Nanomaterials such as carbon nanotubes, gold nanorods, magnetic nanocrystals, and binary nanocrystal superlattices have exciting potential applications. However, before these ideas can be applied, it is imperative to fully understand the materials synthesis. Multiwall carbon nanotubes were synthesized in supercritical toluene using cobaltocene, nickelocene, ferrocene, or metal nanocrystals as catalysts. Toluene served as both the solvent and carbon source for nanotube growth. The reaction was optimized by introducing supplemental carbon sources; either hexane or ethanol increased the yield relative to pure toluene and catalytic amounts of water minimized carbon filament and amorphous carbon formation. Gold nanorods were synthesized by the colloidal seed-mediated, surfactantassisted approach using cetyltrimethylammonium bromide (CTAB) obtained from ten different suppliers. The gold nanorod yield depended strongly on the CTAB used: with the same recipe, three of the CTABs produced only spherical particles, whereas the other CTABs produced nanorods with nearly 100% yield. Inductively coupled plasma mass spectrometry revealed a trace iodide impurity in the CTABs that did not yield nanorods. Further experiments introducing potassium iodide to the nanorod synthesis verified the detrimental effect of iodide on nanorod formation. Multifunctional colloidal core-shell nanoparticles of magnetic nanocrystals or gold nanorods coated with a fluorescent dye (Tris(2,2 -bipyridyl)dichlororuthenium(II) hexahydrate) doped silica shells were also synthesized. The as-prepared magnetic nanocrystals were initially hydrophobic and silica coated using a microemulsion approach, while the gold nanorods were hydrophilic and silica coated using a Stöber process. These colloidal heterostructures have the potential to be used as dual-purpose tags, exhibiting a fluorescent signal that could be combined with either dark-field optical contrast or enhanced contrast in magnetic resonance imaging. Binary superlattices (BSLs) of large iron oxide and small gold nanocrystals were assembled by slow evaporation of colloidal dispersions on tilted substrates. SEM and grazing incidence small angle X-ray scattering (GISAXS) confirmed the BSLs were simple hexagonal AB2 superlattices with long range order. GISAXS also revealed that the superlattice was slightly contracted perpendicular to the substrate as a result of solvent drying during the deposition process. Additionally, in some BSLs nearly periodic superlattice dislocations consisting of inserted half-planes of gold nanocrystals were observed. / text

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Neste trabalho usamos a teoria de Thomas-Fermi para estudar as propriedades eletrônicas de semicondutores planarmente dopados, ou delta-dopados, com densidade de dopantes de moderada a alta. O principal objetivo do trabalho é a verificação de que esta teoria apresenta muito bons resultados com os do método auto-consistente na aproximação de Hartree quando aplicada a este tipo de problema. Verificamos que muitas situações físicas relacionadas a semicondutores delta-dopados podem ser descritas de uma maneira simples e com muito bons resultados. Estudamos o problema de um poço isolado e o problema da super-rede, comparando os resultados de Thomas-Fermi e Hartree. / In this work we have used the Thomas-Fermi theory to study the electronic properties of planar doped semiconductors, or delta-doping, with a moderate to high density of dopants. The main aim of this work is to verify that this theory gives very good results when compared with the self-consistent method in the Hartree aproximation. We have checked that many physical situations related to delta-doping can be described in a simple manner and also with very good results. We have studied the single delta problem and the superlattice problem and we have compared the Thomas-Fermi´s and Hartree´s results.

Energias de ligação do estado fundamental de doadores rasos em super-redes são consideradas teoricamente com o auxílio de um procedimento variacional que leva em conta a mistura do contínuo de estados da minibanda à qual o mesmo está associado. Os cálculos são realizados para um grande número de parâmetros de super-rede e qualquer posição da impureza na mesma. É mostrado que a dependência da energia de ligação com os vários parâmetros envolvidos pode ser completamente explicada em termos de um modelo simples unidimensional (tight-binding) onde a largura da respectiva minibanda de condução e a energia de ligação no Limite de poço isolado são os únicos parâmetros relevantes. A extrema concordância quantitativa entre as energias de ligação derivadas deste modelo e as obtidas pelo método variacional mais rigoroso vem enfatizar o papel fundamental desempenhado pela largura de minibanda com o único parâmetro relevante ao se levar em conta os efeitos de tunelamento existentes nas super-redes. / A variational procedure which takes into account the mixing of a continuum of subband states has been used to investigate the binding energies of shallow donors in superlattices. The calculations where performed for a wide range of superlattices parameters and impurity positions. It is shown that the dependence of the binding energy upon the various superlattice parameters can be completely explained in terms of a simple onedimensional tight-binding model where the bandwidth of the respective conduction subband and the binding energy in the isolated quantum well are the only relevant parameters. The quantitative overall agreement between the binding energies derived from this model and those found variationally is excellent and emphasizes the fundamental role played by the bandwidth as the only relevant parameter accounting for the tunneling effects.

Neste trabalho apresentamos um cálculo teórico para o espalhamento Raman eletrônico via flutuações de densidade de spin de uma super-rede &#948-dopada de GaAs. A estrutura eletrônica da super-rede é determinada utilizando-se a teoria do funcional densidade dentro da aproximação de densidade local. O cálculo da seção de choque revela que sob condições de extrema ressonância existe uma forte dependência das formas de linha com a freqüência de excitação indicando a coexistência de um gás bi e tri-dimensional de elétrons nesta estrutura. Os resultados obtidos mostram excelente acordo entre teoria e experimento. / In this work we theoretically investigate the electronic Raman scattering by spin density fluctuations in periodically &#948-doped GaAs. The electronic structure of the superlattice is determined using density functional theory within the local-density-functional approximation. The calculation of the cross section reveals a strong dependence of the line shape on the exciting frequency under conditions of extreme resonance, which indicates the coexistence of a two and three-dimensional electron gas. The results show an excellent agreement between theory and experiment.

O estudo do ordenamento de nanopartículas em estruturas bi e tridimensionais, também conhecidas como superredes, é de grande interesse científico e tecnológico, tanto pelo interesse em se explicar a origem e as consequências deste fenômeno, quanto pelas possibilidades de aplicação oriundas das propriedades observadas nestes sistemas. Quando são utilizados dois tipos de nanomateriais diferentes em tamanho e/ou composição química, tem-se a formação de superredes binárias. Estas estruturas apresentam propriedades que são resultado das propriedades individuais de seus constituintes e, além disso, do conjunto de interações que existem no sistema. Graças a este conjunto de propriedades e interações coletivas, o princípio de se empregar nanopartículas como \"building blocks\" para a criação ou aprimoramento de dispositivos funcionais. Assim, neste trabalho são discutidas as sínteses de óxidos magnéticos do tipo MFe2O4 (com M = Co, Fe ou Mn) e as características necessárias para o emprego destes na formação de superredes de nanopartículas. Os materiais foram sintetizados procurando-se alcançar uma estreita distribuição de tamanho e homogeneidade quanto à forma. Foram empregados sistemas de nanopartículas nos estudos para a formação de superredes que apresentaram polidispersividade entre 6 e 20%, de forma a discutir o efeito desta propriedade no ordenamento das nanopartículas. Observou-se que o ordenamento em escala macroscópica é fortemente influenciado pela tensão de superfície da subfase, enquanto que o arranjo local das nanopartículas em relação aos seus vizinhos mais próximos é mais influenciado pela taxa de evaporação do solvente e pelas interações interpartículas. Para a formação de superestruturas binárias foram empregadas as nanopartículas de CoO/CoFe2O4 com 9,6 nm ou de Fe3O4 de 10,7 nm, com nanopartículas de CdSe de 3,6 nm. Os sistemas de nanopartículas binárias apresentaram arranjos do tipo AlB2 e tiveram, em sua maioria, crescimento na forma de supercristais facetados. A formação de estruturas bidimensionais com crescimento ao longo do plano da membrana foi favorecida pelo aumento na proporção das nanopartículas de maior diâmetro em relação às menores. A compreensão do fenômeno de auto-organização em membranas de superredes binárias possibilita a obtenção de novos materiais nanoestruturados e que apresentem propriedades moduladas. / Self-assembly nanoparticles into superlattices array have attracted significant attention both for the scientific understanding of nanocrystals ordering process and the development of new functional devices using bottom up techniques. The co-assembly of two types of nanoparticles in binary nanoparticles superlattices provides a new way to design metamaterials with unusual and modulated properties. These unusual properties arise from interparticle interactions in the superlattice structure, and from nanoparticles physical properties. To obtain highly ordered structures, it is required that nanocrystals have narrow size distribution. This thesis presents the synthesis of oxide magnetic nanoparticles (MFe2O4; M = Co, Fe, or Mn) and their application as building blocks in nanocrystal superlattices. Nanoparticles presented size distribution from 6% to 20%, and their assemblies has shown amorphous structure when samples have size distribution above 10%. Self-assembled nanoparticles superlattices in the liquid-air interface were obtained using either single or binary components. Single component superlattices were used as model for the understand of self-assembly process, which depends on subphase surface tension and dispersion evaporation rate. Nanocrystals superlattices were obtained from CdSe nanoparticles, with average size of 3,6 nm, and CoO/CoFe2O4 with size of 9,6 nm, and was observed a AlB2-type superstructure. The same superlattice structure was obtained for CdSe and Fe3O4, with average size of 10,7 nm, which indicate that AlB2 is the equilibrium phase for a rage of radii ratios and nanoparticles stoichiometry. These findings enable to better understand self-assembled binary nanocrystal superlattices formation and how to manipulate interparticle interactions in order to synthesize highly ordered structures.

The present work covers the fabrication and electrical and magnetic investigation of LaNiO3- and LaMnO3- based superlattices (SL). In recent years, several interesting theoretical predictions have been made in these SLs, for example, Mott insulators, metal-insulator transitions, superconductivity, topological insulators, and Chern insulators. Motivated by the promising theoretical predictions, four kinds of SLs with different designed structures and orientations were systematically studied in this thesis. The samples were grown by pulsed laser deposition with in-situ reflection high-energy electron diffraction to monitor the two-dimensional layer-by-layer growth process. In order to ensure the high-quality of SLs, growth parameters were optimised. Characteristic methods like X-ray diffraction, atomic force microscopy, and transmission electron microscopy were used. These measurements proved the high-quality of the SLs and provided the basis for electrical and magnetic measurements. The first studied SL is the (001)-oriented LaNiO3/LaAlO3 SL, which was predicted as a superconductor in theory. Temperature-dependent resistivity measurements revealed a metal-insulator transition by lowering the dimensionality of the LaNiO3 layers in the SLs from three dimensions to two dimensions. The second studied SL is the (111)-oriented LaNiO3/LaAlO3 SL, which was predicted as a topological insulator in theory. The polarity-controlled conductivity was observed and the intrinsic conductivity mechanisms were discussed by means of appropriate modeling. The third studied SL is LaMnO3/LaAlO3 SL, which was predicted as a Chern insulator in theory. By lowering the temperature, a paramagnetic-ferromagnetic phase transition and a thermal activated behavior were observed in the SLs. The last studied SL is the LaNiO3/LaMnO3 SL, in which an exchange bias effect was expected. The studies reveal the exchange bias exists in three kinds of SLs with different orientations.