O desenvolvimento de filmes finos e nanotecnologia tem proporcionado imensos avanços nas áreas científicas e tecnológicas. A nanotecnologia, em sua essência, não pode ser considerada como uma simples redução das dimensões das propriedades dos materiais. Na verdade surgem novas propriedades que não podem ser caracterizadas por técnicas convencionais. Assim surgiram novos sistemas que são empregados na identificação destas novas propriedades e características. Muitas vezes os avanços tecnológicos que podem ser observados no dia a dia são frutos de pesquisas que foram recentemente realizadas. A demanda por óxidos condutores transparentes (TCO) para aplicações em optoeletrônicos, tais como painéis de toque, monitores de tela plana, diodos orgânicos emissores de luz (OLEDs) e outros dispositivos móveis, tem aumentado continuamente e se enquadram neste desenvolvimento. O objetivo desse trabalho é analisar filmes finos de óxido de zinco produzidos por magnetron sputtering. Procuramos quais filmes de óxido de zinco possuem as melhores características de um TCO. Após esta análise temos condições de determinar quais foram os melhores parâmetros de deposição para a construção do filme de óxido de zinco. Os filmes finos foram analisados por: Rutherford backscatering spectroscopy (RBS), CxV, IxV, Efeito Hall, Interferômetria e Espectofotômetria UV-Vis-NIR. / can not be considered as a simple reduction of dimensions and scaling of material properties. In fact, CxV, flat panel monitors, Hall Effect, Interferometry and UV-Vis-NIR Spectrophotometry., has continuously increased and fits into this development. The objective of this work is to analyze thin films of zinc oxide, in its essence, induced by magnetron sputtering. We look for which zinc oxide film have the best characteristics for a TCO. From these results it is possible to concl, IxV, new properties that arise can not be characterized by conventional techniques. Thus new systems have emerged which are employed in the identification , organic light emitting diodes (OLEDs) and other mobile devices, such as touch panels, The development of thin films and nanotechnology has provided immense advances in scientific and technological areas. Nanotechnology

Two identified setbacks for CIGS based devices in order to obtain higher efficiency are parasitic absorption in the window layer structure and losses in open-circuit voltage due to bad interfaces. This study investigated how the performance of the solar cell is affected by depositing intrinsic ZnO (i-ZnO) and ZnMgO with atomic layer deposition (ALD) instead of the conventional sputtering. No significant improvement in fill factor was obtained by the use of ALD compared to sputtering, leading to the conclusion that pinholes in the sputtered film are not a detrimental factor for the cell. As the thickness of the i-layer increased, an increase in FF was observed for the ALD-deposited i-layer, whereas a decrease was observed for the sputtered i-layer. The open-circuit voltage was considered constant between the two series with only small fluctuations, indicating that the defect chemistry of the i-ZnO/CdS interface was not improved with the use of ALD. In this study it is shown that a gain in short-circuit current can be obtained for CIGS solar cells in the high energy region of the spectrum by reducing the thickness of the i-ZnO, as well as alloying the ZnO with Mg. When compared with a baseline layer sample with a sputtered i-layer thickness of around 90 nm, the estimated gain in short-circuit current density without a loss in fill factor was 0.14 and 0.20 mA/cm2 for ALD and sputtering, respectively. For the series with a ZnMgO i-layer, the highest estimated gain was 0.17 mA/cm2. This was observed for the sample with a 4:1 (Zn:Mg) pulse ratio, whereas higher Mg contents yielded a too high band gap that resulted in an electron blocking barrier.

O aumento da vida útil de pneus tem sido uma incessante busca de seus fabricantes. Aumentar a vida de um pneu não significa somente prolongar sua vida, mas também manter estáveis as características e propriedades, para as quais os compostos foram projetados. Para manter estáveis as propriedades e características dos compostos, deve-se ter a estabilidade das ligações cruzadas formadas durante a vulcanização do pneu. Em condições normais de uso, os principais causadores da degradação das ligações cruzadas em compostos de pneus são os ataques térmicos e oxidativos. O objetivo deste trabalho é avaliar a estabilidade de um composto de borracha natural frente às solicitações térmica e oxidativa das ligações cruzadas formadas sob diferentes condições de vulcanização e sistemas vulcanizantes. Foram elaboradas cinco formulações baseadas em borracha natural do tipo RSS-3 e com variações na dosagem de enxofre e óxido de zinco, utilizando sistemas de vulcanização convencional e eficiente. Todos os compostos foram vulcanizados em duas condições, 170°C e 140°C. Os compostos vulcanizados foram avaliados em ensaios físicos e químicos, incluindo medições de módulos de armazenamento e de perda, tensão e alongamentos à ruptura, resistência à laceração, densidade de ligações cruzadas e cinética de vulcanização nas condições novo (original) e envelhecidos na presença e na ausência de oxigênio. Os resultados obtidos permitem afirmar que a utilização de oxido de zinco de alta área superficial e de sistemas de vulcanização eficientes tornam este tipo de composto mais resistentes ao envelhecimento térmico e oxidativo. / The increment of the service life of tires has been a constant challenge for their manufacturers. Increasing the life of a tire does not mean only prolong his life, but also maintain its characteristics and properties stable, whatever the compounds were designed for. To keep stable the properties and characteristics of the compounds, we must have the stability of the crosslinks formed during the vulcanization of the tire. In normal use, the main causes of the degradation of the crosslinks are due to the thermal and oxidative attacks. The objective of this study is to evaluate the thermal and oxidative stability of the crosslinks formed under different conditions and curing systems in a compound with natural rubber. Five formulations were prepared based on the natural rubber RSS-3 and variations in the dosage of sulfur and zinc oxide, as well as the type of the vulcanization system, conventional or efficient, were introduced. All compounds were cured in two conditions, 170°C and 140°C. The vulcanized compounds were evaluated by physical and chemical tests, including measurements of the storage and loss moduli, tension and stretching to break, tear resistance, crosslinking density and kinetics of curing. The performance of the compounds was evaluated under three conditions, namely new (original) and after aging in the presence and in the absence of oxygen. The results allowed us to conclude that the use of zinc oxide of high surface area and the efficient vulcanization systems are more resistant to thermal and oxidative aging.

O desenvolvimento de filmes finos e nanotecnologia tem proporcionado imensos avanços nas áreas científicas e tecnológicas. A nanotecnologia, em sua essência, não pode ser considerada como uma simples redução das dimensões das propriedades dos materiais. Na verdade surgem novas propriedades que não podem ser caracterizadas por técnicas convencionais. Assim surgiram novos sistemas que são empregados na identificação destas novas propriedades e características. Muitas vezes os avanços tecnológicos que podem ser observados no dia a dia são frutos de pesquisas que foram recentemente realizadas. A demanda por óxidos condutores transparentes (TCO) para aplicações em optoeletrônicos, tais como painéis de toque, monitores de tela plana, diodos orgânicos emissores de luz (OLEDs) e outros dispositivos móveis, tem aumentado continuamente e se enquadram neste desenvolvimento. O objetivo desse trabalho é analisar filmes finos de óxido de zinco produzidos por magnetron sputtering. Procuramos quais filmes de óxido de zinco possuem as melhores características de um TCO. Após esta análise temos condições de determinar quais foram os melhores parâmetros de deposição para a construção do filme de óxido de zinco. Os filmes finos foram analisados por: Rutherford backscatering spectroscopy (RBS), CxV, IxV, Efeito Hall, Interferômetria e Espectofotômetria UV-Vis-NIR. / can not be considered as a simple reduction of dimensions and scaling of material properties. In fact, CxV, flat panel monitors, Hall Effect, Interferometry and UV-Vis-NIR Spectrophotometry., has continuously increased and fits into this development. The objective of this work is to analyze thin films of zinc oxide, in its essence, induced by magnetron sputtering. We look for which zinc oxide film have the best characteristics for a TCO. From these results it is possible to concl, IxV, new properties that arise can not be characterized by conventional techniques. Thus new systems have emerged which are employed in the identification , organic light emitting diodes (OLEDs) and other mobile devices, such as touch panels, The development of thin films and nanotechnology has provided immense advances in scientific and technological areas. Nanotechnology

Zinc deficient soils, or soils with low Zn bioavailability, are widespread, which exacerbates Zn deficiency in human as crops grown on these soils have low Zn content. Often crop yields are also compromised. Fertilizers based on soluble Zn salts often have limited efficacy in such soils. In this research, we evaluate the performance of polymer coated and bare ZnO nanoparticles (NPs) in an attempt to overcome limitations of soluble Zn salts in alkaline soils. We first synthesized 20-30 nm bare ZnO NPs with different surface chemistries to impart colloidal stability to the particles. Bare ZnO were treated in phosphate solution under certain conditions leading to the formation of a core made of ZnO NPs that is covered by a shell of amorphous Zn3(PO4)2 (core-shell NPs). This confers a negative charge to the particles over a wide pH range. The addition of nonionic (neutral dextran) and polyelectrolyte (negatively charged dextran sulfate (DEX(SO4)) during the synthesis resulted in the formation of DEX and DEX(SO4) ZnO NPs. Dextran has a minimal effect on the surface charge of ZnO but dextran sulfate confers a net negative charge. Bare and core-shell ZnO NPs were both electrostatically stabilized whereas DEX and DEX(SO4) ZnO NPs were sterically and electrosterically stabilized, respectively. We investigated the effect of treating seeds with ZnO NPs on the growth and accumulation of Zn in wheat (Triticum aestivum) seedlings in comparison to ZnSO4. All ZnO NPs stimulated seedling growth. Seedlings accumulated higher Zn concentrations when treated with ZnO NPs than with ZnSO4. Zinc sulfate was toxic even at the lower exposure concentrations, which was demonstrated by significantly lower germination success and seedling growth. In the second experiment, we investigated the effect of pH on the attachment and dissolution of ZnO NPs in soil, as compared to ZnSO4. Soil pH was adjusted to 6 and 8, then the soil was spiked with 100 mg Zn/kg soil in the form of ZnSO4, bare, DEX, DEX(SO4), and core-shell ZnO NPs. The results showed that DEX and core-shell ZnO NPs had significantly higher total Zn in soil solution compared to ZnSO4 at pH 8, with little dissolution. Dissolved Zn was similar among treatments except ZnSO4 at pH 6, indicating little dissolution of the ZnO NPs at either pH value. We also found that the engineered coatings dictate the behavior of the particles in simple aqueous systems, but their properties are altered in natural soil solutions because of the dominant effect of natural organic matter (NOM) on their surface chemistry. Based on the outcomes of the previous two experiments, we selected DEX and bare ZnO NPs to test the efficacy of ZnO NPs in delivering Zn to the grain of wheat under greenhouse conditions. We performed two independent studies where seeds were either treated with the NPs or grown in a soil spiked with Zn at pH 6 and 8 and spiked with Zn treatments (nano and ionic). We found that treating seeds with bare ZnO NPs significantly enhanced grain Zn concentrations as compared to the control, DEX-ZnO NPs, and ZnSO4. There were no differences in grain Zn concentration of plants treated with ionic or nano Zn treatments regardless of the soil pH. This work has elucidated important principles which will help carry forward efforts at developing effective ZnO NP-based fertilizers. It also suggests that treatment of seeds with ZnO NPs is more effective than amending soil or treating seeds with ZnSO4.

A piezoelectric microspeaker device that could be used in a variety of acoustic applications was designed and fabricated using a thin film ZnO layer that was reactively DC sputtered onto a single crystalline n-type silicon substrate. When tested the microspeaker did not produce sound due to complications in the etching process, the thickness of the diaphragms, and clamping effects. Instead, a characterization approach was taken and the structural, optical, electrical, and piezoelectric properties of the ZnO were investigated. Scanning electron microscopy, x-ray diffraction, and atomic force microscopy were utilized to discover the ZnO’s structural properties. Using the XRD and SEM, the as-sputtered ZnO films were found to have highly c-axis oriented columnar crystals. Optical properties were determined from the reflectance spectrums obtained from a Filmetrics F20 reflectometer and were used to determine the film thickness, the optical constants, and the optical band gap of the ZnO thin films. Using a four-point probe, the as-sputtered ZnO films were found to be highly resistive and insulative, mainly due to voided growth boundaries between the crystals. To improve electrical conductivity and piezoelectric response, ZnO samples were annealed at varying temperatures in a nitrogen environment. The annealing process successfully increased the electrical conductivity and piezoelectric properties of the films. The local piezoelectric properties of the ZnO were discovered with an Asylum MFP-3D and a piezoresponse force microscopy (PFM) technique called DART-PFM. The ZnO films that were sputtered with 70 watts and an argon to oxygen gas ratio of 2:1 were found to have the highest d33 piezoelectric coefficients. The ZnO sample that was annealed at 600°C for 30 minutes had the highest overall d33 value of 4.0 pm/V, which means that the 600°C annealed ZnO films would have the best chance of making a functional microspeaker.

Foi explorado o desenvolvimento de fotocatalisadores híbridos ZnO/Xerogel de carbono, visando aumentar a eficiência quântica do processo de degradação de poluentes orgânicos persistentes. Especificamente, foi estudada a preparação do híbrido ZnO-xerogel de carbono, sendo esta, a maior inovação tecnológica deste projeto, considerando que o efeito catalítico deste híbrido não foi estudado na literatura. O uso do xerogel de carbono na preparação do semicondutor-material carbonoso é justificado pela excelente condutividade elétrica, elevada área superficial e porosidade, além de sua estrutura porosa ser facilmente manipulada por modificações nos parâmetros de síntese. A escolha do tanino como precursor do xerogel visa à diminuição de custos e impactos ambientais, além de acrescentar valor à inovação tecnológica proposta. A influência do pH e rota de síntese foram avaliados, assim como a influência da temperatura de calcinação nas propriedades dos materiais. A espectroscopia por refletância difusa foi a técnica empregada para determinação da energia de gap das amostras. A morfologia, a análise elementar, a estrutura cristalina dos materiais, a estrutura química e a constituição dos materiais foram determinadas por microscopia eletrônica de varredura, espectrometria de energia dispersiva, difratometria de raios X, infravermelho e espectroscopia Raman, respectivamente. O balanço de cargas na superfície do material foi analisado pela metodologia do ponto de carga zero (PZC). A ação fotocatalítica do material foi avaliada através da decomposição de 4-clorofenol e bisfenol A, determinada através da espectroscopia no UV-Visível. Todos os materiais apresentam a estrutura cristalina hexagonal do óxido de zinco (wurtzita). Os materiais sem tanino em sua composição também apresentam a fase de hidroxicloreto de zinco mono-hidratado. Os difratogramas de raios-X e valores de bandgap obtidos confirmam a incorporação do carbono na estrutura cristalina do óxido de zinco. Os materiais produzidos via rota alcoólica apresentam menores valores de tamanho de cristalito e partícula, assim como um maior teor de grafite em sua composição e maior área superficial, enquanto que os materiais produzidos em solução aquosa apresentam menores valores de energia de gap. Todos os materiais apresentaram atividade fotocatalítica quando submetidos à radiação solar e visível, sendo que os materiais com proporções intermediárias entre xerogel de carbono e óxido de zinco se mostraram superiores para o processo de fotodegradação. Os materiais produzidos via alcoólica são superiores aos produzidos em solução aquosa, no que tange o processo de fotocatálise. Os valores máximos encontrados para a degradação de 4-clorofenol e bisfenol A foram de 88% e 78%, respectivamente, obtidos pelo material XZnC 3.0 (EtOH). A temperatura de calcinação e quantidade de hidróxido de potássio utilizados na síntese influenciam significativamente as propriedades dos materiais, de modo que as condições ótimas para a síntese dos materiais foram de calcinação em 300oC e 8 g de hidróxido de potássio utilizadas na síntese. O mecanismo de fotocatálise é fortemente influenciado pela geração de radicais hidroxilas e os materiais apresentam estabilidade para reciclo em processos industriais. / The development of ZnO/Carbon xerogel hybrid photocatalysts was studied, in order to increase the quantum efficiency of the degradation process of persistent organic pollutants. Specifically, the preparation of the ZnO-carbon xerogel hybrid was studied, being this the most significant technological innovation of this project, considering that the catalytic effect of this hybrid was not studied in the literature. The use of carbon xerogel in the preparation of the semiconductor-carbonaceous material is justified by its excellent electrical conductivity, high surface area and porosity, the latter being easily manipulated by modifications in the synthesis parameters. The choice of tannin as the precursor of the xerogel aims at reducing costs and environmental impacts, adding value to the proposed technological innovation. The influence of the pH and route of synthesis were evaluated, as well as the influence of the calcination temperature on the properties of the materials. Diffuse reflectance spectroscopy was the technique used to determine the gap energy of the samples. The morphology, elemental analysis, crystalline and chemical structure of the materials were determined by scanning electron microscopy, dispersive energy spectrometry, X-ray diffractometry, infrared and Raman spectroscopy, respectively. The charge balance on the material surface was analyzed by the point of zero charge methodology (PZC). The photocatalytic action of the material was evaluated by the decomposition of 4-chlorophenol and bisphenol A, determined by UV-Visible spectroscopy. All materials have the hexagonal crystalline structure of zinc oxide (wurtzite). The materials without tannin in their composition also present the zinc hydroxychloride monohydrate phase. The X-ray diffractograms and bandgap values obtained confirm the incorporation of the carbon in the crystalline structure of the zinc oxide. The materials produced via the alcohol route have lower values of crystallite and particle size, as well as a higher content of graphite in their composition and larger surface area, while the materials produced in aqueous solution have lower values of gap energy. All the materials presented photocatalytic activity when subjected to visible and solar radiation, and the materials with intermediate proportions between carbon xerogel and zinc oxide were superior for the photodegradation process. The materials produced via alcohol route are superior to those produced in aqueous solution, as far as the photocatalysis process is concerned. The maximum values found for the degradation of 4-chlorophenol and bisphenol A were 88% and 78%, respectively, obtained by the material XZnC 3.0 (EtOH). The calcination temperature and amount of potassium hydroxide used in the synthesis significantly influence the properties of the materials, so that the optimum conditions for the synthesis of the materials were calcination at 300 °C and 8 g of potassium hydroxide used in the synthesis. The mechanism of photocatalysis is strongly influenced by the generation of hydroxyl radicals and the materials present stability for recycling in industrial processes.

Thesis (Ph. D.)--University of Washington, 2006. / Vita. Includes bibliographical references (leaves 204-217).

The purpose of this thesis work is to design and fabricates organic-inorganic hetero junction White Light Emitting Diode (WLED). In this WLED, inorganic material is n- type ZnO and organic material is p-type conjugated polymer. The first task was to synthesise vertically aligned ZnO nano-rods on glass as well as on plastic substrates using aqueous chemical growth method at a low temperature. The second task was to find out the proper p- type organic material that gives cheap and high efficient WLED operation. The proposed polymer shouldn’t create a high barrier potential across the interface and also it should block electrons entering into the polymer. To optimize the efficiency of WLED; charge injection, charge transport and charge recombination must be considered. The hetero junction organic-inorganic structures have to be engineered very carefully in order to obtain the desired light emission. The layered structure is composed of p-polymer/n-ZnO and the recombination has been desired to occur at the ZnO layer in order to obtain white light emission. Electrical characterization of the devices was carried out to test the rectifying properties of the hetero junction diodes. iv

Zinc oxide (ZnO) nanostructures, especially nanowires, have been one of the most important semiconductive materials used for photocatalysis due to their unique material properties and remarkable performance. In this project, vertically-aligned ZnO nanowires on glass substrate have been synthesized by using the facile hydrothermal methods with the help of pre-coated ZnO seeding layer. The crystalline structure, morphology and UV-Vis transmission spectra of the as-synthesized sample were characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM) and Ultra-violet Visible (UV-Vis) Spectrophotometer. The photocatalytic activity of the sample was examined for the photocatalytic degradation of methyl orange (MO) as the test dye in aqueous solution under UV-A irradiation. The extent of direct hydrolysis of the MO dye under UV light without the photocatalysts was first measured to eliminate the possible contribution from the undesired variables to the overall efficiency. The effects of pH and initial concentration of the MO solution, as well as the nanowire growth time, on the photocatalytic efficiency have been investigated, in order to determine the optimal conditions for photocatalytic applications of ZnO nanowires in the industry. Furthermore, the reproducibility of the experimental methods used in this project was tested to ensure the reliability of the experimental results obtained; and the reusability of the prepared ZnO nanowire arrays were also evaluated to investigate the stability of the products for photocatalytic applications in a large scale. In addition, a micro-chamber based microfluidic device with integrated ZnO nanowire arrays has been fabricated and used for photodegradation studies of MO solution under continuous-flow conditions. As expected, the micro-chamber based approach exhibited much improved photodegradation efficiency as compared to the conventional method using bulk dye solution. The effects of the flow rate and chamber height of the microfluidic device have also been investigated in order to determine the optimal experimental conditions for photodegradation reactions in microfluidic devices.