Ce projet contribue à développer la prochaine génération de nano-emballages en utilisant une approche plus sûre et éco-conçue avec des avantages directs à la fois pour l'environnement et la sécurité des consommateurs. Les emballages alimentaires constituent l’un des principaux secteurs d’applications des nanotechnologies avec des enjeux environnementaux prometteurs de substitution des pétro-plastiques par des bio-plastiques et de réduction des pertes et gaspillages alimentaires grâce à des emballages plus performants, de type actifs et intelligents. Dans le cas de matériaux nano-composites (matrice polymérique contenant des nano-particules) destinés au contact alimentaire, le risque majeur en terme de santé humaine est lié à leur impact sur la migration de composés indésirables de l’emballage vers l’aliment (stabilisants UV, antioxydants, plastifiants, etc) qui peuvent avoir des effets néfastes en fonction des doses et durées d’exposition. Ces interactions contenant/contenu sont soumises à une réglementation européenne dont l’objectif est la protection de la santé du consommateur en fixant des limites de migration spécifique pour tous les composés supposés entrer dans la composition des matériaux plastiques dédiés au contact alimentaire. Dans le cas des nanomatériaux, la présence de nanoparticules est susceptible de modifier les interactions entre le polymère et les additifs et par voie de conséquence leurs propriétés de transfert. Ainsi, la formalisation des phénomènes de migration de l’emballage vers l’aliment établie sur des matériaux plastiques ne contenant pas de nanoparticules ne peut pas être directement transposée au nano-matériaux. De plus la présence de ces nanoparticules peut profondément modifier l’éco-toxicité environnementale du système matrice- nanoparticule -additif.La présente étude vise à comprendre et contrôler l’impact des structures nanocomposites (matrice polymérique contenant des nano-particules) sur les propriétés de transport (diffusivité et solubilité) des nanoparticules et des additifs chimiques en condition d’usage. À cet égard, il est nécessaire de combler le déficit de connaissances dans a caractérisation de la structure 3D, des propriétés physico-chimique et des interactions aux interfaces entre nanoparticules et matrice dans les nanomatériaux. Devant la complexité du système étudié, la modélisation est indispensable pour représenter (simplifier sans pour autant perdre trop de connaissances) la structure 3D des nanomatériaux et simuler, reproduire puis prédire, l’évolution de leurs propriétés de transfert en fonction des paramètres structurels et en condition d’usage. La modélisation des transferts est également indispensable pour, dans une approche d’ingénierie inverse, éco-concevoir et dimensionner à façon des nano-emballages sûrs pour l’Homme et l’Environnement. Dans cette optique une démarche de modélisation multi-échelle des relations structure/propriétés de transfert de masse a été mise en place sur des matériaux nanocomposites ciblés choisis pour leur pertinence dans le domaine de l’emballage alimentaire. / The market of nanotechnologies is dominated by the food packaging area which amounts more than 20% of the total nanotechnologies market in 2015. However, the wide-scale use of nanomaterials raises important questions about environmental and safety issues that could hinder their development. In the case of plastics intended to be in contact with food, the risk of contamination concerns not only the nanoparticles but also all the chemical additives added during the material processing. The presence of nanoparticles is susceptible to modify the interactions between polymer and the additives with a possible change in their transport properties and therefore the food contamination.The present work aims at identifying the relationship between the structural characteristic and the transport properties (diffusivity and solubility) of nanoparticles and chemical additives incorporated in nanocomposites. In this regard, it is necessary to fill the gap of knowledge in 3D nanostructure characterization and a multi-scale modeling of mass transfer properties of nanocomposites in real usage conditions.In this way, polyethylene and nanoclay were selected based on the best compromise between real potential applications and the scientific knowledge previously published and eventually the nanocomposites were synthesized with LLDPE, Cloisite20 and a compatibilizer by melt intercalation method.The nanocomposite structure was characterized using TEM, X-ray nanotomography, TGA and XRD then submitted to migration tests undertaken in contact with different food simulants which represent various types of food (aqueous, acid, alcoholic) following the recommendation of the European regulation on the food contact material. To evaluate the positive or adverse effects of the nanomaterials on the contamination of the food by chemical additives which are usually incorporated with the plastic packaging, the virgin polymer and nanocomposite material were spiked with a mixture of the additives exhibiting various volatility, polarity and molecular weight. Then, the transport properties (i.e inertia) of nanocomposite structure was distinctively investigated on kinetic (apparent diffusion coefficient) and thermodynamic (partition coefficient) considerations.The results indicated that nanoclay addition in plastic materials favorably reduced the migration of additives by modifying both their diffusivity in the polymer and their partition between the polymer and the food simulant. However, while the partition coefficient of additives increases in nanocomposite in comparison to pure LLDPE for the samples in contact with all types of food simulants, the reduction of diffusion coefficient is significantly dependent on the nature of the food simulant in contact. Hence, it can be concluded that the major role in the migration of additives is not played by the imposed tortuosity path, but by the factors such as the affinity between the base polymer and simulants as well as the effects of simulants on swelling and crystallinity of the samples. Moreover, the effect of additive-related parameters and the structural parameters were assessed and put in perspective with their impact on the transport properties of nanostructures. Integrating the results of characterization and transfer properties led to an improved understanding of the influence of structure of nanocomposites on their mass transfer properties and therefore on the suitability of using them as food contact materials.

Estudamos as propriedades eletrônicas de dois sistemas quase-unidimensionais distintos, resolvendo autoconsistentemente as equações de Schrödinger e Poisson.O método usado para calcular a estrutura eletrônica deste sistema e baseada na solução da equação de Schrödinger dependente do tempo usando a técnica do Split-Operator. No primeiro sistema estudamos os efeitos da corrugação periódica da interface da estrutura n-AlxGa1-xAs/GaAs na densidade eletrônica ao longo desta interface. A forma geométrica desta interface e do tipo dente de serra. Nas camadas de inversão convencionais, os elétrons estão distribuídos uniformemente ao longo da interface plana da heteroestrutura, mas devido à forma dente de serra desta estrutura, os elétrons se distribuem de maneira não uniforme ao longo da interface, produzindo um gás de elétrons quase-unidimensional. A estrutura que investigamos possui um período de 806 ANGSTROM e uma densidade residual uniforme de impurezas aceitadoras da ordem de 1015 cm-3. Calculamos a estrutura eletrônica do gás de elétrons unidimensional confinado na interface corrugada em função da voltagem aplicada ao gate, da densidade de impurezas doadoras e da temperatura. Os resultados obtidos para a densidade eletrônica mostram que, dependendo da densidade de impurezas doadoras, haverá formação de u gás de elétrons quase-unidimensional nos vértices da estrutura dente de serra. O segundo sistema que estudamos é constituído por um gás de elétrons bidimensional, formado na interface de uma camada de Al1-xGa1-xAs com uma camada de GaAs, sobre a qual, temos uma estrutura periódica de \"gates\". Aplicando-se uma voltagem negativa sobre os \"gates\" teremos a formação de fios quânticos nas regiões entre os \"gates\". Neste sistema observamos a transição de um sistema quase-bidimensional para um quase-unidimensional. Investigamos suas propriedades eletrônicas em funçãoo da temperatura, da voltagem aplicada aos \"gates\" e da densidade de impurezas doadoras. / We have studied the electronic properties of two different quasi-one-dimensional systems solving self-consistently the Schrödinger and Poisson equation. The method we use to calculate the electronic levels is based on the solution of the time-dependent Schrödinger equation using the split-operator technique. In the first system we have studied, we present a theoretical calculation of the electronic structure of v-groove quantum wires confined in modulation-doped n-AlxGa1-xAs/GaAs. The system investigated is saw tooth corrugated by bendings with period of 850 ANGSTROM. Results of the electronic structure are obtained as a function of the gate voltage and the donor impurity density. The electronic density shows the existence of a quasi one-dimensional electron gas. The second system studied here is composed by a two-dimensional electron gas confined at the interface of an Al1-xGa1-xAs/GaAs heterostructure, on top of which there is a periodic structure of gates. When a negative voltage is applied to the gates, the regions at the interface beneath them are depleted and quantum wires are formed. We have calculated the electronic structure of subband of that system. We investigated the electronic properties of the quantum wires as a function of gate voltage, from which we determine the threshold between the 2D and ID transitions, the temperature and the ionized donor density.

Understanding the structure and dynamics of molecularly thin films or the state of water confined to nanoscale dimensions is an active field of research and has wide applications in areas ranging from biology to geology. The issues concern fundamental aspects related to the manner in which a substrate influences the organization of water, origin of forces present when water is confined to nanoscale dimensions, and the influence on the structure and dynamics of water adjacent to a surface. The focus of this thesis lies in examining the thermodynamics and transport properties of interfacial and confined water. As a prelude to studying the structure of water confined between two mica surfaces, we first investigated the structuring of water adjacent to a single mica surface using grand canonical Monte Carlo (GCMC) simulations. The adsorption isotherm reveals three distinct stages as the relative vapor pressure in increased. The derived film thickness, isotherm shape, and heats of adsorption are in excellent agreement with recent experimental data. Our study does not support the 2D ice hypothesis and indicates that beyond the first adsorbed layer water is liquid-like. The characteristics of water confined to nanometer dimensions between two hydrophilic surfaces are investigated to assess the influence of chemical functionality of the hydrophilic surface on the structure of confined water. Our study shows that hydration of potassium ions on the mica surface has a strong influence on the water structure and solvation force response of confined water. In contrast to the disrupted hydrogen bond network observed for water confined between mica surfaces, water between silica surfaces is able to retain its hydrogen bond network displaying bulk-like structural features down to surface separations as small as 0.45 nm. An oscillatory solvation force response is observed only for water confined between silica surfaces. We evaluate and contrast the water density, dipole moment distributions, pair correlation functions and the solvation forces as a function of the surface separation. Recent experimental studies have shown that even for subnanometer confinement, the shear viscosity of water between mica surfaces is only three times larger than the free water viscosity. The dynamics of confined water between mica surfaces is evaluated using molecular dynamics simulations. Our analysis shows that the residence time for water in the contact layer is about two orders of magnitude larger than water in the central bulk-like regions between the surfaces. The K+ ions have a strong influence on the dynamics of confined water, leading to a decoupling in the translation and orientational motions. Our analysis also shows the presence of orientational jump dynamics in the contact layer near the mica surface. We also investigate the influence of confinement on the hydration characteristics of NaCl solutions both as a function of the salt concentration and the surface separation, H between graphite surfaces. A hydration limit is defined as the concentration at which a rapid drop in the hydration number is observed with increasing salt concentration. Despite a high degree of confinement, ions are able to form a quasi two-dimensional hydration shell between the two surfaces. The hydration number, reduces to about 4.15 at a pore width of H =8 A, when compared with the bulk hydration number of 6.25. In many practical situations, surfaces that are separated by an intervening fluid can be dissimilar giving rise to the so called Janus interface. In order to probe the fluid structure in such systems, we studied non-polar fluids confined between two asymmetric surfaces. By varying the degree of asymmetry between the two surfaces a wide variety of adsorption situations are examined using GCMC simulations and a mean field lattice model. The degree of asymmetry is found to influence the presence of frozen phases and can also support co-existing liquid and solid phases.

The principal aim of this thesis is to study the electrical transport properties of metal nanowires. Specifically, we have focussed on investigating the resistance fluctuations of Ag and Cu nanowires of diameters ranging from 15nm to 200nm and studied the instabilities that set in when the diameter is reduced below a certain range. The nanowires were grown electrochemically inside polycarbonate and alumina templates. X-ray diffraction studies on the samples showed the presence of a HCP 4H phase in the Ag nanowires in addition to the usual FCC phase, which is seen in bulk Ag. The relative ratios of these two phases were a maximum for nanowires of diameter 30nm. The X-ray diffraction studies also showed that the samples were of high chemical purity. TEM studies revealed that the wires are single crystalline in nature. Once the wires are released from the template, the wires of diameter 15nm were seen to break down spontaneously into globules due to Rayleigh instability. Wires of larger diameter tended to neck down to smaller radius but did not break down completely into globules. Both the Ag and Cu nanowire arrays had a fairly linear temperature dependence of resistance down to about 100K and reached a residual resistance below 40-50K. The temperature dependence of resistance could be fitted to a Bloch-Grüneisen formula over the entire temperature range. We found that n = 5 gave the best fit for the wires of all diameters showing that the dominant contribution to the temperature dependence of the resistivity in theses nanowires come from electron-acoustic phonon interactions. The resistivities of the wires were seen to increase as the wire diameter was decreased. This increase in the resistivity of the wires could be attributed to surface scattering of conduction electrons. In nanowires of diameter 15nm of both Ag and Cu, the relative variance of resistance fluctuations <(ΔR)2>/R2 showed a prominent peak at around ~ 220K for the Ag nanowire and ~ 260K for the Cu wire. Ag wires of diameter 20nm showed a much-reduced peak in noise at a somewhat higher temperature while this feature was completely absent in wires of larger diameter as also for the reference Ag film. The noise in wires of diameter larger than 20nm was similar to that of the reference film. For wires of diameter 15nm as we approach T*, the power spectral density showed a severe deviation from 1/f nature. We could establish that the extra fluctuation seen in the nanowires of the narrowest diameters could originate from the Rayleigh instability. The measured resistance fluctuation was found to have a magnitude similar to that estimated from a simple model of a wire showing volume preserving fluctuation. In the temperature range T ≤ 100K we observed very large non-Gaussian resistance fluctuations in a narrow temperature range for Ag and Cu wires of diameter 30nm with the fluctuations becoming much smaller as the diameter of the wires deviated from 30nm. In wires of diameter larger than 50nm the noise was almost independent of temperature in this range. The power spectrum of the resistance fluctuations also developed a large additional low frequency component near TP. We could establish that the appearance of this noise at a certain temperature (~30 – 50K) is due to the onset of martensite strain accommodation in these nanowires. To summarize, we measured the resistance and resistance fluctuations of Ag and Cu nanowires of diameters ranging from 15nm to 200nm in the temperature range 4.2-300K. The temperature dependence of resistance could be fitted to a Bloch-Grüneisen formula over the entire temperature range of measurement (4.2K-300K). The contribution of electron-phonon scattering to the resistivity was found to be similar to that of bulk. The defect free nature of our samples allowed us to identify two novel sources of noise in these nanowires. At high temperatures Rayleigh instability causes the noise levels in wires of diameter around 15nm to increase. At lower temperatures the formation of martensite state leads to an increase in noise in wires of small diameters.

Die vorliegende Arbeit befasst sich mit dem Einfluss der elektrischen Polarisation auf Eigenschaften freier Träger in ZnO basierten Halbleiterheterostrukturen. Dabei werden insbesondere Transporteigenschaften freier Träger sowie deren Rekombinationsdynamik untersucht. Die Arbeit behandelt vier inhaltliche Schwerpunkte. Der erste Schwerpunkt liegt auf den physikalischen Eigenschaften der verwendeten Materialen, hier wird der Zusammenhang der Bandlücke und der Gitterkonstanten von MgZnO Dünnfilmen und deren Magnesiumgehalt beschrieben. Weiterhin wird die Morphologie solcher Filme diskutiert. Auf unterschiedliche Substrate und Abscheidebedingungen wird dabei detailliert eingegangen. Der zweite Schwerpunkt behandelt die Eigenschaften undotierter und phosphordotierter ZnO und MgZnO Dünnfilme. Die strukturellen, Transport- und Lumineszenzeigenschaften werden hier verglichen und Rückschlüsse auf die Züchtungsbedingungen gezogen. Im dritten Schwerpunkt werden Quanteneffekte an ZnO/MgZnO Grenzflaechen behandelt. Hierbei wird insbesondere auf den Einfluss der elektrischen Polarisation eingegangen. Die Präsenz eines zweidimensionalen Elektronengases wird nachgewiesen, und die notwendigen Bedingungen zur Entstehung des sogenannten qunatum confined Stark-effects werden dargelegt. Insbesondere wird hier auf züchtungsrelevante Parameter eingegangen. Den vierten Schwerpunkt stellen Kopplungsphänomene in ZnO/BaTiO3 Heterostrukturen dar. Dabei werden zuerst die experimentell beobachten Eigenschaften verschiedener Heterostrukturen die auf unterschiedlichen Substraten gezüchtet wurden aufgezeigt. Hier stehen strukturelle und Transporteigenschaften im Vordergrund. Ein Modell zur Beschreibung der Ausbildung von Raumladungszonen in derartigen Heterostrukturen wird eingeführt und zur Beschreibung der experimentellen Ergebnisse angewandt. Die Nutzbarkeit der ferroelektrischen Eigenschaften des Materials BaTiO3 in Kombination mit halbleitendem ZnO wurden untersucht. Hierzu wurden ferroelektrische Feldeffekttransistoren unter Verwendung beider Materialien hergestellt. Die prinzipielle Eignung der Bauelemente als nichtflüchtige Speicherelemente wurde nachgewiesen.

In this thesis, we investigate spin-dependent transport through ferromagnet-contacted single-walled carbon nanotubes (SWCNTs), in which charge transport shows the Fabry-Perot (FP) interference effect, the Kondo effect and the Coulomb blockade effect at low temperatures. Hysteric magnetoresistance (MR) is observed in all three transport regimes, which can be controlled by both the external magnetic field and the gate voltage. The MR in the FP interference regime can be well understood by a model considering the intrinsic electronic structure of SWCNTs and the quantum interference effect. In the strongly interacting Kondo regime, the Kondo effect is not suppressed by the presence of nearby ferromagnetism. Several observed MR features including the non-splitted zero-bias Kondo peak and positive MR switching can be explained by the strong Kondo effect and weak ferromagnetism in the leads. In the Coulomb blockade regime, several effects that can be associated with the magneto-Coulomb effect have been observed, and isolated spin accumulation and transport through the SWCNT quantum dot have been realized by a four-probe non-local measurements. We also studied charge transport behavior through organic semiconductor pentacene thin film transistors (OTFTs) in the limit of single- or a few molecular layers of pentacene films. The charge transport in these devices can be well explained by the multiple trapping and release model. The structural disorders induced by the physical and chemical causes, such as grain boundaries, interactions with gate insulator, metal contacts and ambient conditions can be responsible for the localized trap states in the ultrathin layer OTFTs, which are further confirmed by the electric force microscopy (EFM) measurements. / text

The aim of this present research is to improve the containment properties of clayey soil by the use of bentonite and polymers as the additives. Clayey soils are generally used for the control of soil and water pollutions as they are inexpensive material. However, their applications are limited when it comes to durability of such liners in the field condition. Addition of additives to increase their efficiency by reducing the hydraulic conductivity can overcome this limitation. Generally, bentonite is used as the effective barrier additives because of their ability to render high swell and reduced hydraulic conductivity to the soil-bentonite mixtures. Due to high specific surface area and large cation exchange capacity, bentonite is always preferred for containment application. Despite their wide applicability in containment barrier, the problem with bentonite is its reduction of swell when the contaminant of interest consists of multivalent ions. Higher valency ions attach to the exchange site of bentonite and thus reduce its efficiency. To overcome these constraints the bentonite has, polymers are being used for containment applications. Normally, anionic polymers are used for such containment applications which help in increase negative charge concentration of the clayey soils. Previous studies have also proved the effectiveness of polymer in increasing the retardation factor of the soil which is due to the adsorption of contaminants to the negatively charged surface of clay. Hence attempt is also made in this thesis to study the effectiveness of super absorbent polymers when used as additive to the clayey soil. In this thesis, effectiveness of the local Bangalore soil for its use as barrier material is studied. Tests are done on the compacted sample to determine its contaminant transport properties. Because of their low hydraulic conductivities, advective flux through the barriers is negligible. In such cases, contaminant migration takes place due to the difference in concentration and this transport mechanism is known as diffusion. Laboratory test have been done to determine the diffusion coefficient of soil when the soil is saturated. For barriers and liner systems which are not fully saturated, suction adds to the hydraulic head. For unsaturated samples, although the liquid phase diffusion have been found to be nominal, head difference caused due to suction facilitates the migration of contaminants. Hence, effects of initial degree of saturation and density in contaminant transport process through soils have been examined. An attempt has been made to study unsaturated transport properties by using saturated transport parameters and unsaturated soil parameters obtained from soil-water characteristics curve. Another focus of this thesis has been towards enhancing the containment property of local soil by using additives. Effects of addition of bentonite and polymer on contaminant transport parameters of the soil have been studied. An attempt has been made to reduce the hydraulic conductivity of soil by using additives like bentonite. In addition, use of super-absorbent polymer as a novel material for barrier application has been studied to determine its suitability for local conditions. Experiments have been conducted to determine free swell, hydraulic conductivity and diffusion coefficient of soil-bentonite and soil-polymer mixes and compare them to those of local soil. To determine the effectiveness of soil-bentonite and soil-polymer mixes under the attack of concentrated solution over a long duration, chemical compatibility tests have been carried out. Micro-structural changes in the soil on addition of bentonite and polymer have been studied with the help of scanning electron microscope (SEM) images. Mineralogical changes occurring in the soil due to the additives have been studied using X-Ray Diffraction (XRD) plots. Effects of salt solution on soil-bentonite and soil-polymer mixes have also been studied by the help of SEM images and XRD plots. The final section of this thesis is on analysis of barrier performance for different conditions of densities, compaction and saturation by using numerical software CODE_BRIGHT. Transport parameters obtained from the experiments conducted in previous sections have been used as input for the analysis. A field condition of Bingipura landfill site in South Bangalore, Bangalore city has been simulated as a case study for this thesis. Time taken for contaminants to migrate from landfill to the nearby water body which is at a distance of about 122 meters is calculated for no barrier case. When barrier is provided, concentration variations of contaminant through the barrier with time are plotted and the results are compared for soil barrier, soil-bentonite barrier and soil-polymer barrier. v

Orientadora: Profa. Dra. Raquel de Almeida Ribeiro / Tese (doutorado) - Universidade Federal do ABC, Programa de Pós-Graduação em Física, 2015. / O crescente interesse em novos materiais com propriedades eletrônicas promissoras, tais como termoeletricidade e supercondutividade entre outras, tem levado a comunidade científica a estudar intensivamente por muitos anos uma classe de materiais conhecida como compostos Zintl. Nesse sentido que propomos nesta Tese o estudo de novos materiais termoelétricos, caracterizando e avaliando suas propriedades, buscando um melhor entendimento das propriedades físicas destes materiais em baixa temperatura, utilizando como ponto de partida à família de compostos Zintl. Compostos do tipo Zintl são governados pelo balanço de cargas entre íons doadores e complexas estruturas, geralmente presentes em grandes células unitárias. Duas famílias complexas de compostos Zintl que tem sido investigadas são formadas por RE14MPn11, AE14MPn11, RE11MPn9 e AE11MPn9 (RE = Yb, Eu; AE = Ca, Sr; M = metal de transição; Pn = pictanídeos). Monocristais de Yb11AlSb9 cristalizam com estrutura ortorrômbica de grupo espacial Iba2 com parâmetros de rede a = 11.76 Å, b = 12.39 Å and c = 16.68 Å. Dados de resistividade elétrica do composto Yb11AlSb9 entre 300 K e 0.4 K, nos mostram um comportamento metálico acima de 100 K e semicondutor abaixo desta temperatura indicando a formação de um estado semicondutor de gap pequeno, apresentando um dependência com a temperatura e com o campo magnético entre 0.4 K > T > 2 K. Medidas de calor específico nos mostram que o composto apresenta uma significante dependência de amostra, como observado também nas medidas de resistividade. Observamos também uma dependência com o campo magnético de Cp para T < 4 K até T = 0.4 K. A contribuião eletrônica foi extraída do ajuste linear da curva Cp/T em função T para T < 2 K e nos mostrou uma dependência do parâmetro de Sommerfeld com a temperatura e com o campo magnético, (T,H), com valores de 230 mJ/mol.K2 e 0 mJ/mol.K2 para H = 0 e 3 T, respectivamente. / The growing interest in new materials with promising electronic properties, such as thermoelectricity and superconductivity among others, has lead the scientific community to intensively study a class of materials known as Zintl compounds for many years. In this sense that we propose in this work the study of new thermoelectric materials, characterizing and evaluating their properties, seeking a better understanding of the physical properties of these materials at low temperatures, using as a starting point the family of Zintl compounds. Zintl compounds are governed by charge balance between donor ions and complex structures, and generally present large unit cells. Tow families of complex Zintl phases that has been recently investigated is comprised of RE14MPn11, AE14MPn11, RE11MPn9 and AE11MPn9 compounds (RE = Yb, Eu; AE = Ca, Sr; M = Transition metal; Pn = Pictogens). Single crystals have been grown by the flux method using Sn flux. Yb11AlSb9 crystallized in an orthorhombic structure (space group Iba2) with lattice parameters a = 11.76 Å, b = 12.39 Å and c = 16.68 Å. The Yb11AlSb9 electrical resistivity data from 300 to 0.4 K shows metallic behavior until 100 K, below which there is an increase indicative of a small gap semiconducting ground state and present H-dependence between 0.4 K > T > 2 K. Specific heat data show us the significant sample and H-dependence,as observed in resistivity measurements. We also observed a dependence with the magnetic field of Cp to T < 4 K at T = 0.4 K. The electronic contribution was extracted from the linear fit of the curve Cp/T depending on T to T < 2 K and showed a dependence on the Sommerfeld parameter with the temperature and the magnetic field, (T,H), with values 230 mJ/mol.K2 and 0 mJ/mol.K2 for H = 0 and 3 T, respectively.

Le tantale est un métal à utilisation stratégique notamment dansle domaine de l'électronique et des implants biomédicaux,domaines qui requièrent la réalisation de dépôts de tantale encouches minces. L’objectif de cette thèse est de déposer par voieélectrochimique et à température ambiante du tantale métalliqueà partir d'un sel de tantale solubilisé dans un électrolyte liquideionique qui possède à la fois les propriétés d’un solvant et d’unélectrolyte. Ils ont une fenêtre électrochimique large qui les rendprometteurs pour l’électrodéposition des matériaux réfractairescomme le tantale. Nous avons établis au cours de cette thèse denouvelles connaissances sur les propriétés physico-chimiques etde transport de l’électrolyte formé du sel de tantale TaF5 et duliquide ionique [BMPyr][TFSI]. Ces études corrélées à desanalyses électrochimiques et des analyses de la morphologie etde la composition élémentaire du dépôt ont conduit à proposerun mécanisme de réduction du sel de tantale pentavalent entantale métallique. Du tantale métallique sous une formeamorphe existe dans les couches profondes du dépôtaccompagné de résidus du liquide ionique enfermé dans lespores des couches déposées. / Tantalum is a metal of strategic uses such as in the field ofelectronics and biomedical implants. These fields require thedeposition of thin metallic tantalum films on different substrates.The aim of this thesis is to perform tantalum electrodepositionfrom tantalum salt at room temperature using room temperatureionic liquids as electrolytes. Tantalum electrodeposition isimpossible in aqueous solutions; therefore ionic liquids are thebest choice for this application because of their largeelectrochemical window. Room temperature ionic liquidsaccomplish both the roles of a solvent and an electrolyte. Theirperspectives are encouraging for the electrodeposition ofrefractory metals as tantalum. We have established in this thesisnew knowledge about the physicochemical and transportproperties of the electrolyte formed by tantalum salt TaF5 andthe room temperature ionic liquid [BMPyr][TFSI]. These studiescorrelated with electrochemical analysis, morphology andelemental composition analysis of the layers deposited served usin the understanding of the reduction mechanism of tantalumsalt into its metallic form. An amorphous metallic form oftantalum exists in deeper layers of the deposit in addition toresidues of the ionic liquid trapped in the pores of the layers.

Estudamos as propriedades eletrônicas de dois sistemas quase-unidimensionais distintos, resolvendo autoconsistentemente as equações de Schrödinger e Poisson.O método usado para calcular a estrutura eletrônica deste sistema e baseada na solução da equação de Schrödinger dependente do tempo usando a técnica do Split-Operator. No primeiro sistema estudamos os efeitos da corrugação periódica da interface da estrutura n-AlxGa1-xAs/GaAs na densidade eletrônica ao longo desta interface. A forma geométrica desta interface e do tipo dente de serra. Nas camadas de inversão convencionais, os elétrons estão distribuídos uniformemente ao longo da interface plana da heteroestrutura, mas devido à forma dente de serra desta estrutura, os elétrons se distribuem de maneira não uniforme ao longo da interface, produzindo um gás de elétrons quase-unidimensional. A estrutura que investigamos possui um período de 806 ANGSTROM e uma densidade residual uniforme de impurezas aceitadoras da ordem de 1015 cm-3. Calculamos a estrutura eletrônica do gás de elétrons unidimensional confinado na interface corrugada em função da voltagem aplicada ao gate, da densidade de impurezas doadoras e da temperatura. Os resultados obtidos para a densidade eletrônica mostram que, dependendo da densidade de impurezas doadoras, haverá formação de u gás de elétrons quase-unidimensional nos vértices da estrutura dente de serra. O segundo sistema que estudamos é constituído por um gás de elétrons bidimensional, formado na interface de uma camada de Al1-xGa1-xAs com uma camada de GaAs, sobre a qual, temos uma estrutura periódica de \"gates\". Aplicando-se uma voltagem negativa sobre os \"gates\" teremos a formação de fios quânticos nas regiões entre os \"gates\". Neste sistema observamos a transição de um sistema quase-bidimensional para um quase-unidimensional. Investigamos suas propriedades eletrônicas em funçãoo da temperatura, da voltagem aplicada aos \"gates\" e da densidade de impurezas doadoras. / We have studied the electronic properties of two different quasi-one-dimensional systems solving self-consistently the Schrödinger and Poisson equation. The method we use to calculate the electronic levels is based on the solution of the time-dependent Schrödinger equation using the split-operator technique. In the first system we have studied, we present a theoretical calculation of the electronic structure of v-groove quantum wires confined in modulation-doped n-AlxGa1-xAs/GaAs. The system investigated is saw tooth corrugated by bendings with period of 850 ANGSTROM. Results of the electronic structure are obtained as a function of the gate voltage and the donor impurity density. The electronic density shows the existence of a quasi one-dimensional electron gas. The second system studied here is composed by a two-dimensional electron gas confined at the interface of an Al1-xGa1-xAs/GaAs heterostructure, on top of which there is a periodic structure of gates. When a negative voltage is applied to the gates, the regions at the interface beneath them are depleted and quantum wires are formed. We have calculated the electronic structure of subband of that system. We investigated the electronic properties of the quantum wires as a function of gate voltage, from which we determine the threshold between the 2D and ID transitions, the temperature and the ionized donor density.