O objetivo do trabalho, foi o desenvolvimento de uma metodologia de preparação de amostras de ZnO e Zn(1-X)Co(X)O de alta pureza baseada no processo químico sol-gel, e a análise das mesmas com a técnica de Correlação Angular γ-γ Perturbada (CAP). As técnicas de Difração de Raios X e Microscopia Eletrônica de Varredura também foram utilizadas para a caracterização das amostras. Além disso, foram produzidas amostras de Zn(1-X)Co(X)O na tentativa de observar comportamento ferromagnético à temperatura ambiente, através da variação da concentração de Co com diferentes atmosferas e temperaturas de tratamento. As medidas de CAP foram realizadas em um espectrômetro γ com quatro detectores de BaF2, que possibilita a aquisição simultânea de 12 espectros de coincidências γ-γ atrasadas. O núcleo de prova utilizado foi o 111In → 111Cd, que possui cascata γ de 172 - 245 keV populado no decaimento do 111In por captura eletrônica. Os campos hiperfinos foram medidos a partir do nível intermediário de energia de 245 keV do 111Cd com spin I = 5/2 e T1/2 = 85 ns. Os resultados mostram, que a metodolo- gia desenvolvida é adequada para a produção das amostras, fato que é comprovado pela concordância dos valores obtidos com os reportados na literatura. / The aim of this work was the development of high-purity ZnO and Zn(1-X)Co(X)O sample preparation methodology based on sol-gel chemical process, as well as the analysis of these samples by means of Perturbed Angular γ-γ Correlation technique (PAC). Also, X-ray Diffraction and Scanning Electron Microscopy were used to characterize the samples produced. In addition, Zn(1-X)Co(X)O samples were produced in an attempt to observe ferromagnetic behavior at room temperature, through the variation of Co concentration, with different atmospheres and annealing temperatures. The PAC measurements were performed in a BaF2 four-detector γ spectrometer, which allows simultaneous acquisition of 12 γ-γ delayed coincidence spectra. 111In→111Cd nuclear probe was used for these measurements, which has γ cascade of 172 - 245 keV populated in the decay of 111In by electron capture. The hyperfine fields were measured from the intermediate energy level of 245 keV in 111Cd with spin I = 5/2 and T1/2= 85 ns. The results show that the developed methodology is suitable for the production of these samples, which is evidenced by the agreement with values reported on literature.

Ce travail s’intéresse à la synthèse de films minces composites Zn-Si-O et Ti-Si-O à l’aide d’un procédé hybride combinant le dépôt de silice par PECVD (Plasma Enhanced Chemical Vapour Deposition) à partir du précurseur organométallique hexaméthyldisiloxane (HMDSO-Si2C6H180), et la pulvérisation réactive de zinc ou de titane. L’élaboration de revêtements dont la composition s’échelonne d’un oxyde métallique ZnOx ou TiOx à la silice est rendue possible en agissant sur le débit du précurseur. L’ajout de silicium dans le revêtement fait évoluer sa morphologie de colonnaire à dense. De plus un phénomène de compétition entre les composantes PECVD et pulvérisation du procédé est mis en évidence. Ainsi la mesure des vitesses de dépôt en fonction du débit d’HMDSO permet de déterminer les valeurs de débits critiques de précurseurs à partir desquelles le dépôt de silice par PECVD est initié, et pour lesquelles le recouvrement de la cible par le dépôt de silice se produit. Les caractérisations des revêtements montrent que ceux-ci sont constitués, dans une zone proche de l’interface avec l’acier d’un mélange d’oxydes non stoechiométriques qui diffère de manière importante d’un mélange ZnO+SiO2 ou TiO2+SiO2. Pour les revêtements de type Ti-Si-O le titane est en excès dans la zone proche de l’interface tandis que dans les revêtements de type Zn-Si-O le silicium est en excès. On observe alors une décroissance progressive de la concentration atomique respectivement de titane et de silicium lorsqu’on approche de la surface du revêtement. Ces évolutions peuvent être reliées à un effet de l’augmentation de la température dans la première phase de l’élaboration, qui agit sur la cinétique de dépôt par PECVD et conditionne l’état de contamination de la cible / The present work deals with the synthesis of Zn-Si-O and Ti-Si-O composite thin films by a hybrid process. The coatings are prepared by combining PECVD (Plasma Enhanced Chemical Vapour Deposition) of silicon oxide from hexamethyldisiloxane (HMDSO-Si2C6H180) and reactive sputtering of a zinc or a titanium target. Any composition of the deposited layer can be obtained from zinc oxide or titanium oxide to silicon oxide, by controlling the HMDSO flow rate in the reactor. The morphologies evolve from columnar to dense by adding silicon in the coating. Moreover, a competitive deposition process takes place between PECVD and sputtering. The critical flow rates above which the PECVD silicon oxide deposition takes place on the substrate and on the target can be described from measurements of the thin film deposition rates as a function of the HMDSO flow rate. The coating caracterisations show that they are, near the coating-substrate interface, made of a mixture of non-stoechiometric oxides whose composition is different from a ZnO+SiO2 or a TiO2+SiO2 mixing. Titanium and silicon are in excess near the coating-substrate interface, respectively in the Ti-Si-O and Zn-Si-O thin films. Then the atomic concentrations of titanium and silicon progressively decrease when reaching the surface of the thin film. These behaviours are correlated with an increase of the temperature during the first phase of deposition that increases the PECVD deposition kinetics and determines the contamination state of the target

Ces dernières années, les énormes progrès réalisés en nanotechnologie ainsi qu’en science des matériaux ont conduit à la préparation de nombreuses nouvelles nanoparticules sans réellement connaître l’ensemble des propriétés associées à leurs dimensions. La première partie de notre travail vise à évaluer les risques et les problèmes associés aux nanomatériaux, en termes de toxicité, en utilisant des nanoparticules de ZnO. Nous avons tout d’abord étudié la capacité de ces nanoparticules à générer des espèces réactives d’oxygènes (EROs) sous irradiation UV en utilisant trois types des quantum dots (QDs) comme modèles, ZnO, ZnO dopé avec des ions Cu2+ et ZnO avec des ions Cu2+ adsorbés à sa surface. Les trois types des QDs ont montré une forte capacité à générer des EROs mais ceux modifiés par les ions Cu2+ en périphérie sont les plus producteurs. Ces QDs inhibent également le plus fortement la croissance de la bactérie E. coli. La toxicité n’est cependant pas dépendante des EROs photo-produits ni du zinc (+2) libéré par les QDs et montre qu’un mécanisme plus complexe doit être considéré. Dans une second partie, nous avons tenté d’améliorer l’activité photocatalytique de nanobâtonnets de ZnO en les associant à de l’oxyde de graphène réduit (rGO). Des nanocomposites ZnO/rGO ont été préparés par voie solvothermale et utilisés pour la phototodégradation du colorant Orange II comme modèle de polluant. Les résultats obtenus montrent que le photocatalyseur ZnO/rGO est très efficace sous irradiation solaire ou visible et qu’il est peu sensible à des variations de pH ou à la présence de perturbateurs dans le milieu. Finalement, le photocatalyseur est très stable et peut être réutilisé plus de dix fois sans perte notable d’activité. / In recent years, tremendous advances in nanotechnology and materials science have led to the synthesis of many new nanoparticles without really knowing all the properties associated with their dimensions. The first part of our work aims to evaluate the risks and problems associated with nanomaterials, in terms of toxicity, using ZnO nanoparticles. We first studied the ability of these nanoparticles to produce reactive oxygen species (ROS) under UV irradiation using three ZnO-based quantum dots (QDs) as models, ZnO, ZnO doped with Cu2+ ions and ZnO with chimisorbed Cu2+ ions at their periphery. The three QDs have a strong capacity of generating ROS but those modified with Cu2+ at their surface were found the be the highest producers. These dots were also found to inhibit more markedly the growth of the E. coli bacteria. The toxicity does neither depend on the amount of photo-generated ROS nor on the amount of Zn(+2) leaked by the QDs, thus indicating that a more complex mechanism should be considered. In a second part, we tried to improve the photocatalytic efficiency of ZnO nanorods by associating these nanomaterials with reduced graphene oxide (rGO). ZnO/rGO composites were prepared by a solvothermal method and applied for the photodegradation of Orange II used as model pollutant. Results obtained demonstrate that the ZnO/rGO photocatalyst is highly efficient under solar and under visible light irradiation and weakly sensitive to pH changes and to the presence of perturbators in the reaction medium. Finally, the photocatalyst is stable and can be reused up to ten times without significant loss of catalytic activity.

O grande impacto ambiental causado pelo chorume proveniente de aterros sanitários impulsiona as pesquisas para o seu tratamento, com o objetivo de se obter a máxima degradação possível dos seus contaminantes recalcitrantes e tóxicos, diminuindo-se assim a sua toxicidade. O desenvolvimento de uma tecnologia eficiente e econômica para o tratamento é indispensável devido ao grande volume gerado e à legislação ambiental cada vez mais restritiva. Desta forma, os Processos Oxidativos Avançados (POAs) são avaliados como uma estratégia para o pré-tratamento, com um alto poder de degradação não seletivo e relação custo-benefício vantajosa. Dos diversos tipos de POAs existentes, aqueles que utilizam semicondutores para a fotocatálise heterogênea e luz solar como fonte de irradiação são os de maior interesse, devido a sua relativa eficiência, estabilidade fotoquímica, natureza não tóxica e baixo custo. Este estudo consistiu em avaliar o nível de degradação do chorume proveniente do aterro sanitário de Cachoeira Paulista - SP, utilizando como catalisador o ZnO irradiado pela luz solar, que possui um vasto espectro de fotoativação aliado ao seu baixo custo. As variáveis de entrada em dois níveis, foram o pH, o tempo de reação, a espessura da camada de ZnO impregnada sobre uma placa metálica e a concentração do efluente. Como variável resposta os valores de concentração expressa em Carbono Orgânico Total (COT) foi a mais adequada. O planejamento de experimentos utilizado foi o fatorial 23 com duplicata no ponto central. Na etapa delineatória, reduções de 28 % de COT foram alcançadas. A utilização da fotocatálise heterogênea utilizando ZnO fotoirradiado com luz solar se mostrou promissora para ser utilizada como um pré-tratamento do chorume. / The major environmental impact of leachate from landfills drives research to treat it, and aims to obtain the maximum degradation of their recalcitrant and toxic contaminants. The development of an efficient and economical treatment technology is indispensable due to the large volume generated and the increasingly restrictive environmental legislation. Thus, Advanced Oxidation Processes (AOPs) are evaluated as a strategy to pre-treatment with a high power non-selective degradation and advantageous cost-benefit ratio. From various types of POAs, those which use the heterogeneous photocatalytic semiconductor and solar light as the source of irradiation are the most interesting, because of its relative efficiency, photochemical stability, low cost and non-toxic nature. This study have assessed the level of degradation of the leachate from the landfill of Cachoeira Paulista - SP, using ZnO irradiated by sunlight as catalyst, which has a wide spectrum of photoactivation combined with its low cost. The input variables on two levels, were pH, reaction time, the thickness of the ZnO layer impregnated on a metal plate and concentration of the effluent. The most appropriate output variable was concentration, expressed in means of Total Organic Carbon (TOC). For the photocatalytic process, a factorial design (23) was used for the design of experiments. In final stage, reductions of 28% TOC were achieved. The use of heterogeneous photocatalysis using solar photoirradiated ZnO seems to be a great alternative as a pre-treatment of leachate.

O objetivo do trabalho, foi o desenvolvimento de uma metodologia de preparação de amostras de ZnO e Zn(1-X)Co(X)O de alta pureza baseada no processo químico sol-gel, e a análise das mesmas com a técnica de Correlação Angular γ-γ Perturbada (CAP). As técnicas de Difração de Raios X e Microscopia Eletrônica de Varredura também foram utilizadas para a caracterização das amostras. Além disso, foram produzidas amostras de Zn(1-X)Co(X)O na tentativa de observar comportamento ferromagnético à temperatura ambiente, através da variação da concentração de Co com diferentes atmosferas e temperaturas de tratamento. As medidas de CAP foram realizadas em um espectrômetro γ com quatro detectores de BaF2, que possibilita a aquisição simultânea de 12 espectros de coincidências γ-γ atrasadas. O núcleo de prova utilizado foi o 111In → 111Cd, que possui cascata γ de 172 - 245 keV populado no decaimento do 111In por captura eletrônica. Os campos hiperfinos foram medidos a partir do nível intermediário de energia de 245 keV do 111Cd com spin I = 5/2 e T1/2 = 85 ns. Os resultados mostram, que a metodolo- gia desenvolvida é adequada para a produção das amostras, fato que é comprovado pela concordância dos valores obtidos com os reportados na literatura. / The aim of this work was the development of high-purity ZnO and Zn(1-X)Co(X)O sample preparation methodology based on sol-gel chemical process, as well as the analysis of these samples by means of Perturbed Angular γ-γ Correlation technique (PAC). Also, X-ray Diffraction and Scanning Electron Microscopy were used to characterize the samples produced. In addition, Zn(1-X)Co(X)O samples were produced in an attempt to observe ferromagnetic behavior at room temperature, through the variation of Co concentration, with different atmospheres and annealing temperatures. The PAC measurements were performed in a BaF2 four-detector γ spectrometer, which allows simultaneous acquisition of 12 γ-γ delayed coincidence spectra. 111In→111Cd nuclear probe was used for these measurements, which has γ cascade of 172 - 245 keV populated in the decay of 111In by electron capture. The hyperfine fields were measured from the intermediate energy level of 245 keV in 111Cd with spin I = 5/2 and T1/2= 85 ns. The results show that the developed methodology is suitable for the production of these samples, which is evidenced by the agreement with values reported on literature.

Ce travail de thèse a été dans un premier temps consacré à l’influence des points quantiques (QDs) de ZnO de taille 5 nm, synthétisés par voie sol-gel sur les propriétés physiques et physico-chimiques des réseaux enregistrés par holographie dans des photopolymères de type acrylate. L’amorceur, ici la camphorquinone, étant un élément clé de la photopolymérisation, une double approche expérimentale/théorique a permis de comprendre ses modifications photochimiques en fonction de la composition du système photosensible. L’introduction de 1 % en masse des QDs améliore les propriétés physiques des matériaux photostructurés (augmentation du rendement de diffraction due à la répartition spatiale des QDs) sans modifier la cinétique de polymérisation. Dans un deuxième temps, l’influence des QDs sur la durabilité des matériaux sous irradiation à λ 300 nm a été examinée. L’exposition des polymères purs et dopés entraîne des modifications chimiques de la matrice polymère et le dégagement de gaz. Cependant, la présence de QDs de ZnO (1 % en masse) a un effet photocatalytique sur la durabilité du matériau. Cet effet implique la contribution de l’électron et du trou photogénérés au mécanisme de dégradation, conduisant à une extinction partielle de la fluorescence des QDs. Il est d’autant plus important que le taux de QDs augmente dans le milieu et souligne le rôle de l’interface polymère/nanoparticule. En revanche, l’introduction de 1 % de nanocristaux semi-conducteurs de ZnO (taille 10-30 nm) entraîne une stabilisation de la matrice qui traduit un effet photoprotecteur inattendu de ces nanoparticules. / This work was first devoted to the influence of ZnO quantum dots (QDs) with 5 nm diameter, synthesized by sol-gel method on the physical and physico-chemical properties of the gratings recorded in acrylate photopolymers by holography. Since the photosensitizer (in our study camphorquinone) is a key element in the photopolymerization process, a double experimental/theoretical approach was applied to understand its photochemical modifications as a function of the content of the photosensitive system. The introduction of 1 wt % of Qds improves the physical properties of the photo-patterned materials (increase of the diffraction efficiency due to the spatial distribution of QDs) without modifying the kinetics of polymerization. Secondly, the influence of QDs on the durability of materials under irradiation at λ 300 nm was investigated. The exposure of pure and doped polymers leads to the chemical modifications of the polymer matrix and the release of gas. However, ZnO QDs (1 wt % loading) negatively influenced the durability by their photocatalytic effect. This effect points out the contribution of the photo-generated charge carriers to the mechanism of degradation, leading to a partial quenching of the fluorescence of QDs. It also increases with increasing QDs content and underlines the role of the polymer/nanoparticule interface. On the contrary, the presence of 1 wt % of semi-conductor nanocrystals of ZnO (size 10-30 nm) induces a stabilization of the matrix. This reveals an unexpected photo-protective effect of these nanoparticules.

With the recent development of in situ transmission electron microscopy (TEM) characterization techniques, the real time study of property-structure correlations in nanomaterials becomes possible. This dissertation reports the direct observations of deformation behavior of Al2O3-ZrO2-MgAl2O4 (AZM) bulk ceramic nanocomposites, strengthening mechanism of twins in YBa2Cu3O7-x (YBCO) thin film, work hardening event in nanocrystalline nickel and deformation of 2wt% Al doped ZnO (AZO) thin film with nanorod structures using the in situ TEM nanoindentation tool. The combined in situ movies with quantitative loading-unloading curves reveal the deformation mechanism of the above nanomaterial systems. At room temperature, in situ dynamic deformation studies show that the AZM nanocomposites undergo the deformation mainly through the grain-boundary sliding and rotation of small grains, i.e., ZrO2 grains, and some of the large grains, i.e., MgAl2O4 grains. We observed both plastic and elastic deformations in different sample regions in these multi-phase ceramic nanocomposites at room temperature. Both ex situ (conventional) and in situ nanoindentation were conducted to reveal the deformation of YBCO films from the directions perpendicular and parallel to the twin interfaces. Hardness measured perpendicular to twin interfaces is ~50% and 40% higher than that measured parallel to twin interfaces, by ex situ and in situ, respectively. By using an in situ nanoindentation tool inside TEM, dynamic work hardening event in nanocrystalline nickel was directly observed. During stain hardening stage, abundant Lomer-Cottrell (L-C) locks formed both within nanograins and against twin boundaries. Two major mechanisms were identified during interactions between L-C locks and twin boundaries. Quantitative nanoindentation experiments recorded during in situ experiments show an increase of yield strength from 1.64 to 2.29 GPa during multiple loading-unloading cycles. In situ TEM nanoindentation has been conducted to explore the size dependent deformation behavior of two different types (type I: ~ 0.51 of width/length ratio and type II: ~ 088 ratio) of AZO nanorods. During the indentation on type I nanord structure, annihilation of defects has been observed which is caused by limitation of the defect activities by relatively small size of the width. On the other hand, type II nanorod shows dislocation activities which enhanced the grain rotation under the external force applied on more isotropic direction through type II nanorod.

A new set of thermal neutron detectors has been developed as a near term 3He tube replacement. The zinc oxide scintillator is an ultrafast scintillator which can be doped to have performance equal to or superior to 3He tubes. Originally investigated in the early 1950s, this room temperature semiconductor has been evaluated as a thermal neutron scintillator. Zinc oxide can be doped with different nuclei to tune the band gap, improve optical clarity, and improve the thermal neutron detection efficiency. The effects of various dopant effects on the scintillation properties, materials properties, and crystal growth parameters have been analyzed. Two different growth modalities were investigated: bulk melt grown materials as well as thin film scintillators grown by metalorganic chemical vapor deposition (MOCVD). MOCVD has shown significant advantages including precise thickness control, high dopant incorporation, and epitaxial coatings of neutron target nuclei. Detector designs were modeled and simulated to design an improved thermal neutron detector using doped ZnO layers, conformal coatings and light collection improvements including Bragg reflectors and photonic crystal structures. The detectors have been tested for crystalline quality by XRD and FTIR spectroscopy, for scintillation efficiency by photo-luminescence spectroscopy, and for neutron detection efficiency by alpha and neutron radiation tests. Lastly, a novel method for improving light collection efficiency has been investigated, the creation of a photonic crystal scintillator. Here, the flow of optical light photons is controlled through an engineered structure created with the scintillator materials. This work has resulted in a novel radiation detection material for the near term replacement of 3He tubes with performance characteristics equal to or superior to that of 3He.

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.

ZnO window layers for CIGS solar cells are grown with a DC sputtering technique instead of a conventional RF sputtering technique. Transparent window layers and buffer layers are sputtered from the Zn target in the presence of Oxygen. The window layer is doped with Aluminum in order to achieve high electrical conductivity and thermal stability. The effect of different sputtering parameters on the electrical and optical properties of the films is elaborately studied. Sets of annealing experiments are also performed. Combinations of different deposition parameters are examined to design the optimum fabrication conditions. We are able to deposit 85% transparent, Al doped ZnO films having 002-axis orientation and 4e-4 ohm-cm resistivity, which is successfully, used on CIGS solar cells. Resistivity of undoped ZnO buffer layers is varied form 10-2 ohm-cm to unmeasurable by varying the sputtering parameters. The performance of a reactively sputtered window layer and a buffer layer have matched the performance of the RF sputtered ZnO on CIGS solar cells. There has been considerable effort to eliminate Chemical Bath Deposition of the CdS buffer layer from CIS solar cell fabrication. The performance of an undoped DC sputtered ZnO layer is examined on Cd free CIGS solar cells. The ZnO buffer layer is directly sputtered on an underlying CIGS material. The performance of Cd free solar cells is highly susceptible to the presence of Oxygen in the sputtering ambient of the buffer layer deposition [6]. As Oxygen is a growth component in reactive sputtering, the growth mechanisms of the DC-sputtered buffer layer are studied to improve the understanding. The performance of all reactively sputtered ZnO devices matched the values reported in the literature and the results for DC sputtered ZnO on Cd-free solar cells were encouraging.