Nowadays ferromagnetism is often found in potential diluted magnetic semiconductor systems. However, many authors question the origin of this ferromagnetism, i.e. if the observed ferromagnetism stems from ferromagnetic precipitates rather than from carriermediated magnetic coupling of ionic impurities, as required for a diluted magnetic semiconductor. In this thesis, this question will be answered for transition-metal implanted ZnO single crystals. Magnetic secondary phases, namely metallic Fe, Co and Ni nanocrystals, are formed inside ZnO. They are - although difficult to detect by common approaches of structural analysis - responsible for the observed ferromagnetism. Particularly Co and Ni nanocrystals are crystallographically oriented with respect to the ZnO matrix. Their structure phase transformation and corresponding evolution of magnetic properties upon annealing have been established. Finally, an approach, pre-annealing ZnO crystals at high temperature before implantation, has been demonstrated to sufficiently suppress the formation of metallic secondary phases.

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[pt] Esta tese investigou a síntese de metanol via hidrogenação do CO2 empregando dois conjuntos de catalisadores. O primeiro é composto pelos tradicionais catalisadores de Cu/ZnO/Al e o segundo aborda os catalisadores de In2O3 e ZrO2. Com relação ao Cu/ZnO/Al, foram preparados quatro amostras via coprecipitação. Os resultados mostraram que há um teor ótimo (3,8 por cento at.) de Al para a qual se observa uma maior taxa de formação de metanol. Os catalisadores foram caracterizados por fisissorção de N2, titulação com N2O,espectroscopia de absorção atômica, ICP, DRX, XPS, TPD-(CO2,NH3 e H2O), TPSR-CO2/H2, TEM/HRTEM/EDS. Uma correlação entre a taxa de formação de metanol e a quantidade de vacâncias de oxigênio superficiais do catalisador foi observada. Foi verificado que o Al atua como um promotor na geração de vacâncias de oxigênio. Com relação aos sistemas de In2O3, foi realizado um screening e selecionado nove catalisadores. Esses sólidos foram caracterizados pelas seguintes técnicas: DRX, TPD-NH3, TPD-CO2, TPR-H2 e TPSR-CO2/H2. Foi realizado um estudo em dinâmica molecular clássica investigando os efeitos da dopagem do In2O3 e da interação entre o In2O3 e o ZrO2 e relacionando os resultados com a performance dos catalisadores. O melhor desempenho catalítico foi obtido para o inédito catalisador de 0,6Pt-In2O3+6ZnZrO2, sendo esse desempenho associado à presença de vacâncias. Além disso, pelos cálculos teóricos de dinâmica molecular foi verificado que tanto a mistura física quanto a dopagem do In2O3 podem promovem a mobilidade de oxigênio da rede dos óxidos, o que facilita a formação de vacâncias de oxigênio. Sendo assim, os dois conjuntos de catalisadores estudados mostram que as vacâncias de oxigênio têm papel central na formação do metanol a partir da hidrogenação do CO2. As informações geradas neste trabalho contribuirão para o desenvolvimento de catalisadores promissores para a futura exploração industrial da geração de metanol a partir de CO2. / [en] This thesis investigated methanol synthesis via CO2 hydrogenation using two sets of catalysts. The first set consists of the traditional Cu/ZnO/Al catalysts and the second set involves In2O3 and ZrO2 catalysts. Concerning Cu/ZnO/Al, four samples were prepared via coprecipitation. The results showed that there is an optimum Al content (3.8 percent at.) for which a higher methanol formation rate is observed. The catalysts were characterized by N2 physisorption, titration with N2O, atomic absorption spectroscopy, ICP, XRD, XPS (CO2,NH3 and H2O)-TPD, CO2/H2-TPSR, TEM/HRTEM/EDS. A correlation was observed between the rate of methanol formation and the amount of surface oxygen vacancies on the catalyst. It was found that Al acts as a promoter in the generation of oxygen vacancies. Regarding the In2O3 systems, a screening was carried out and nine catalysts were selected. These solids were characterized using the following techniques: XRD, NH3- TPD, CO2-TPD, TPR-H2 and CO2/H2-TPSR. A classical molecular dynamics study was carried out investigating the effects of doping In2O3 and the interaction between In2O3 and ZrO2 and relating the results to the performance of the catalysts. The best catalytic performance was obtained for the new 0,6Pt-In2O3+6ZnZrO2 catalyst, and this performance was associated with the presence of vacancies. In addition, molecular dynamics calculations showed that both the physical mixture and the doping of In2O3 can promote the mobility of oxygen in the oxide lattice, facilitating the formation of oxygen vacancies. Thus, the two sets of catalysts studied show that oxygen vacancies play a central role in the formation of methanol from the hydrogenation of CO2. The information generated in this work will contribute to the development of promising catalysts for the future industrial exploitation of methanol generation from CO2.

The photocatalytic degradation of the wastewater dye pollutant methylene blue (MB) at ZnO nanostructured porous thin films, deposited by direct current reactive magnetron sputtering on Si substrates, was studied. It was observed that over 4 photocatalytic cycles (0.3 mg · l−1 MB solution, 540 minUV irradiation), the rate constant k of MB degradation decreased by ∼50%, varying in the range (1.54 ÷ 0.78) · 10–9 (mol·l−1·min−1). For a deeper analysis of the photodegradation mechanism, detailed information on the nanostructured ZnO surface morphology and local surface and subsurface chemistry (nonstoichiometry) were obtained by using scanning electron microscopy (SEM) and x-ray photoelectron spectroscopy (XPS) as complementary analytical methods. The SEM studies revealed that at the surface of the nanostructured ZnO thin films a coral reef structure containing polycrystalline coral dendrites is present, and that, after the photocatalytic experiments, the sizes of individual crystallites increased, varying in the range 43 ÷ 76 nm for the longer axis, and in the range 28 ÷ 58 nm for the shorter axis. In turn, the XPS studies showed a slight non-stoichiometry, mainly defined by the relative [O]/[Zn] concentration of ca. 1.4, whereas [C]/[Zn] was ca. 1.2, both before and after the photocatalytic experiments. This phenomenon was directly related to the presence of superficial ZnO lattice oxygen atoms that can participate in the oxidation of the adsorbed MB molecules, as well as to the presence of surface hydroxyl groups acting as hole-acceptors to produce OH· radicals, which can be responsible for the generation of superoxide ions. In addition, after experiments, the XPS measurements revealed the presence of carboxyl and carbonyl functional groups, ascribable to the oxidation by-products formed during the photodegradation of MB.

Les diodes électroluminescentes (LEDs) bleues ou blanches actuelles sont constituées de couches épitaxiales planaires, essentiellement à base de GaN. Sans autres opérations technologiques, la réflexion totale interne aux interfaces réduit le nombre de photons extraits à quelques pourcents du nombre de photons émis. Cette thèse s'intéresse à un concept en rupture : les LEDs à nanofils GaN ou ZnO. Plus précisément elle vise à préciser l'intérêt de ces couches pour l'augmentation du rendement d'extraction. Nous nous sommes plus particulièrement intéressés à trois types de couches (taille des fils, arrangement), chacune mettant en jeu un processus d'extraction différent. La première géométrie, basée sur des fils relativement gros (rayons 50-100nm minimun) et distants vise à profiter des résonances ou du guidage optique pouvant exister au sein de chaque fil pour canaliser l'émission spontanée. Les coefficients de couplage de la couche active sur ces modes ainsi que la réflectivité des modes guidés en bout de fils ont notamment été évalué numériquement en fonction de la taille des fils. La seconde approche, issue de l'étude goniométrique de couches de fils MBE sur substrat Silicium, vise à profiter des propriétés d'indice effectif des couches de fils sublongueurs d'onde pour éviter le phénomène de réflexion totale à l'origine des faibles rendements d'extraction des couches planaires. Le modèle anisotrope numérique développé montre qu'un rendement d'extraction proche de 70% est envisageable sur ce type de couche épitaxiée sur Silicium. Enfin la troisième approche, plus prospective, vise à initier une étude sur l'émission dans des réseaux de fils agencés périodiquement.

<p>In this work we investigated fabrication of semiconductor nanomaterials and evaluated their potential for photo-chemical and photovoltaic applications. We investigated two different II-VI semiconductor nanomaterial systems; (i) ZnO oriented nanowire arrays non-epitaxially grown from a substrate; and (ii) colloidal CdTe nanotetrapods synthesized by solution-based thermal decomposition of organo-metallic precursors. In both the cases our main focus has been optimizing material synthesis for improving potential applications based on photon-electron interactions.</p><p>We have studied the synthesis of vertically aligned ZnO nanowire arrays (NWA), by a wet chemical process on various substrates. The synthesis is based on epitaxial growth of ZnO seed-layer on a substrate in a chemical bath consisting of an aqueous solution of zinc nitrate and hexamethylenetetramine (HMT). We have suggested an additional role played by HMT during the synthesis of ZnO nanowire arrays. We have also extended this synthesis method to fabricate hierarchical nanostructures of nanofibers of poly-L-lactide acting as a substrate for the radially oriented growth of ZnO nanowires. The combination of high surface area of the nanofibrous substrate with the flexibility of the PLLA-ZnO hierarchical nanostructure enabled the proof-of-principle demonstration of a ‘continuous-flow’ water treatment system that could effectively decompose single and combination of known organic pollutants in water, as well as render common waterborne bacteria nonviable.</p><p>We have studied another chemical synthesis that is commonly used for size controlled synthesis of colloidal quantum dots, which was modified to obtain anisotropic nanocrystals mainly for CdE (E=S, Se, Te) compositions. In this work we demonstrate by use of oleic acid (instead of alkylphosphonic acids) it is possible to synthesize CdTe and CdSe nanotetrapods at much lower temperatures (~180 ºC) than what is commonly reported in the literature, with significantly different  formation mechanism in the low-temperature reaction.</p><p>Finally, we have performed preliminary photoconduction measurements with CdTe nanotetrapods using gold ‘nanogap’ electrodes fabricated in-house, and obtain up to 100 times enhancement in current levels in the <em>I–V </em>measurements under illumination with a white light source.</p> / QC20100607

Interfacial charge transfer between metal oxides and organic semiconductors has been found to limit the efficiency of organic optoelectronic devices. Although a number of investigations of inorganic/organic systems exist, very few generally applicable rules for oxide/organic interfaces have been developed and many questions about these systems remain unanswered. Thus the studies presented in this dissertation were designed to improve the understanding of the fundamental interface physics of metal oxide/organic systems. Single molecule fluorescence microscopy was employed to determine the charge transfer mechanism while photoelectron spectroscopy was used to determine the energy level alignment of model systems. Additional computational studies allowed the examination of the properties of the charged organic molecules involved in charge transfer and modeling of the molecule-surface interaction. Calculations of the ground state properties and excited state transitions of the neutral and singly charged states of a modified perylene molecule were performed to provide insight into the orbitals of the initial and final states involved in the interfacial charge transfer process. The design and implementation of a novel UHV single molecule microscope is described. This microscope was used to observe the excited state charge transfer between a modified perylene molecule and Al₂O₃ (0001). The charge transfer mechanism was identified as involving activated trapping and detrapping of the defect derived states within the Al₂O₃ band gap, which resulted in the observation of strongly distributed kinetics for this system. The influence of defects and adsorbates on the electronic structure of ZnO and its interface with organic semiconductors was determined from photoelectron spectroscopy. Modified perylene molecules were found to have strong chemisorptive interactions with the ZnO surface involving charge transfer from defect derived ZnO states to the LUMO, while magnesium phthalocyanine molecules appear to have only weak physisorptive interactions with the ZnO surface. The interfacial investigations of the organic/oxide systems demonstrate the rich defect structure present in metal oxides. In both cases, defects were found to control the interfacial interactions between the metal oxide surface and the modified perylene molecules. Thus the manipulation of these defects states is of fundamental importance for optoelectronic device design.

Ce travail concerne l'intégration, par épitaxie sous jets moléculaires (EJM), de matériaux nitrures d'éléments III (en particulier GaN) sur des substrats et couches tremplins à base d'oxyde de zinc (ZnO). L'objectif était la réalisation et l'étude d'hétérostructures nitrures de type puits quantiques (PQs) (Al,Ga)N/GaN et (In,Ga)N/GaN, en vue d'évaluer leurs potentialités pour la réalisation de diodes électroluminescentes (LEDs). En particulier, deux orientations cristallographiques ont été étudiées : le plan " polaire " (0001) (dit plan C) et le plan " non polaire " (11-20) (dit plan A). Les couches de GaN orientées suivant le plan A (11-20), " a-GaN ", ont été épitaxiées sur des tremplins de (Zn, Mg)O (11-20) / saphir (10-12) réalisés par EJM. L'anisotropie de la morphologie de surface, de la microstructure cristalline, ainsi que de l'émission optique des couches de a-GaN, a été mise en évidence. Une série d'échantillons de PQs de a-(GaN/Al0.2Ga0.8N) avec des épaisseurs de puits différentes a été fabriquée, et l'absence d'effet Stark quantique confiné dans ces hétérostructures a été établie. Des procédés de croissance de GaN sur des substrats de ZnO massifs d'orientation A, " a-ZnO ", et C, " c-ZnO ", ont également été développés. En particulier, des couches de GaN (0001), " c-GaN ", avec une polarité Ga- ou N- ont été épitaxiées sur la face O de substrats c-ZnO. Les mécanismes de détermination de la polarité ont été analysés. Des LEDs bleues contenant une zone active constituée de PQs (In, Ga)N / GaN ont été réalisées sur des substrats c-ZnO. Des puissances de sortie atteignant 40 µW à 20 mA et 0,1 mW à 60 mA ont été mesurées. Enfin, des PQs (In, Ga)N / GaN ont été fabriqués sur substrats a-ZnO et comparés à des PQs fabriqués sur c-ZnO avec des conditions de croissance équivalentes. Les résultats indiquent une concentration en In plus importante dans le cas des PQs épitaxiés sur c-ZnO et une polarisation de l'émission de PL suivant la direction <1-100> dans le cas des PQs épitaxiés sur a-ZnO.

Les capteurs de gaz à base d'oxydes métalliques connaissent un engouement croissant pour des applications industrielles, militaires et environnementales. Néanmoins, ces capteurs se montrent peu sélectifs et nécessitent des températures de travail élevées pour obtenir une bonne sensibilité. La nanostructuration des matériaux permet d'augmenter la surface de réaction entre le gaz et le matériau hôte, améliorant ainsi la performance du capteur. ZnO est un semi-conducteur à large gap direct (3,37 eV) possédant de nombreuses propriétés physico-chimiques intéressantes, et aussi un matériau très prometteur pour les capteurs de gaz de type oxyde métallique. L'Elaboration de nanostructures de ZnO a conduit à un grand nombre d'études pour divers domaines d'applications. Dans ce contexte, cette thèse a pour objectif la synthèse des réseaux de nanofils de ZnO par voie hydrothermale et l'étude de leurs propriétés de détection. La première partie de ce travail porte sur l'étude systématique des différents paramètres influençant la synthèse des nanofils de ZnO. Les résultats montrent que la température de croissance, le pH de la solution et le temps de croissance influent sur la morphologie des nanofils de ZnO. Des nanofils avec un facteur d'aspect proche de 30 ont été obtenus sous conditions d'élaboration optimisées. La seconde partie de ce travail consiste en l'étude des propriétés de détection de nanofils de ZnO, par des méthodes électrique et optique. Les mesures électriques montrent une variation de résistance des nanofils, tandis que l'absorption UV révèle un déplacement du bandgap en présence du gaz. Une diminution de la résistance et un blue-shift de bandgap ont été observés lors de la présence d'un gaz réducteur tel que l'éthanol