Orientador: Bernardo Laks / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin / Made available in DSpace on 2018-08-12T11:04:39Z (GMT). No. of bitstreams: 1 Marcal_Nei_D.pdf: 86929566 bytes, checksum: 04c8aa7c4176175d973ff0990de45bad (MD5) Previous issue date: 2008 / Resumo: Antes da década de 70, todos os materiais poliméricos eram considerados como isolantes e suas aplicações tecnológicas levavam em conta esta característica. De lá para cá, uma nova classe desses materiais, os polímeros conjugados, determinaram uma nova forma de aplicação de sistemas poliméricos baseados em suas propriedades elétricas e de ótica não-linear. Um maior estímulo surgiu a partir do experimento de Mac Diarmid, Heeger e Shirakawa [1] que, expondo o Poliacetileno a agentes oxidantes, demonstraram ser possível obter um sistema no estado metálico. Atualmente encontramos filmes de Poliacetileno com condutividade elétrica da ordem do cobre (105 S/cm). O Poliacetileno, quando no regime metálico, i.e., sob alta dopagem, apresenta algumas características de metal comum: alta condutividade elétrica (cresce 13 ordens de grandeza), susceptibilidade de Pauli finita e absorção no infravermelho. Já outras propriedades como a presença de modos vibracionais localizados no infravermelho e o não comportamento da condutividade com o inverso da temperatura evidenciam ser este um material não usual. Estes polímeros conjugados que apresentam uma extensiva delocalização de elétrons são considerados semicondutores orgânicos com gap de energia relativamente pequeno, da ordem de 1,5 a 2,0 eV. O comportamento semicondutor e as propriedades decorrentes entre os elétrons e a luz têm originado a construção de vários dispositivos semicondutores e optoeletrônicos [2, 7, 3]. Problemas técnicos como estabilidade ao ambiente, processabilidade e solubilidade destes materiais provocaram a produção de uma nova classe de materiais poliméricos que foi obtida por polimerização eletroquímica [57, 58, 59] cuja estrutura molecular trata-se de sistemas que introduzem grupos vinilas (V) entre anéis de tiofeno (T). Experimentos de voltametria cíclica, espectroscopia de absorção ótica e ressonância eletrônica de spin indicam que esses sistemas possuem potencial de ionização e gap de energia menores que o apresentado pelo Politiofeno. Estudos com oligômeros de tiofeno (T) com vinilenos (V) sugerem a possibilidade de escolha desse material como alternativa ao politiofeno. O objetivo deste trabalho foi investigar teoricamente a influência do grupo vinila (V) sobre as propriedades eletrônicas nestes polímeros, reproduzir os resultados experimentais e determinar qual proporção de vinilenos (V) e tiofenos (T) que provoque o menor gap de energia de forma que quando sobre dopagem possibilite uma transição isolante metal. Desta maneira, primeiramente, determinamos as geometrias dos sistemas de interesse utilizando métodos semi-empíricos. Posteriormente investigamos a estrutura eletrônica dos polímeros de tiofeno (T) com vinilenos (V), sendo que estes polímeros foram estudados para o caso neutro e na presença de defeitos conformacionais do tipo pólaron e bipólaron. Finalizamos o estudo investigando as absorções ópticas UV-vis dos sistemas de interesse através de cálculos semi-empíricos utilizando o código ZINDO/S. / Abstract: Before the 1970s, all polymeric materials were considered insulators; therefore their technological applications would take this trait into account. Since then, a new development on these materials, the conjugated polymers, determined new applications for polymeric systems based in their electrical and nonlinear optical properties. Greater interest arose from the experiment by Mac Diarmid, Heeger and Shirakawa [1] who, by using polyacetylene and oxidizing agents, showed that it is possible to obtain a system in the metallic state. Nowadays it is possible to find polyacetylene films with electrical conductivity of the order of copper (10-5 S/cm). Polyacetylene, when in its metallic behavior, i.e., under high dopage, presents some characteristics of real metal: high electrical conductivity (increased by 13 orders of magnitude), finite Pauli susceptibility and infrared absorption. On the other hand, other properties such as the presence of vibrational modes localized on infrared and the odd behavior of conductivity versus the inverse of temperature make clear that this is a unusual material. These conjugated polymers, presenting an extensive delocalization of electrons, are considered organic semiconductors with relatively low energy gap, of the order of 1.5 to 2.0 eV. The semiconductive behavior and the resulting properties of the interaction between electrons and light have been the drive for the manufacturing of several semiconductor and optoelectronic devices [2, 7, 3]. Technical problems, such as environmental stability, processability and solubility of these materials, gave rise to the production of a new kind of polymeric materials that were obtained by electrochemical polymerization [57, 58, 59], in which the molecular structure is a system that introduces vinylene groups (V) between tiophene rings (T). Experiments involving cyclic voltametry, optical absorption spectrometry and spin electronic ressonance indicate that these systems have ionization potential and energy gap smaller than those presented by Polythiophene. Studies with thiopene oligomers (T) with vinylene (V) suggest this material can be chosen as an alternative to Polytiophene. The goal of this work is to theoretically investigate the in uence of the vinyle group (V) on the electronic properties on these polymers, reproduce experimental results and determine what is the vinylene (V) to thiophene (T) rate that causes the smallest energy gap, such that doping will produce a insulator-metal transition. Therefore, we first determine the target systems' geometry using semi-empirical methods. Then we investigate the electronic structure of the tiophene (T) and vinylene (V) polymers both for neutral systems and in the presence of conformational defects of polaron and bipolaron types. We nalized the study by investigating the UV-vis optical absorption of the target systems through semi-empirical calculations using ZINDO/S code. / Doutorado / Estrutura Eletronica de Atomos e Moleculas ; Teoria / Doutor em Ciências

by Tsai Yau Moon = 錳氧化物的金屬-絶緣體轉變 : 多層薄膜及異構結 / 蔡友滿. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2006. / Includes bibliographical references. / Text in English; abstracts in English and Chinese. / by Tsai Yau Moon = Meng yang hua wu de jin shu-jue yuan ti zhuan bian : duo ceng bo mo ji yi gou jie / Cai Youman. / Abstract / 論文摘要 / Acknowledgements / Table of Contents / List of Figures / List of Tables / Chapter Chapter 1 --- Introduction / Chapter 1.1 --- Perovskite-type structure / Chapter 1.2 --- Metal-insulator transition / Chapter 1.3 --- Magnetoresistance / Chapter 1.3.1 --- Giant magnetoresistance (GMR) / Chapter 1.3.2.1 --- Colossal magnetoresistance (CMR) in perovskite manganites / Chapter 1.3.2.2 --- Possible origin of CMR / Chapter 1.4 --- Brief review of p-n junction between perovskite manganites and STON (001) / Chapter 1.5 --- Our project / Chapter 1.6 --- Scope of this thesis work / References / Chapter Chapter 2 --- Preparation and characterization of manganite thin films / Chapter 2.1 --- Thin film deposition / Chapter 2.1.1 --- Facing-target sputtering (FTS) / Chapter 2.1.2 --- Vacuum system / Chapter 2.1.3 --- Deposition procedure / Chapter 2.1.4 --- Deposition conditions / Chapter 2.1.5 --- Oxygen annealing system / Chapter 2.1.6 --- Silver electrode coating system / Chapter 2.2 --- Characterization / Chapter 2.2.1 --- Alpha step profilometer / Chapter 2.2.2 --- X-ray diffraction (XRD) / Chapter 2.2.3 --- Transport property measurement / References / Chapter Chapter 3 --- [LCSMO/PCMO] multilayers / Chapter 3.1 --- [LCSMO (100 A)/PCMO (X A)] multilayers / Chapter 3.1.1 --- Sample preparation / Chapter 3.1.2 --- Results and discussion / Chapter 3.1.2.1 --- Structural analysis / Chapter 3.1.2.2 --- Transport properties / Chapter 3.2 --- [LCSMO (50 A)/PCMO (X A)] multilayers / Chapter 3.2.1 --- Sample preparation / Chapter 3.2.2 --- Results and discussion / Chapter 3.2.2.1 --- Structural analysis / Chapter 3.2.2.2 --- Transport properties / References / Chapter Chapter 4 --- [LSMO/PCMO] multilayers and LSMO/STON p-n junction / Chapter 4.1 --- [LSMO/PCMO] multilayers / Chapter 4.1.1 --- Sample preparation / Chapter 4.1.2 --- Results and discussion / Chapter 4.1.2.1 --- Structural analysis / Chapter 4.1.2.2 --- Magnetization / Chapter 4.2 --- LSMO/STON heterojunction / Chapter 4.2.1 --- Sample preparation / Chapter 4.2.2 --- Results and discussion / Chapter 4.2.2.1 --- Structural analysis / Chapter 4.2.2.2 --- Metal insulator transition of LSMO revealed by four point I-V measurement / Chapter 4.3 --- Conclusion / References / Chapter 5 Conclusion / Chapter 5.1 --- Conclusion / Chapter 5.2 --- Future outlook

In this thesis I present studies of some transport and spectroscopic properties for two di erent materials exhibiting large magnetoresistance. Both of these materials are oxides of transition metals, showing exotic magnetic and transport properties. Despite these similarities, they are very different in many other aspects. One of them is an oxide of Manganese, along with a rare-earth metal, and exhibits large magnetoresistance under certain conditions, when doped by an alkaline earth metal. They are known as doped rare-earth manganites. The other material, Sr2FeMoO6, exhibits large magnetoresistance in the parent compound, without any doping, but only in the polycrystalline state. The manganites, on the other hand, show magnetoresistance under appropriate conditions in both single crystal and in polycrystalline state. Moreover, manganites exhibit several Metal-Insulator Transitions (MIT) as a function of doping, temperature and magnetic field. Sr2FeMoO6, on the other hand, is usually always metallic. In the first chapter, a brief introduction is provided regarding different types of magnetoresistance (MR) phenomena observed in different materials, namely Anisotropic MR (AMR), Giant MR (GMR), Collosal MR (CMR), Tunneling MR (TMR), Powder MR (PMR) etc. Out of these, CMR and PMR are found in doped manganites, while Sr2FeMoO6 exhibits PMR only. Next, a brief overview of the structure, properties and theories for both of these materials is provided. For the case of doped manganites, a short introduction is given for a novel two-fluid hamiltonian (called l - b model) which was proposed recently by Ramakrishnan et. al.. This model reproduces several exotic transport and magnetic properties of manganites which were inexplicible by earlier theories. The model was solved within the Dynamical Mean Field Theory (DMFT) framework by Hassan et. al.. A brief description of this DMFT solution is given. Many of the DMFT results for this model have been used in the subsequent chapters. In the second chapter, the hysteresis behaviour of the magnetoresistance and the magnetization (M ) of powdered Sr2FeMoO6 is considered in detail. In a recent experi- ment by Sarma et. al., it was found that this material, when powdered exhibits an exotic variety of PMR. In ordinary PMR, the hysteresis behaviour of the MR is supposed to follow that of M, in the sense that the coercive fields should be identical in both cases. Also, the MR is supposed to be roughly proportional to the square of the magnetization. However, in the experiments by Sarma et. al. on cold-pressed Sr2FeMoO6 powder, it was observed that the M R did not appear to be determined purely by the magnetization. Rather, the coercive fields for the hysteresis of the MR was almost 6 times that of M . Moreover, the quantity M R/M2, instead of remaining constant with changing magnetic field, itself has a hysteresis loop. Apart from establishing the exotic nature of the PMR, the experiment also tries to determine whether the MR originates from intra-grain or inter-grain tunneling. In the second chapter we present a simple toy model to reproduce the experimental results, and provide theoretical explanations. A combination of Monte Carlo and transfer matrix methods are used to simulate the hysteresis behaviour of the M R as well as of M . We show that the observed data can be understood if it is as- sumed firstly that the MR arises predominantly from inter-grain rather than intra-grain tunneling, and that the inter-grain boundaries are themselves magnetic with a coercive field higher than that of the grains. In order to motivate the use of Monte Carlo method for studying hysteresis, a brief survey of main results obtained for some simple models using this technique is also provided. In the third chapter, we study the doping and temperature dependence of core-level photoemission spectra in doped rare-earth manganites. In some recent experiments on Strontium doped (LSMO) and Barium doped (LBMO) samples, it has been observed that the M n2p3/2 core-level spectra shows an intriguing spectral weight transfer over a range of several eV , as a function of doping (x) and temperature (T ), in the ferromagnetic metallic phase. Specifically, there appears a shoulder adjacent to the main peak on the side of lower binding energy, which increases in weight and intensity as the doping increases or the temperature decreases. In LSMO samples, another shoulder was noticed on the higher binding energy side also. Moreover, in data obtained from LBMO samples, the spectra at different temperatures was subtracted from the spectra at/above Tc, and then this difference spectrum was integrated. The integrated weight, when normalized by the weight at the lowest temperature, appears to follow the square of the measured magnetization almost exactly. In order to understand the experimental data, we extended the aforementioned l - b model to include a core-level, and the attractive interaction due to a core-hole on the local valence levels. The impurity problem arising in DMFT, consisting of a single impurity site coupled to a bath, was tailored for the photoemission problem, by including this extra core-level at the impurity site. The hybridization parameters for the bath were determined self-consistently from the DMFT, and then the single particle spectral function for the core-hole was determined. This spectral function is proportional to the photo emission intensity. We found that our calculations reproduced the observed spectral weight transfer as a function of x and T both in trends and in magnitude. The integrated difference spectra weight was found to follow the square of the DMFT magnetization, just as in the experiment. Linear discretization of the conduction bath was used for all the above-mentioned cases. In one particular case, a logarithmic discretization was also undertaken for comparison, and also to obtain the exponents of the edge singularities in the theoretical spectra. In the fourth chapter, the possibility of Anderson Localization in manganites is in- vestigated, using the l - b model. According to this model, a large fraction of the valence electrons are polaronically self-trapped even in the ferromagnetic metallic phase. Due to strong on-site Coulomb interaction, these polarons provide a strongly scattering background, which can localize the mobile-electron band states close to the band edges. Since the fraction of valence electrons which are truly mobile is small, hence the Fermi energy lies close to the lower band edge. Hence, there is a possibility of an Anderson Insulator phase where all charge carriers are localized. To investigate this, we studied the behaviour of the mobility edges as a function of doping. DMFT alone does not include the physics of localization. Hence, in order to obtain the mobility edges, we combined the DMFT results with the Self-consistent Theory of Localization (STL), using a simplified prescription called Potential Well Analogy (PWA) due to Economou et. al.. We found that there is indeed an Anderson Insulator phase in a certain region of doping, which would otherwise have been supposed to be metallic based on purely DMFT results. Finally, we have compared this result, obtained using effective field theories, with an actual real space simulation of the l - b model at T=0. In this case, the mobility edge trajectories were obtained by studying the Inverse Participation Ratio (IPR), as a function of band energy and doping. In the concluding chapter, the principal results presented in this thesis are summa- rized. The limitations of the approach or approximations used are discussed, and future possibilities for overcoming these limitations outlined.

Orientador: Eduardo Miranda / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Física Gleb Wataghin / Made available in DSpace on 2018-08-16T08:19:56Z (GMT). No. of bitstreams: 1 Andrade_EricdeCastroe_D.pdf: 5537554 bytes, checksum: 1391d5fcc710b5e471f0814a4a6d484f (MD5) Previous issue date: 2010 / Resumo: Sistemas eletrônicos fortemente correlacionados desordenados possuem dois mecanismos básicos para a localização eletrônica e a subsequente destruição do estado metálico: o de Mott (causado pela interação elétron-elétron) e o de Anderson (causado pela desordem). Nesta tese, estudamos como estes mecanismos competem dentro da fase metálica e também como afetam o comportamento crítico do sistema, empregando uma generalização para o caso desordenado do cenário de Brinkman-Rice para a transição de Mott. Investigamos os efeitos de desordem fraca e moderada sobre a transição metal-isolante de Mott a T = 0 em duas dimensões. Para desordem sucientemente baixa, a transição mantém sua característica do tipo Mott, na qual temos os pesos de quasipartícula Zi indo a zero na transição e uma forte blindagem da desordem na região crítica. Em contraste com o comportamento encontrado para d = 8 , no nosso caso as flutuações espaciais dos pesos de quasipartícula são fortemente amplificadas próximo à transição de Mott de tal forma que eles adquirem uma distribuição do tipo lei de potência P (Z) ~ Z a-1 ,com a --> 0 na transição. Tal comportamento altera completamente as características desta transição com relação ao caso limpo, e é um indício robusto da emergência de uma fase de Griffiths eletrônica precedendo a transição metal-isolante de Mott, com uma fenomenologia surpreendentemente similar àquela do "ponto fixo de desordem infinita" encontrada em magnetos quânticos. Uma consequência imediata dessas novas características introduzidas pela desordem é que estados eletrônicos próximos à superfície de Fermi tornam-se mais homogêneos na região crítica, ao passo que estados com maiores energias têm o comportamento oposto: eles apresentam uma grande inomogeneidade precisamente nas vizinhanças da transição de Mott. Sugerimos que uma desordem efetiva dependente da interação é uma característica comum a todos os sistemas de Mott desordenados. Estudamos também como os efeitos bem conhecidos das oscilações de longo alcance de Friedel são afetados por fortes correlações eletrônicas. Primeiramente, mostramos que sua amplitude e alcance são consideravelmente suprimidos em líquidos de Fermi fortemente renormalizados. Posteriormente, investigamos o papel dos espalhamentos elásticos e inelásticos na presença dessas oscilações. Em geral, nossos resultados analíticos mostram que um papel proeminente das oscilações de Friedel é relegado a sistemas fracamente interagentes. Abordamos, por m, os efeitos das interações sobre o isolante de Anderson em uma dimensão. Construímos a função de escala ß (g) e mostramos que a escala de "crossover" g *, que marca a transição entre o regime ôhmico e o localizado da condutância, é renormalizada pelas interações. Como consequência, embora não haja a emergência de estados verdadeiramente estendidos, o regime ôhmico de g estende-se agora por uma região consideravelmente maior do espaço de parâmetros. / Abstract: Disordered strongly correlated electronic systems have two basic routes towards localization underlying the destruction of the metallic state: the Mott route (driven by electron-electron interaction) and the Anderson route (driven by disorder). In this thesis, we study how these two mechanisms compete in the metallic phase, and also how they change the critical behavior of the system, within a generalization to the disordered case of the Brinkman-Rice scenario for the Mott transition. We investigate the effects of weak to moderate disorder on the Mott metal-insulator transition at T = 0 in two dimensions. For sufficiently weak disorder, the transition retains the Mott character, as signaled by the vanishing of the local quasiparticle weights Zi and strong disorder screening at criticality. In contrast to the behavior in d = 8, here the local spatial fluctuations of quasiparticle parameters are strongly enhanced in the critical regime, with a distribution function P(Z) ~ Z a-1 and a --> 0 at the transition. This behavior indicates the robust emergence of an electronic Griffiths phase preceding the MIT, in a fashion surprisingly reminiscent of the " Infinite Randomness Fixed Point" scenario for disordered quantum magnets. As an immediate consequence of these new features introduced by disorder, we have that the electronic states close to the Fermi energy become more spatially homogeneous in the critical region, whereas the higher energy states show the opposite behavior: they display enhanced spatial inhomogeneity precisely in the close vicinity to the Mott transition. We suggest that such energy-resolved disorder screening is a generic property of disordered Mott systems. We also study how well-known effects of the long-ranged Friedel oscillations are affected by strong electronic correlations. We first show that their range and amplitude are signifficantly suppressed in strongly renormalized Fermi liquids. We then investigate the interplay of elastic and inelastic scattering in the presence of these oscillations. In the singular case of two-dimensional systems, we show how the anomalous ballistic scattering rate is conned to a very restricted temperature range even for moderate correlations. In general, our analytical results indicate that a prominent role of Friedel oscillations is relegated to weakly interacting systems. Finally, we discuss the effects of correlations on the Anderson insulator in one dimension. We construct the scaling function ß(g) and we show that the crossover scaling g*, which marks the transition between the ohmic and the localized regimes of the conductance, is renormalized by the interactions. As a consequence, we show that, although truly extend states do not emerge, the ohmic regime covers now a considerably larger region in the parameter space. / Doutorado / Física da Matéria Condensada / Doutor em Ciências

Orientador: Iakov Veniaminovitch Kopelevitch / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin / Made available in DSpace on 2018-08-13T05:43:34Z (GMT). No. of bitstreams: 1 GutierrezYatacue_DiegoFernando_M.pdf: 13276293 bytes, checksum: 707c38ac7116b9830e881ac37cc37b9e (MD5) Previous issue date: 2009 / Resumo: No intuito de verificar a existência de correlações supercondutoras em grafite, estudamos a possível existência do fenômeno conhecido como efeito de proximidade gigante em amostras de grafite pirolítica altamente orientada (HOPG). Medidas de magneto-transporte realizadas em amostras de HOPG com eletrodos supercondutores de In ou In-Pb revelaram a ocorrência de efeito de proximidade em uma escala muito maior que o comprimento de coerência dos eletrodos supercondutores, o que indica que a grafite pode ser considerada um supercondutor com flutuações de fase. Além disso, nossos estudos revelaram uma supressão do efeito de proximidade para campos magnéticos da ordem de 1 kOe aplicado perpendicularmente aos planos de grafite. Adicionalmente, realizamos estudos comparativos do efeito de proximidade em bismuto metálico. Discutimos os resultados obtidos em termos de modelos teóricos propostos para este assunto. / Abstract: In order to verify the existence of superconducting correlations in graphite, in this work we studied the possibility of the so-called giant proximity effect in highly oriented pyrolytic graphite (HOPG) samples. Magnetoresistance measurements performed on various thoroughly characterized HOPG samples with attached superconducting In or Pb-In electrodes revealed the occurrence of proximity effect on a scale much bigger than a coherence length of superconducting electrodes, indicating that graphite can be considered as a phase-fluctuating superconductor, indeed. Besides, our studies revealed a suppression of the proximity effect in magnetic field H ~ 1 kOe applied perpendicularly to graphene planes. Additionally, we performed comparative studies of the proximity effect in semimetallic bismuth. We discuss the obtained results in terms of available theoretical models. / Mestrado / Física da Matéria Condensada / Mestre em Física

Within condensed matter physics, systems with strong electronic correlations give rise to fascinating phenomena which characteristically require a physical description beyond a one-electron theory, such as high temperature superconductivity, or Mott metal-insulator transitions. In this thesis, a class of strongly correlated electron systems is considered. These systems exhibit fractionally charged excitations with charge +e/2 or -e/2 in two dimensions (2D) and three dimensions (3D), a consequence of both strong correlations and the geometrical frustration of the interactions on the underlying lattices. Such geometrically frustrated systems are typically characterized by a high density of low-lying excitations, leading to various interesting physical effects. This thesis constitutes a study of a model of spinless fermions on the geometrically frustrated kagome lattice. Focus is given in particular to the regime in which nearest-neighbour repulsions V are large in comparison with hopping t between neighbouring sites, the regime in which excitations with fractional charge occur. In the classical limit t = 0, the geometric frustration results in a macroscopically large ground-state degeneracy. This degeneracy is lifted by quantum fluctuations. A low-energy effective Hamiltonian is derived for the spinless fermion model for the case of 1/3 filling in the regime where |t| << V . In this limit, the effective Hamiltonian is given by ring-exchange of order ~ t^3/V^2, lifting the degeneracy. The effective model is shown to be equivalent to a corresponding hard-core bosonic model due to a gauge invariance which removes the fermionic sign problem. The model is furthermore mapped directly to a Quantum Dimer model on the hexagonal lattice. Through the mapping it is determined that the kagome lattice model exhibits plaquette order in the ground state and also that fractional charges within the model are linearly confined. Subsequently a doped version of the effective model is studied, for the case where exactly one spinless fermion is added or subtracted from the system at 1/3 filling. The sign of the newly introduced hopping term is shown to be removable due to a gauge invariance for the case of hole doping. This gauge invariance is a direct result of the bipartite nature of the hole hopping and is confirmed numerically in spectral density calculations. For further understanding of the low-energy physics, a derivation of the model gauge field theory is presented and discussed in relation to the confining quantum electrodynamic in two dimensions. Exact diagonalization calculations illustrate the nature of the fractional charge confinement in terms of the string tension between a bound pair of defects. The calculations employ topological symmetries that exist for the manifold of ground-state configurations. Dynamical calculations of the spectral densities are considered for the full spinless fermion Hamiltonian and compared in the strongly correlated regime with the doped effective Hamiltonian. Calculations for the effective Hamiltonian are then presented for the strongly correlated regime where |t| << V . In the limit g << |t|, the fractional charges are shown to be effectively free in the context of the finite clusters studied. Prominent features of the spectral densities at the Gamma point for the hole and particle contributions are attributed to approximate eigenfunctions of the spinless fermion Hamiltonian in this limit. This is confirmed through an analytical derivation. The case of g ~ t is then considered, as in this case the confinement of the fractional charges is observable in the spectral densities calculated for finite clusters. The bound states for the effectively confined defect pair are qualitatively estimated through the solution of the time-independent Schroedinger equation for a potential which scales linearly with g. The double-peaked feature of spectral density calculations over a range of g values can thus be interpreted as a signature of the confinement of the fractionally charged defect pair. Furthermore, the metal-insulator transition for the effective Hamiltonian is studied for both t > 0 and t < 0. Exact diagonalization calculations are found to be consistent with the predictions of the effective model. Further calculations confirm that the sign of t is rendered inconsequential due to the gauge invariance for g in the regime |t| << V . The charge-order melting metal-insulator transition is studied through density-matrix renormalization group calculations. The opening of the energy gap is found to differ for the two signs of t, reflecting the difference in the band structure at the Fermi level in each case. The qualitative nature of transition in each case is discussed. As a step towards a realization of the model in experiment, density-density correlation functions are introduced and such a calculation is shown for the plaquette phase for the effective model Hamiltonian at 1/3 filling in the absence of defects. Finally, the open problem of statistics of the fractional charges is discussed.

<p>    </p> <p>In this thesis, a thermodynamically consistent phase field formulation was developed to identify the physical origin of interfacial transitions that drive macroscopic phenomena, start- ing at the single-particle length scale and building up to the polycrystalline length scale. At the single-particle length scale, the framework identified two interfacial phases that are stable at the surface of Sn nanoparticles: 1) a disordered interfacial phase, i.e., the experimentally observed premelted surface layer; and 2) an ordered surficial phase displaying a remnant de- gree of order in fully melted particles. Regimes of melting behavior as a function of particle size and temperature are discussed. To bridge the gap between single-particle and densified polycrystals, an analytical model was developed to capture the physical driving forces for densification during electric field-assisted sintering. Here, the model acknowledges the struc- tural contributions of particle-particle interfaces to the strength of mechanical, electrical, and surficial driving forces for densification, and shows good agreement with experimental flash sintering data. Finally, the theory was applied to polycrystalline LiCoO₂ (LCO) and shows that the experimentally observed metal-insulator transition is driven by grain bound- ary lithium segregation, the interfacial misorientation, and the size of the abutting grains. A critical misorientation as a function of the macroscopic lithium content exists above which the grain boundaries undergo a metal-insulating transition, suggesting that the fabrication of textured LCO microstructures will delay the metal-insulator transition. </p>

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Les oxydes doubles lamellaires de cobalt et les oxydes de vanadium ont récemment suscité un vifintérêt suite à la découverte de leurs propriétés thermoélectriques prometteuses. Nos efforts visentà synthétiser de nouveaux composés dérivés de ces systèmes en utilisant la synthèse à l'étatsolide, l'échange d'ions et/ou les techniques hydrothermales. Afin de moduler et d'optimiser leurscaractéristiques thermoélectriques, nous avons ajusté la composition des oxydes de cobalt grâce àdes substitutions appropriées. Au sein du dioxyde de vanadium quasi-1D, nous avons considérétrois différentes structures polymorphes : M1, A et B. Nous avons exploré les différents systèmesen construisant l’ensemble des diagrammes de phases. Nous avons également étudié l'effet de lasubstitution du vanadium par le molybdène et le chrome sur la stabilité de ces structurespolymorphes et caractérisé leurs propriétés électroniques en relation avec les mécanismes detransition de phase. / Lamellar cobalt double oxides and vanadium oxides have recently attracted tremendous interestafter the discovery of their interesting thermoelectric properties. Our efforts aimed at synthesizingnovel related compounds using standard solid state, ion exchange and/or hydrothermaltechniques. In order to modulate and optimize their thermoelectric characteristics, we have tunedthe composition of cobalt double oxides by appropriate substitutions. In quasi 1D vanadiumoxides, the interplay between spin, charge and orbital degrees of freedom often leads toremarkable properties. Here we dealt with three different polymorphs of vanadium dioxide,namely M1, A and B. We explored the several novel systems by constructing systematic phasediagrams. We also studied the effect of Mo and Cr:V substitution on the stability of thesepolymorphs and characterized their electronic properties in relation with the structural phasetransition mechanisms. Finally, we explored their potentiality for thermoelectric applications.

The discovery of superconductivity in iron-based pnictides in 2008 gave rise to a high advance in the research of high-temperature superconductors. But up to now there is no generally admitted theory of the non-BCS mechanism of these superconductors. The electron and hole doped Ba122 (BaFe2As2) compounds investigated in this thesis are supposed to be suitable model systems for studying the electronic behavior in order to shed light on the superconducting mechanisms. The 3d-transiton metal doped Ba122 compounds are investigated using the X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XAS), X-ray emission spectroscopy (XES) and X-ray magnetic circular dichroism (XMCD), while the completely hole doped K122 is observed using XPS. The experimental measurements are complemented by theoretical calculations. A further new class of superconductors is represented by the electride 12CaO*7Al2O3: Here superconductivity can be realized by electrons accommodated in the crystallographic sub-nanometer-sized cavities, while the mother compound is a wide band gap insulator. Electronic structure investigations, represented by XPS, XAS and resonant X-ray photoelectron spectroscopy (ResPES), carried out in this work, should help to illuminate this unconventional superconductivity and resolve a debate of competing models for explaining the existence of superconductivity in this compound.