functions, that were studied through their structure factor, we found in some cases a dependency in 'T IND. C' of the correlations oscillation period. / Mestre

¡@Complex nano-architectures of different materials have very interesting geometry. Combining different metallic nanoparticles should allow the manufacture of novel nanocomposite materials with a plethora of exploitable electronic, optical, and magnetic properties. ¡@Thiolate-capped Au nanoparticles prepared by Brust-Schiffrin two phase method and carboxylate-capped Ag nanoparticles prepared by our one-step synthetic method are reported. ¡@We also developed and prepared Ag colloidal solution which can be used to form a high valuable conductive thin film by spin coating on Si wafer. Specific resistivity of 6.097 £g£[¡Ecm for the silver metallic film (0.7 £gm) on the Si wafer can be simply produced by thermal annealing of Ag MPCs film under an atmosphere of 10 % H2-90 % N2 at 300 ¢J for 1 h. Furthermore, it can be applied to make a micro-circuit by ink-jet printing technique. ¡@The characterizations of TEM, PXRD, UV-Visible, NMR, FT-IR, ESCA, TGA, TA-MS, EI-MS and SEM of Au and Ag nanoparticles are described. ¡@We hope the thiolate-capped Au nanoparticles and carboxylate-capped Ag nanoparticles could spontaneously self-connect to form the nanoscale alloy superlattice structure by the molecular recognizable bifuctional linkage.

Oxide interfaces have attracted considerable attention in recent years due to emerging novel properties that do not exist in the corresponding parent compounds. Furthermore, modern atomic-scale growth and probe techniques enable the formation and study of new artificial interface states distinct from the bulk state. A central issue in controlling the novel behavior in oxide heterostructures is to understand how various physical variables (spin, charge, lattice and/or orbital hybridization) interact with each other. In particular, density function theory (DFT) has provided significant insight into underlying physics of materials at the atomic level, giving quantitative results consistent with experiment. In this dissertation using density functional theory methods, we explore the electronic, magnetic and structural properties developed near the interface in SrTiO3/LaAlO3, EuO/LaAlO3, Fe/PbTiO3/Pt, Fe//BaTiO3/Pt and Cs/SrTiO3 heterostructures. We study the interplay between physical interactions, and quantify parameters that determine physical properties of hetetrostructures. These theoretical studies help understanding how physical variables couple with each other and how they determine new properties at oxide interfaces. / text

InAs/GaSb superlattices are a material system well suited to growth via molecular beam epitaxy. The ability to tune the band gap over the entire mid and long wave infrared spectrum gives a large number of applications for devices made from InAs/GaSb superlattice material. The growth of high quality InAs/GaSb superlattice material requires a careful study of the parameters used during epitaxial growth. This work investigates the growth of tunnel junctions for InAs/GaSb based superlattice light emitting diodes, the presence of defects in GaSb homoepitaxial layers, and variations in the growth rate of InAs/GaSb superlattice samples. Tunnel junctions in cascaded structures must provide adequate barriers to prevent carriers from leaking from one emission region to the next without first recombining radiatively, while at the same time remain low in tunneling resistance for current recycling. A variety of tunnel junction designs are compared in otherwise identical four stage InAs/GaSb superlattice light emitting diodes, which past studies have found hole confinement to be problematic. GaSb was used on the p-side of the junction, while various materials were used on the n-side. Al0.20In0.80As0.73Sb0.27 tunnel junctions function best due to the combination of favorable band alignment and ease of growth. Pyramidal defects have been observed in layers of GaSb grown by molecular beam epitaxy on GaSb substrates. These defects are typically 3-8 nanometers high, 1-3 microns in diameter, and shaped like pyramids. Their occurrence in the growth of GaSb buffer layers can propagate into subsequent layers. Defects are nucleated during the early stages of growth after the thermal desorption of native oxide from the GaSb substrate. These defects grow into pyramids due to a repulsive Ehrlich-Schwoebel potential on atomic step edges leading to an upward adatom current. The defects reduce in density with growth of GaSb. The insertion of a thin AlAsSb layer into the early stages of the GaSb buffer increases the rate of elimination of the defects, resulting in a smooth surface within 500nm. The acceleration of defect reduction is due to the temporary interruption of step-flow growth induced by the AlAsSb layer. This leads to a reduced isolation of the pyramids from the GaSb epitaxial layer, and allows the pyramidal defects to smooth out. Investigations into varying the superlattice growth rate have not been reported widely in the literature. Due to the frequent use of soaks, growth interrupts, and other interface structuring steps the superlattice growth rate and the interface layer sequence are linked. In order to properly study the effects of growth rate variations and interface design changes it is necessary to account for the effect on growth rate due to the interfaces. To this end it is useful to think of the effective growth rate of the superlattice, which is the total layer thickness divided by the total time, per superlattice period. Varying the effective growth rate of superlattice photoluminescence samples shows a peak in output at ˜ 0.5 monolayers per second. Investigations into the structural properties of the superlattices show no decrease in structural uniformity for effective growth rates up to ˜ 1.4 monolayers per second.