Submitted by Tiago Carneiro Gomes (tiagogomes.prof@gmail.com) on 2018-06-30T16:46:33Z No. of bitstreams: 1 Gomes_T_C_tese_de_Doutorado.pdf: 5694002 bytes, checksum: 22bc5318ec502694cd7a4a087cec549f (MD5) / Approved for entry into archive by Lucilene Cordeiro da Silva Messias null (lubiblio@bauru.unesp.br) on 2018-07-02T19:06:37Z (GMT) No. of bitstreams: 1 gomes_tc_dr_bauru.pdf: 5485212 bytes, checksum: 22c574afd417cd26b3380c78e8274909 (MD5) / Made available in DSpace on 2018-07-02T19:06:37Z (GMT). No. of bitstreams: 1 gomes_tc_dr_bauru.pdf: 5485212 bytes, checksum: 22c574afd417cd26b3380c78e8274909 (MD5) Previous issue date: 2018-03-27 / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Transistores de filme fino de ZnO, cujo desempenho depende das condições de preparação da camada de ZnO e do dielétrico de gate, tem sido aplicados como sensores de radiação ultravioleta (UV), visando prevenir danos à saúde da pele. Este trabalho tem como objetivo a fabricação de transistores de ZnO/Al2O3, mediante o estudo simultâneo dos parâmetros relacionados à preparação das camadas de ZnO e Al2O3, bem como, o de transistores com dielétrico padrão (ZnO/SiO2) submetidos a diferentes condições de funcionamento. Estes estudos visam encontrar quais condições viabilizam as aplicações dos transistores como sensor UV. Os experimentos englobam a deposição de filmes de ZnO tanto por sputtering de um alvo de ZnO, quanto por spray pirolise de uma solução de acetato de zinco. O dielétrico SiO2 foi obtido comercialmente, enquanto que o Al2O3 foi crescido por anodização. Os transistores foram fabricados em diversas condições, as quais foram estabelecidas pelos métodos de planejamento experimental Taguchi e Plackett-Burman. As respostas das caracterizações foram interpretadas por técnicas de estatística (ANOVA). Os resultados demonstram que Al2O3 otimizado exibe correntes de fuga de até 10E-10 A e constante dielétrica de ~13. A identificação dos parâmetros mais importantes na preparação de filmes de ZnO por spray pirólise, permitiram produzir transistores de ZnO/Al2O3 com mobilidades de ~4,5 cm2/Vs. Os sensores UV, usando transistores de ZnO/SiO2 apresentaram mobilidades de 0,1 a 12 cm2/Vs, e indicaram que a sensibilidade do sensor UV depende de parâmetros relacionados as condições de operação do dispositivo. Portanto, mostra-se que é fundamental a compreensão dos parâmetros envolvidos na produção dos dispositivos, pois isto permite refinar o processo na busca pela alta performance de dispositivos de baixo custo, bem como, otimizar os dispositivos para aplicações como sensor de radiação UV. / ZnO thin film transistors have been applied as ultraviolet (UV) radiation sensors in order to prevent damage to skin's health. However, the performance of ZnO transistor depends on the preparation conditions of both ZnO layer and gate dielectric. This work aims to produce and evaluate ZnO/Al2O3 transistors by studying simultaneously the parameters regarding the preparation of ZnO and Al2O3 layers, as well as the fabrication of ZnO transistors with a standard dielectric (ZnO/SiO2), under different conditions of working. It is intended to investigate the conditions to apply ZnO transistors as UV sensor. The experiments involve the deposition of ZnO films by sputter coating and spray pyrolysis of a solution of zinc acetate. SiO2 dielectric was commercially purchased, while Al2O3 was grown by anodization. The transistors were fabricated under different conditions, which were established by both experimental design Taguchi and Plackett-Burman methods. The responses from the characterization were interpreted by statistical techniques (ANOVA). The results showed that optimized Al2O3 films exhibit leakage current until 10E-10 A and dielectric constant of ~13. It was essential to identify the most important parameters regarding to preparation of ZnO films by pyrolysis spray in order to fabricate ZnO/Al2O3 transistors with mobilities of ~4,5 cm2/Vs. UV sensors based on ZnO/SiO2 transistors showed mobilities from 0,1 to 12 cm2/Vs and demonstrated that the sensitivity of the UV sensor depends on parameters related to working conditions. Therefore, it is of great importance the understanding of the parameters involved in the production of the devices, as it allows to refine the process in the search for the high performance of low cost materials as well as optimize the device for application as UV sensor. / FAPESP: 2014/13904-8

Le but de cette thèse était de fabriquer des structures cœur / coquille à base de nanofils d’oxyde de zinc (ZnO) pour des applications en photovoltaïques principalement, et ensuite pour des détecteurs UV. Des réseaux de nanofils de ZnO de dimensions contrôlées ont été synthétisés en utilisant la méthode d’électrodéposition de ZnO (ECD). Nous avons également synthétisé des oursins organisés à base de nanofils de ZnO (U-ZnO NWs) en combinant les méthodes de nanostructuration de surface (auto-assemblage de sphères de polystyrène), dépôt de couche atomique (ALD) et ECD de ZnO. Plusieurs approches concernant le contrôle des dimensions de ces nanofils ont été envisagées. Les diamètres, la densité et la morphologie de ces nanofils ont été ajustés soit en modifiant les diamètres des sphères utilisés soit en modulant les paramètres expérimentaux durant la déposition (ALD et/ou ECD). Des monocouches et des multicouches de U-ZnO NWs de longueur variant de 750 nm jusqu'à 1500 nm ont été obtenus dans une large gamme de diamètre (57-170 nm).Ces matériaux ont été utilisés pour la construction de cellules solaires à colorant (DSSC) à base de réseaux de nanofils et des U-ZnO NWs, recouverts de couches minces d’oxyde de titane (TiO2) par dépôt de couches atomiques (ALD). Des rendements de conversion solaire de ~ 2% ont été atteints, sachant que le ZnO absorbe seulement dans l’UV. Ces matériaux ont été également utilisés pour la construction de cellules solaires de type II formés des U-ZnO NWs recouverts de couches d’oxyde de cuivre (Cu2O) de différentes épaisseurs par ECD. Les effets de la morphologie et des dimensions des nanofils et des U-ZnO NWs sur la diffusion de la lumière et la performance électronique des dispositifs ont été étudiés. Des capteurs d’ultraviolet ont été testés en utilisant les nanofils et les U-ZnO NWs. Une amélioration significative de la performance et de la stabilité en matière de détection UV a été observée en utilisant ces nanostructures de ZnO. Cela est dû à l'augmentation de la surface active offerte par les nanofils et les U-ZnO NWs en comparaison avec la performance obtenue avec les couches minces de ZnO. Finalement, une bioélectrode à base de nanofibres de polyacrylonitrile (PAN) recouverts par une couche d’or a été préparée pour la réduction électrochimique du CO2 en biocarburants utiles. L'électrode de PAN / Or a été préparée en utilisant une méthode de synthèse basée sur l'électrofilage suivi d'une pulvérisation d'Or. Une amélioration significative de l'activité électrochimique et de la stabilité de la bioélectrode a été observée. / The aim of this thesis was to fabricate core / shell structures based on zinc oxide (ZnO) nanowires for photovoltaic applications mainly, and UV sensors as well. ZnO nanowire arrays of controlled size were grown using electrodeposition method (ECD). We also synthesized organized urchins based on ZnO nanowires by combining methods of surface nanostructuring (self-assembly of polystyrene spheres), atomic layer deposition (ALD) and electrodeposition of ZnO (ECD). Several approaches concerning the control of dimensions on these nanowires have been investigated. The diameter, density and morphology of these nanowires were adjusted either by modifying the diameters of spheres or by modulating the experimental parameters during deposition (ALD and / or ECD). Organized monolayers and multilayers of urchins based on ZnO nanowires ranging between 750 -1500 nm in length were obtained in a diameter range between 50-170 nm. The construction of dye solar cells (DSSC) was based on nanowire arrays and organized urchins based on ZnO nanowires coated with thin shells of titanium oxide (TiO2) obtained by atomic layer deposition (ALD). As proof of concept, solar conversion efficiencies of ~ 2% were achieved, bearing in mind that ZnO absorbs only in UV range. These materials have also been used for solar cells construction of type II based on organized urchin-like ZnO nanowires coated with copper oxide (Cu2O) layers of different thicknesses by electrodeposition of Cu2O. The effects of the morphology and the dimension of the organized nanowires and urchin-like ZnO nanowires on light scattering and electronic performance of the devices have been studied. UV sensors were tested using nanowires and urchin-like ZnO nanowires. A significant improvement in the performance and stability in UV detection was observed when using these ZnO nanostructures. This is due to the increase in active area offered by the ZnO nanowires and urchins compared to the performance obtained with ZnO thin films. Finally, a bioelectrode based on polyacrylonitrile nanofibers (PAN) coated with a layer of gold has been prepared for the electrochemical reduction of CO2 into useful biofuels. The PAN/gold electrode was prepared using a homemade synthesis method, based on electrospinning followed by gold sputtering. A significant improvement in the electrochemical activity and the stability of the bioelectrode was observed.

We have performed a first principles density functional theory (DFT) calculations to study the thermal conductivity in ZnO nanotubes, ZnO nanowires, and Si/Ge shell-core nanowires. We found the equilibrium configuration and the electric band structure of each nanostructure using DFT, the interatomic force constants and the phonon dispersion relations were calculated using DFPT as implemented in Quantum Espresso. In order to fundamentally understand the effect of atomic arrangements, we calculated the phonon conductance in a ballistic approach using a Green's function method. All ZnO nanostructures studied exhibit semiconducting behavior, with direct bandgap at the Gamma point. The calculated values for the bandgaps were larger than the value of the bandgap of the bulk ZnO. We were able to identify phonon modes in which the motion of Zn atoms is significant when it is compared with the motion of oxygen atoms. The thermal conductivity depends on the diameter of the nanowires and nanotubes and it is dramatically affected when the nanowire or nanotube is doped with Ga. For Si/Ge nanowires, the slope and the curvature of acoustic modes in the phonon dispersion relation increases when the diameter increases. For nanowires with the same number of atoms, the slope and curvature of acoustic modes depends on the concentration of Si atoms. We were able to identify phonon modes in which the motion of core atoms is significant when it is compared with motion of atoms on the nanowire's shell. The thermal conductivity in these nanostructures depends on the nanowire's diameter and on the Si atoms concentration.

Fundação de Amparo à Pesquisa do Estado do Rio de Janeiro / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Conselho Nacional de Desenvolvimento Científico e Tecnológico / As indústrias consomem volumes elevados de água e outras substâncias químicas na síntese dos seus produtos e geram grande quantidade de rejeitos. Entre os mais importantes poluentes encontrados nos efluentes dessas indústrias estão os corantes sintéticos que representam um problema, pois não são facilmente destruídos por tratamentos convencionais. A fotocatálise heterogênea tem sido considerada como uma alternativa efetiva no tratamento de efluentes contendo esses corantes. Neste trabalho, estudou-se a cinética de descoloração e o grau de mineralização dos corantes sintéticos reativos Yellow 145, Black 5, Red 4 e Blue 21 através da fotocatálise utilizando ZnO puro e impregnado com íons Fe2+ e Co2+. Testes preliminares foram realizados para otimizar a concentração dos corantes e a massa mínima de catalisador a ser utilizado nos experimentos fotocatalíticos. Além da fotocatálise, experimentos individuais de fotólise e adsorção também foram realizados, porém se mostraram poucos eficientes. Através da espectrofotometria UV-Vis, verificou-se o total descoramento individual dos corantes em aproximadamente 30 minutos de irradiação com ZnO. O grau de mineralização de cada corante foi determinado através de análise de carbono orgânico total (COT), atingindo-se cerca de 70 a 80% de mineralização após 240 minutos de tratamento fotocatalítico. Foram comparadas, ainda, as eficiências de cada fotocatalisador ZnO, Fe/ZnO e Co/ZnO na mineralização de uma solução contendo a mistura dos quatro corantes já mencionados após 240 minutos de reação. A eficiência na mineralização da mistura dos corantes seguiu a seguinte ordem: Co/ZnO (32%), ZnO (78%) e Fe/ZnO (87%). A reação de degradação fotocatalítica do corante Black 5 seguiu uma cinética de primeira ordem, enquanto que os corantes Yellow 145, Red 4 e Blue 21 seguiram uma cinética de ordem zero. / Industries consume a huge amount of water and other chemical substances in the synthesis of their products and generate an elevated quantity of waste. Among the most important pollutants found in textile wastewaters are the synthetic dyes, that are not destroyed by conventional treatments. Alternatively, the heterogeneous photocatalysis is considered an affective treatment for wastewaters containing strong coloration. In this work, it was studied the decoloration kinetics and the degree of mineralization of four reactive dyes (Yellow 145, Black 5, Red 4 and Blue 21) in presence of UV irradiation and pure ZnO or impregnated ZnO with ions Fe2+ and Co2+ as photocatalysts. Preliminary tests indicated the optimal initial dyes concentration and the minimum amount of catalyst to be used in the photocatalytic experiments. In addition to the photocatalitic tests, individual experiments of photolysis and adsorption were also conducted, but they were not efficient. Results from UV-VIS spectrophotometry revealead the total color removal after 30 minutes of photocatalytic treatment with ZnO. Mineralization determined by total organic carbon (TOC) analyses showed that photocatalytic treatments were quite efficient achieving up to 80% of mineralization after 240 minutes of irradiation with ZnO. The efficiency of each photocatalyst ZnO, Fe/ZnO and Co/ZnO in the mineralization of a solution containing the four dyes mixture was also compared. After 240 minutes of irradiation, the mineralization of the dyes mixture presented the following order: Co/ZnO (32%), ZnO (78,8%) and Fe/ZnO (87,26%). The photocatalytic degradation of Black 5 dye followed a first order kinetic, while Yellow 145, Red 4 and Blue 21 dyes decoloration followed a zero order model

Les oxydes conducteurs transparents (TCO) sont une classe importante de matériaux possédant de nombreux domaines d’application, telles que les revêtements à faible émissivité ou comme électrodes transparentes pour les panneaux photovoltaïques et écrans plats. Parmi les matériaux TCO possibles, le ZnO dopé à l'Al (AZO) est couramment étudié notamment à cause de son coût relativement faible et de l'abondance en matières premières des éléments qui le compose. Les films minces d'AZO sont généralement produits par l’intermédiaire de procédés de dépôts physiques en phase vapeur, tels que la pulvérisation cathodique magnétron. Cependant, l’une des limitations de ces techniques repose sur l’homogénéité des films en utilisant la pulvérisation magnétron réactive (DCMS). Ce problème d'homogénéité peut être lié au bombardement du film en croissance par des ions négatifs d'oxygène, lesquels peuvent induire la présence de défauts accepteurs supplémentaires et la formation de phases secondaires isolantes. Dans ce travail, les films d'AZO sont déposés par pulvérisation cathodique magnétron en régime d’impulsions haute puissance (HiPIMS), un procédé dans laquelle des densités de courant instantanées élevées sont obtenues par l’intermédiaire de courtes impulsions de faible rapport cyclique. Dans la première partie de cette thèse, la possibilité d'améliorer l'homogénéité des films AZO par HiPIMS est démontrée. Cette amélioration peut être liée à un important taux de pulvérisation instantanée pendant chaque impulsion HiPIMS, de sorte que le processus puisse avoir lieu en régime métallique. Ceci permet de réduire l’impact du bombardement en ions d'oxygène pendant la croissance du film, évitant ainsi la formation de phases secondaires. Un autre problème de l'AZO est la stabilité des propriétés intrinsèques dans des environnements humides. Pour évaluer ce problème, la dégradation des propriétés électriques après une procédure de vieillissement a été étudiée pour des films déposés à la fois par DCMS et HiPIMS. Une méthode a été proposée pour restaurer les propriétés des films qui consiste en un recuit à basse température sous atmosphère de N2. L'amélioration des propriétés électriques des films peut être liée à un processus de diffusion dans lequel l’eau est évacuée hors des films. Ensuite, l'influence de la température du substrat sur les propriétés des films d'AZO déposés par HiPIMS a été étudiée. Les propriétés électriques, optiques et structurelles ont été améliorées avec l'augmentation de la température du substrat jusqu'à 600°C. Cette amélioration peut s’expliquer par l'augmentation de la qualité cristalline et le recuit des défauts. Dans une dernière partie, le dépôt de films d'AZO sur des substrats flexibles de PET a été étudié. Les films se développent sous la forme d'une couche épaisse, poreuse et composés de colonnes orientées de manière préférentielle selon l’axe c au-dessus d’une fine couche de départ. L’analyse de la résistance électrique après déformation mécanique a permis de déterminer une relation de proportionnalité inverse ou la résistance électrique augmente avec la diminution du rayon de courbure, cette dernière étant moins prononcée pour des films plus épais / Transparent conducting oxides (TCOs) are an important class of materials with many applications such as low emissivity coatings, or transparent electrodes for photovoltaics and flat panel displays. Among the possible TCO materials, Al-doped ZnO (AZO) is studied due to its relatively low cost and abundance of the raw materials. Thin films of AZO are commonly produced using physical vapour deposition techniques such as magnetron sputtering. However, there is a problem with the homogeneity of the films using reactive direct current magnetron sputtering (DCMS). This homogeneity problem can be related to the bombardment of the growing film with negative oxygen ions, that can cause additional acceptor defects and the formation of insulating secondary phases. In this work AZO films are deposited by high power impulse magnetron sputtering (HiPIMS), a technique in which high instantaneous current densities are achieved by short pulses of low duty cycle. In the first part of this thesis, the possibility to improve the homogeneity of the deposited AZO films by using HiPIMS is demonstrated. This improvement can be related to the high instantaneous sputtering rate during the HiPIMS pulses, so the process can take place in the metal mode. This allows for a lower oxygen ion bombardment of the growing film, which can help to avoid the formation of secondary phases. Another problem of AZO is the stability of the properties in humid environments. To assess this problem, the degradation of the electrical properties after an aging procedure was investigated for films deposited by both DCMS and by HiPIMS. A method was proposed, to restore the properties of the films, using a low temperature annealing under N2 atmosphere. The improvement of the electrical properties of the films could be related to a diffusion process, where water is diffusing out of the films. Then, the influence of the substrate temperature on the properties of AZO films deposited by HiPIMS was studied. The electrical, optical and structural properties were found to improve with increasing substrate temperature up to 600°C. This improvement can be mostly explained by the increase in crystalline quality and the annealing of defects. Finally, the deposition of AZO films on flexible PET substrates was investigated. The films are growing as a thick porous layer of preferentially c-axis oriented columns on top of a thin dense seed layer. The evolution of the sheet resistance of the films after bending the films with different radii was studied. There is an increase in the sheet resistance of the films with decreasing bending radius, that is less pronounced for thicker films

Made available in DSpace on 2014-06-11T19:25:33Z (GMT). No. of bitstreams: 0 Previous issue date: 2009-11-30Bitstream added on 2014-06-13T20:14:08Z : No. of bitstreams: 1 lunas_fr_me_ilha.pdf: 2221556 bytes, checksum: 09a4e6c925da4d7d80d38288c167af3d (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Neste trabalho foram depositados em substrato vítreo, filmes finos de Óxido de Zinco puro (ZnO) e dopados com alumínio (ZnO:Al) e manganês (ZnO:Mn), utilizando a técnica spray-pirólise. Foram investigadas as propriedades estruturais, ópticas e elétricas dos filmes, assim como, a dependência com a temperatura de deposição e concentração. As temperaturas utilizadas para deposição dos filmes finos foram 400 ºC e 450 ºC, e a concentração de dopantes variaram de 1 a 5 átomo por cento (at%). As técnicas de difração de raios-X e espectroscopia por refletância no infravermelho foram utilizadas para avaliar as características estruturais dos filmes. A Espectroscopia de transmitância na região do UV-Vis foi utilizada como uma das técnicas no estudo das propriedades ópticas, fornecendo valores da banda proibida. A técnica do ângulo de Brewster, foi utilizada com o intuito de avaliar o índice de refração e a espessura dos filmes finos. A avaliação da resistividade foi realizada com a finalidade de estudar a propriedade elétrica, e medidas do efeito Hall para investigar a densidade dos portadores de carga e mobilidade dos filmes semicondutores. A análise dos difratogramas de raio-X, revela picos de difração típicos de uma estrutura policristalina tipo wurtzita. As medidas de refletância especular por FTIR identificam ligações de estiramento do Zn-O na região de 450 cm-1. A técnica do ângulo de Brewster fornece resultados das espessuras dos filmes finos na faixa de 150 a 240 nm. As medidas de espectroscopia de transmitância na região UV-vis é avaliada em torno de 85%. Com os resultados da espessura dos filmes pelo ângulo de Brewster e medidas de transmitância foi calculado na região de forte absorção o coeficiente de absorção destes filmes. O valor do coeficiente de absorção é um parâmetro fundamental para determinação da banda de energia proibida... / In this work were deposited in glass substrate, thin films of pure zinc oxide (ZnO) and doped with aluminum (ZnO: Al) and manganese (ZnO: Mn) used the spray-pyrolysis technique. The structural, electrical and optical properties of thin films were investigated in dependence the concentration and temperatures deposition. The thin films temperatures deposition were 400 °C and 450 º C, and the doping concentration were from 1 at% to 5 at% range. The deposition technique used aims to obtain good adhesion to the substrate and uniformity of the films. The X-ray diffraction spectroscopy and infrared reflectance were used to evaluate the structural characteristics of the films. The UV-Vis transmittance spectroscopy was used in the study of optical properties, providing values of band gap. The other technique for this purpose is the Brewster angle technique in order to evaluate the refractive index and thickness of thin films deposited on a glass substrate. The resistivity and Hall Effect measurements were used for to investigate the charge carriers density and mobility in semiconductor films. The analysis of the X-ray diffraction shows typical peaks of polycrystalline wurtzite structure. Measurements the FTIR specular reflectances identify bond stretching of Zn-O in the region of 450 cm-1. The Brewster angle technique provides results the thin films thickness in the 150 to 240 nm range. The thin films UV/VIS transmittance measurements are valued around 85%. With the results of the thin film thickness by Brewster angle and measures transmittance were calculated the absorption coefficient data values in strong absorption region. The absorption coefficient is an important parameter for determination the band gap energy. These values, for the ZnO semiconductor is in 3.2 eV range. The resistivity’s measurements by Van der Pauw method showed the resistivity of ZnO thin films doped with... (Complete abstract click electronic access below)

Dans cette thèse, nous avons étudié les propriétés expérimentales des polaritons unidimensionnels dans les microfils de ZnO dans le but d'étudier le régime de dégénérescence quantique des polaritons à haute température et en régime de confinement de basse dimensionnalité. ZnO est en effet un matériau semiconducteur à grand gap dans lequel l'exciton bénéficie d'une très forte énergie de liaison qui garantit leur stabilité à température ambiante. D'autre part, la géométrie en "fil" de section hexagonale et de diamètre micrométrique confine les modes photoniques et les rend unidimensionnels. On montre que l'interaction entre l'exciton et ces modes photoniques est en régime de couplage fort, et que les polariton-excitoniques qui en résultent sont eux aussi en régime de confinement unidimensionnel. Cette thèse propose une étude détaillée de la physique de ces polaritons 1D. Dans un premier temps, on démontre que le régime de couplage fort unidimensionnel est conservé jusqu'à température ambiante avec une très grande énergie de Rabi de 300 meV pour une largeur de raie typique 75 fois plus faible. Cette faible largeur de raie, même à température ambiante, est une conséquence inattendue de la grande énergie de Rabi en comparaison de l'énergie maximum des phonons dans ZnO. Cet effet isole très efficacement les polaritons des vibrations thermiques du réseau. Nous nous sommes intéressés aussi à une structure similaire: les microfils de GaN. Dans ces fils, on profite d'une zone fortement dopée pour comparer expérimentalement le spectre en régime de couplage faible et en régime de couplage fort dans le même fil. Nous avons ensuite étudié les propriétés des gaz de polaritons dans les microfils de ZnO sous forte excitation dans le but d'atteindre le régime de dégénérescence quantique 1D. Nous démontrons qu'un régime de laser à polaritons est atteint à basse température en régime de couplage fort dans une situation inédite où les polaritons sont à 97% excitoniques. Cette propriété est comprise grâce à une étude détaillée des propriétés de relaxation des excitons vers les états de polaritons en régime de faible et forte excitations. Cette thèse donne les bases de la compréhension des polaritons unidimensionnels dans les microfils de ZnO. Les propriétés observées montrent que les microfils de ZnO sont particulièrement adaptés à l'étude des gaz de polaritons dégénérés 1D à haute température. / In this thesis, we have studied the experimental properties of one-dimensional polaritons in the ZnO microwires in order to study the quantum degenerate regime in a one-dimensional polariton gas at high temperature. ZnO is a wide gap semiconductor material in which the exciton is stable at room temperature thanks to its high binding energy. The "wire" geometry with a micrometric scale hexagonal cross-section results in a one-dimensional confinement of the light. The ZnO excitons and these photonic modes are in the strong coupling regime resulting in new light-matter eigenstates called exciton-polaritons which are, as well, in the one-dimensional confinement regime. This thesis provides a detailed study of the Physics of these 1D polaritons. As a first step, we demonstrate that the one-dimensional strong coupling regime is preserved up to room temperature with a very high Rabi splitting of 300 meV for a typical linewidth 75 times smaller. This small linewidth, even at room temperature, is an unexpected consequence of the high Rabi energy compared to the maximum phonon energy in ZnO. This effect efficiently isolates the polaritons from the thermal fluctuations of the lattice. We have studied as well a similar structure: the GaN microwires. Because of a highly doped part in these wires, it is possible to compare experimentally the spectrum in weak and strong coupling regime in a single wire. We have studied the properties of such polariton gas in ZnO microwires in the high excitation regime in order to reach the 1D quantum degeneracy limit. We have demonstrated that the polariton lasing regime is obtained at low temperature in the strong coupling regime and that it exhibits an unusual situation: the lasing polariton mode is made up of 97% of exciton. This property is understood thanks to a detailed study of the relaxation properties of the excitons towards the polariton states below and above the polariton lasing threshold. This thesis provides the basics to understand the one-dimensional polaritons in ZnO microwires. The properties described in this thesis demonstrate that the ZnO microwires are particularly suitable for the study of 1D degenerate polariton gas at room temperature.

Submitted by Reginaldo Toshihiro Konatu (rtkonatu@gmail.com) on 2018-05-03T17:15:41Z No. of bitstreams: 1 Tese KONATU 2018.pdf: 3998865 bytes, checksum: 9ed8e8c75039aad725b37cff903fad84 (MD5) / Rejected by Pamella Benevides Gonçalves null (pamella@feg.unesp.br), reason: Solicitamos que realize correções na submissão seguindo as orientações abaixo: Você realizou duas submissões favor desconsiderar esta. Agradecemos a compreensão. on 2018-05-04T17:53:18Z (GMT) / Submitted by Reginaldo Toshihiro Konatu (rtkonatu@gmail.com) on 2018-05-04T18:50:12Z No. of bitstreams: 1 Tese Konatu 2018.pdf: 4232195 bytes, checksum: e32103c38cfbff0ac3d36adba585b7ad (MD5) / Approved for entry into archive by Pamella Benevides Gonçalves null (pamella@feg.unesp.br) on 2018-05-04T19:25:28Z (GMT) No. of bitstreams: 1 konatu_rt_dr_guara.pdf: 4232195 bytes, checksum: e32103c38cfbff0ac3d36adba585b7ad (MD5) / Made available in DSpace on 2018-05-04T19:25:28Z (GMT). No. of bitstreams: 1 konatu_rt_dr_guara.pdf: 4232195 bytes, checksum: e32103c38cfbff0ac3d36adba585b7ad (MD5) Previous issue date: 2018-03-06 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / O presente trabalho tem como objetivo a obtenção de revestimentos poliméricos bactericidas formados por ácido hialurônico/quitosana/ZnO na superfície da liga Ti15Zr15Mo após crescimento de nanotubos de TiO2 empregando oxidação anódica. A liga Ti15Zr15Mo foi processada em forno a arco voltaico com atmosfera controlada e tratados termicamente. Os nanotubos de TiO2 foram obtidos por meio de oxidação anódica. Para obtenção dos revestimentos, as amostras foram recobertas com camadas de ácido hialurônico/quitosana/ZnO. As superfícies foram avaliadas empregando microscopia eletrônica de varredura (MEV), analise por difração de raios-X (DRX), espectroscopia de fotoelétrons excitados por raios-X (XPS) e ângulo de contato. A condição ideal para obtenção dos nanotubos ordenados de TiO2 na superfície da liga foi 30V, eletrólito formado por glicerol, água deionizada (1:1 em volume) e fluoreto de amônio (2,7 g/L) e tempo de 24 horas. Para esses parâmetros, os nanotubos formados apresentaram diâmetro médio de 130 nm e espessura de 1290 nm. O revestimento polimérico escolhido foi de 2 bicamadas de ácido hialurônico/quitosana contendo partículas de ZnO. Os estudos in vitro realizados para avaliar adesão bacteriana de Staphylococcus aureus mostraram que não houve diferença significativa entre as amostras com e sem recobrimento. / Nowadays the development of new materials for biomedical application has become of extreme importance due to the need of new materials with excellent mechanical properties, physicochemical and biocompatibility for use in the manufacture of biomedical devices. In addition to the material presenting the necessary bulk properties, it is of utmost importance that they present a response from the host to the implant. For this, the surface of the material must have characteristics that can be obtained with superficial treatments. This work aims at the analysis of the surface of nanotubes grown on the Ti15zr15Mo alloy functionalized with thin film of hyaluronic acid, chitosan and ZnO nanoparticles. The surface was analyzed by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and contact angle. The nanotubes formed had a mean diameter of 130 nm and a thickness of 1290 nm. The coating with the polymeric bilayers, with a number of more than 4 bilayers, closed the nanotubes and increased the contact angle, being used 2 biacamadas for the incorporation of ZnO. The concentration of the ZnO solution was very low for incorporation and bactericidal effect.

Fundação de Amparo à Pesquisa do Estado do Rio de Janeiro / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Conselho Nacional de Desenvolvimento Científico e Tecnológico / As indústrias consomem volumes elevados de água e outras substâncias químicas na síntese dos seus produtos e geram grande quantidade de rejeitos. Entre os mais importantes poluentes encontrados nos efluentes dessas indústrias estão os corantes sintéticos que representam um problema, pois não são facilmente destruídos por tratamentos convencionais. A fotocatálise heterogênea tem sido considerada como uma alternativa efetiva no tratamento de efluentes contendo esses corantes. Neste trabalho, estudou-se a cinética de descoloração e o grau de mineralização dos corantes sintéticos reativos Yellow 145, Black 5, Red 4 e Blue 21 através da fotocatálise utilizando ZnO puro e impregnado com íons Fe2+ e Co2+. Testes preliminares foram realizados para otimizar a concentração dos corantes e a massa mínima de catalisador a ser utilizado nos experimentos fotocatalíticos. Além da fotocatálise, experimentos individuais de fotólise e adsorção também foram realizados, porém se mostraram poucos eficientes. Através da espectrofotometria UV-Vis, verificou-se o total descoramento individual dos corantes em aproximadamente 30 minutos de irradiação com ZnO. O grau de mineralização de cada corante foi determinado através de análise de carbono orgânico total (COT), atingindo-se cerca de 70 a 80% de mineralização após 240 minutos de tratamento fotocatalítico. Foram comparadas, ainda, as eficiências de cada fotocatalisador ZnO, Fe/ZnO e Co/ZnO na mineralização de uma solução contendo a mistura dos quatro corantes já mencionados após 240 minutos de reação. A eficiência na mineralização da mistura dos corantes seguiu a seguinte ordem: Co/ZnO (32%), ZnO (78%) e Fe/ZnO (87%). A reação de degradação fotocatalítica do corante Black 5 seguiu uma cinética de primeira ordem, enquanto que os corantes Yellow 145, Red 4 e Blue 21 seguiram uma cinética de ordem zero. / Industries consume a huge amount of water and other chemical substances in the synthesis of their products and generate an elevated quantity of waste. Among the most important pollutants found in textile wastewaters are the synthetic dyes, that are not destroyed by conventional treatments. Alternatively, the heterogeneous photocatalysis is considered an affective treatment for wastewaters containing strong coloration. In this work, it was studied the decoloration kinetics and the degree of mineralization of four reactive dyes (Yellow 145, Black 5, Red 4 and Blue 21) in presence of UV irradiation and pure ZnO or impregnated ZnO with ions Fe2+ and Co2+ as photocatalysts. Preliminary tests indicated the optimal initial dyes concentration and the minimum amount of catalyst to be used in the photocatalytic experiments. In addition to the photocatalitic tests, individual experiments of photolysis and adsorption were also conducted, but they were not efficient. Results from UV-VIS spectrophotometry revealead the total color removal after 30 minutes of photocatalytic treatment with ZnO. Mineralization determined by total organic carbon (TOC) analyses showed that photocatalytic treatments were quite efficient achieving up to 80% of mineralization after 240 minutes of irradiation with ZnO. The efficiency of each photocatalyst ZnO, Fe/ZnO and Co/ZnO in the mineralization of a solution containing the four dyes mixture was also compared. After 240 minutes of irradiation, the mineralization of the dyes mixture presented the following order: Co/ZnO (32%), ZnO (78,8%) and Fe/ZnO (87,26%). The photocatalytic degradation of Black 5 dye followed a first order kinetic, while Yellow 145, Red 4 and Blue 21 dyes decoloration followed a zero order model

A utilização descontrolada de pesticidas tem provocado no decorrer dos anos a intoxicação de milhares de pessoas no mundo, uma vez que, seus resíduos têm sido depositados em alimentos, em solos e em ambientes aquáticos. Assim, a construção de duas novas plataformas sensoras para a detecção de pesticidas é o objetivo desse trabalho. Na primeira plataforma foi utilizado o polieletrólito catiônico polietilenoimina (PEI) em conjunto com o polissacarídeo extracelular algal (PSE) produzido pela microalga criptofícea Cryptomonas tetrapirenoidosa preparados através da técnica de deposição \"spin-coating\". E a segunda plataforma foi produzida por eletrodeposição pulsada, entre um potencial de redução e um de oxidação, utilizando nanoestruturas de óxido de zinco (ZnO). Para caracterizar as plataformas, foram utilizadas as técnicas de microscopia eletrônica de varredura com fonte de emissão de campo (FEG-SEM), difração de raios X (XRD), espectroscopia de absorção ultravioleta-visível (UV-Vis), microscopia de força atômica (AFM) e espectroscopia de reflexão-absorção no Infravermelho com modulação da polarização (PM-IRRAS). Através da imobilização da enzima polifenol oxidase na forma de extrato bruto em sua fonte natural (fruto abacate), as plataformas de PEI/PSE e ZnO, foram avaliadas como biossensores de catecol e do inseticida carbaril. De modo comparativo, as plataformas de PEI/PSE sem a presença imobilizada da enzima também foram estudadas para a detecção do catecol e do carbaril. A simplicidade na formação e na construção dessas plataformas vem qualificá-las como viáveis a serem produzidas em escala industrial e com baixo custo de processamento. E diante dos resultados obtidos no desenvolvimento desses biossensores destaca-se a eficiência e a rapidez de detecção, o que os tornam economicamente promissores e competitivos em termos de aplicações ambientais. / The uncontrolled use of pesticides has resulted over the years the intoxication of thousands of people in the world, since their waste has been deposited in food, in soil and aquatic environments. Thus, the construction of two new sensors platforms for pesticide detection is the objective of this work. At first platform was used cationic polyelectrolyte polyethyleneimine (PEI) along with the extracellular algal polysaccharide (EPS) produced by microalgae criptofícea Cryptomonas tetrapirenoidosa prepared by deposition technique \"spin-coating\". The second platform was produced by pulsed electrodeposition between a reduction and an oxidation potential using nanostructures zinc oxide (ZnO). To characterize the platforms, we used the techniques of field emission gun scanning electron microscopy (FEG-SEM), X-ray diffraction (XRD), ultraviolet visible absorption spectroscopy (UV-Vis), atomic force microscopy (AFM), and polarization modulation infrared reflection-absorption spectroscopy (PM-IRRAS). By immobilization of the polyphenol oxidase enzyme as a crude extract in their natural source (avocado fruit), platforms PEI/PSE and ZnO, they were evaluated as catechol and carbaryl insecticide biosensors. In a comparative way, the platforms PEI/PSE without the presence of immobilized enzyme were also studied for detection of catechol and carbaryl. The simplicity in the formation and construction of these platforms comes qualify them as viable to be produced on an industrial scale and low cost processing. And on the results obtained in the development of such biosensors stand out the efficiency and speed of detection, which make them economically promising and competitive in terms of environmental applications.