Transparent oxide semiconducting films have continued to receive considerable attention, from a fundamental and application-based point of view, primarily because of their useful fundamental properties. Of particular interest is zinc oxide (ZnO), an n-type semiconductor that exhibits excellent optical, electrical, catalytic and gas-sensing properties, and has many applications in various fields. In this work, thin film transistor (TFT) arrays based on ZnO have been prepared by reactive radio frequency (RF) magnetron sputtering. Prior to the TFT fabrication, ZnO layers were sputtered on to glass and silicon substrates, and the deposition parameters optimised for electrical resistivities suitable for TFT applications. The sputtering process was carried out at room temperature with no intentional heating. The aim of this work is to prepare ZnO thin films with stable semiconducting electrical properties to be used as the active channel in TFTs; and to understand the role of intrinsic point defects in device performance and stability. The effect of oxygen (O2) adsorption on TFT device characteristics is also investigated. The structural quality of the material (defect type and concentration), electrical and optical properties (transmission/absorption) of semiconductor materials are usually closely correlated. Using the Vienna ab-initio simulation package (VASP), it is predicted that O2 adsorption may influence film transport properties only within a few atomic layers beneath the adsorption site. These findings were exploited to deposit thin films that are relatively stable in atmospheric ambient with improved TFT applications. TFTs incorporating the optimised layer were fabricated and demonstrated very impressive performance metrics, with effective channel mobilities as high as 30 cm2/V-1s-1, on-off current ratios of 107 and sub-threshold slopes of 0.9 – 3.2 V/dec. These were found to be dependent on film thickness (~15 – 60 nm) and the underlying dielectric (silicon dioxide (SiO2), gadolinium oxide (Gd2O3), yttrium oxide (Y2O3) and hafnium oxide (HfO2)). In this work, prior to sputtering the ZnO layer (using a ZnO target of 99.999 % purity), the sputtering chamber was evacuated to a base pressure ~4 x 10-6 Torr. Oxygen (O2) and argon (Ar) gas (with O2/Ar ratio of varying proportions) were then pumped into the chamber and the deposition process optimised by varying the RF power between 25 and 500 W and the O2/Ar ratio between 0.010 to 0.375. A two-level factorial design technique was implemented to test specific parameter combinations (i.e. RF power and O2/Ar ratio) and then statistical analysis was utilised to map out the responses. The ZnO films were sputtered on glass and silicon substrates for transparency and resistivity measurements, and TFT fabrication respectively. For TFT device fabrication, ZnO films were deposited onto thermally-grown silicon dioxide (SiO2) or a high-k dielectric layer (HfO2, Gd2O3 and Y2O3) deposited by a metal-organic chemical deposition (MOCVD) process. Also, by using ab initio simulation as implemented in the “Vienna ab initio simulation package (VASP)”, the role of oxygen adsorption on the electrical stability of ZnO thin film is also investigated. The results indicate that O2 adsorption on ZnO layers could modify both the electronic density of states in the vicinity of the Fermi level and the band gap of the film. This study is complemented by studying the effects of low temperature annealing in air on the properties of ZnO films. It is speculated that O2 adsorption/desorption at low temperatures (150 – 350 0C) induces variations in the electrical resistance, band gap and Urbach energy of the film, consistent with the trends predicted from DFT results.

Nanomaterials are the heart of nanoscience and nanotechnology. Research into nanostructures has been vastly expanding worldwide and their application spreading into numerous branches of science and technology. The incorporation of these materials in commercial products is revolutionising the current technological market. Nanomaterials have gained such enormous universal attention due to their unusual properties, arising from their size in comparison to their bulk counterparts. These nanosized structures have found applications in major devices currently under development including fuel cells, computer chips, memory devices, solar cells and sensors. Due to their aforementioned importance nanostructures of various materials and structures are being actively produced and investigated by numerous research groups around the world. In order to meet the market needs the commercialisation of nanomaterials requires nanomaterial fabrication mechanisms that will employ cheap, easy and low temperature fabrication methods combined with environmentally friendly technologies. This thesis investigates low temperature growth of various one-dimensional nanostructures for their potential application in chemical sensors. It proposes and demonstrates novel materials that can be applied as catalysts for nanomaterial growth. In the present work, zinc oxide (ZnO) and silicon (Si) based nanostructures have been fabricated using low temperature growth methods including hydrothermal growth for ZnO nanowires and plasma-enhanced chemical vapour deposition (PECVD) technique for Si nanostructures. The structural, optical and electrical properties of these materials have been investigated using various characterisation techniques. After optimising the growth of these nanostructures, gas and biosensors have been fabricated based on Si and ZnO nanostructures respectively in order to demonstrate their potential in chemical sensors. For the first time, in this thesis, a new group of materials have been investigated for the catalytic growth of Si nanostructures. Interesting growth observations have been made and theory of the growth mechanism proposed. The lowest growth temperature in the published literature is also demonstrated for the fabrication of Si nanowires via the PECVD technique. Systematic studies were carried out in order to optimise the growth conditions of ZnO and Si nanostructures for the production of uniformly shaped nanostructures with consistent distribution across the substrate. v The surface structure and distribution of the variously shaped nanostructures has been analysed via scanning electron microscopy. In addition, the crystallinity of these materials has been investigating using Raman and X-ray diffraction spectroscopies and transmission electron microscopy. In addition to the fabrication of these one-dimensional nanomaterials, their potential application in the chemical sensors has been tested via production of a glucose biosensor and an isopropyl alcohol vapour gas sensor based on ZnO and Si nanostructures respectively. The operation of the devices as sensors has been demonstrated and the mechanisms explored.

Nanotechnology is a rapidly growing industry of global economic importance, with new technologies exploiting the novel characteristics of materials manufactured at the nanoscale being developed for use within the biomedical, electronic, energy production and environmental sectors. The unusual properties of engineered nanomaterials (ENMs) that make them useful in such applications have led to concerns regarding their potential impact on the environment. The aquatic environment is particularly at risk of exposure to ENPs, yet, there is currently little known about their behaviour in aquatic systems, their capacity to be taken up by aquatic organisms or their potential toxic effects. The studies that were conducted during this work sought to investigate the ecotoxicology of a range of metal and metal oxide nanoparticles using fish as a vertebrate model. In order to gain a better understanding of the uptake and effects of ENMs in fish, rainbow trout (Oncorhynchus mykiss) were exposed to nanoparticulate (34 nm) and bulk (>100 nm) titanium dioxide particles via the water column (500 and 5000 µg L-1), and to titanium dioxide nanoparticles via the diet (0.1 and 1 mg g-1 food) and via intravenous injection (1.3 mg kg-1 body weight). Uptake of titanium dioxide into the tissues of trout after waterborne and dietary exposure was found to be very low, suggesting limited bioavailability of the nanoparticles to the fish, although small amounts of uptake of titanium dioxide across the gill epithelial membrane were observed using coherent anti-stokes Raman scattering. Intravenously injected titanium dioxide accumulated and was retained in the kidneys for up to 21 days, but no adverse effect on kidney function was detected. Silver nanoparticles are already in widespread use in a variety of consumer products such as wound dressings, food containers, sock fabrics and paints, principally for their antimicrobial activity. Despite its growing commercialisation, there is little known about the environmental effects of the use of nanoparticulate silver in these products. In order to investigate these potential effects, rainbow trout were also exposed to 10 nm, 35 nm and bulk (0.6-1.6 µm) silver particles via the water column at concentration of 10 and 100 µg L-1. Uptake of silver in the gills and liver of trout occurred, with smaller nanoparticles showing a greater propensity for association with gill tissue, but with no significant differences in uptake between particles of different sizes in the liver. No increases in lipid peroxidation were detected in gills, liver or blood plasma of trout, however, expression of cyp1a2 was significantly up-regulated in exposures to 10 nm silver particles in the gill, suggesting an increase in oxidative metabolism. In an attempt to develop an effective high through-put in vitro screening assay for ENMs, the suitability of isolated rainbow trout primary hepatocytes was examined as a potential model for in vitro screening of a range of toxicological endpoints in response to nanoparticles and for studying uptake of nanoparticles into cells. The hepatocytes retained a good level of functionality after culturing as evidenced by vitellogenin production in response to the synthetic oestrogen, 17β-oestradiol. The cultured hepatocytes, however, showed limited responses on exposure to titanium dioxide, zinc oxide, cerium oxide and silver nanoparticles for lipid peroxidation and glutathione-s-transferase activity assays. Furthermore, the hepatocytes were unresponsive to the induction of these biological responses in the positive controls, suggesting they are not a good model for investigating the potential toxic effects of ENMs in terms of these endpoints. Uptake of the nanoparticles into the cells, however, was demonstrated by coherent anti-stokes Raman spectroscopy, indicating that this in vitro assay may provide a useful model for studying uptake of ENPs into cells. The studies conducted in this thesis contribute the science base regarding the bioavailability of ENPs in aquatic media as well as highlighting the importance of characterisation of ENPs in understanding their behaviour, uptake and effects in aquatic systems and in fish.

Structural and optical properties of ZnO nanostructures synthesized by low energy ion implantation technique were examined. ZnO molecular ions were implanted into Si/SiO2 substrates at room temperature and then furnace annealed under different temperatures and environments. In all as-implanted samples only Zn nanostructures with varying diameters distributed into the Si/SiO2 matrices were observed. No trace of ZnO was found. The distributions of Zn nanostructures in Si/SiO2 closely matched results from Stopping and Range of Ions in Matter (SRIM) simulations. During annealing at 750 oC, Zn diffused both toward and away from the surface of the substrate and combine with oxygen to form ZnO nanostructures. At higher annealing temperatures ZnO bonding started to break down and transfer to zinc silicate (Zn2SiO4), and at 900 oC the ZnO was completely converted into Zn2SiO4. The average sizes of Zn/ZnO nanostructures depended on the ion fluence. If the fluence increased the average sizes of nanostructures also increased and vice versa. For room temperature photoluminescence (RT-PL), band-edge emission in the ultraviolet (UV) region was observed from all samples annealed at 700 oC/750 oC and were slightly blue shifted as compare to bulk ZnO. Donor-bound exciton (D,X) and acceptor-bound exciton (A,X) transitions were observed in low temperature photoluminescence (PL). The lifetime of both donor-bound excitonic emission (D, X) and acceptor-bound excitonic emission (A, X) were found to be in the picosecond (ps) range.

Semiconductor nanowires have attracted considerable attention as possible source for lasers and optical storage media. We report the fabrication and optical characterization of ZnO and CdS nanowires. The former are produced by electrochemical deposition of Zn inside nanoporous alumina films containing regimented arrays of 10nm, 25nm and 50 nm diameter pores, followed by room temperature chemical oxidization. Fluorescence spectroscopy shows different characteristics associated with different sample diameter. The 50 nm ZnO nanowires show an exciton recombination peak and an additional peak related to the deep trap levels. 25 nm ZnO nanowires show a only the exciton recombination peak, which is red shifted, possibly due to quantum confined Stark effect associated with built in charges in the alumina. This feature can be exploited to produce light emitting devices whose frequency can be modulated with an external electric field. Such devices could be novel ultra-violet frequency modulators for optical communication and solar blind materials. In addition, we have investigated fluorescence spectra of 10-, 25- and 50-nm diameter CdS nanowires (relative dielectric constant = 5.4) self assembled in a porous alumina matrix (relative dielectric constant = 8-10). The spectra reveal peaks associated with free electron-hole recombination. The 10-nm wire spectra show an additional lower energy peak due to exciton recombination. In spite of dielectric de-confinement caused by the insulator having a higher dielectric constant than the semiconductor, the exciton binding energy increases almost 8-fold from its bulk value in the 10 nm wires. This increase is most likely due to quantum confinement accruing from the fact that the exciton Bohr radius (~5 nm) is comparable to or larger than the wire radius, especially if side depletion is taken into account. Such an increase in the binding energy could be exploited to make efficient room temperature luminescent devices in the visible range.

The Micro-Raman scattering technique has been used for the study of GaN and ZnO. Capabilities of the Raman technique and existing literature on Raman spectroscopy in GaN and ZnO are reviewed. About 50 GaN and ZnO samples with a wide range of properties are studied. From the analysis of positions of the E2H and A1(LO) phonon modes, biaxial stress and plasmon coupling of the Al(LO) mode are observed and compared to a bulk GaN sample. The stress-related shift rate for the AI(LO) mode in hexagonal GaN is established to be 2.7 ± 0.4 cm-1/GPa through series of GaN with low free carrier concentration. Bulk ZnO and ZnO layers grown on sapphire have been studied, and no biaxial stress is found in ZnO layers. Doping and impurity modes resulted in disorder-activated scattering in ZnO. The choice of the laser for study of GaN and ZnO layers on sapphire substrate is discussed.

O presente trabalho tem por objetivo o desenvolvimento de um novo material nanocompósito com propriedades biocidas, alta porosidade e alta permeabilidade ao ar, possibilitando sua aplicação na área biomédica. Neste trabalho, foram desenvolvidas membranas compósitas de poliuretano termoplástico (TPU) contendo prata (Ag) e óxido de zinco (ZnO), a partir da evaporação de soluções durante o processo de eletrofiação. Mediu-se as propriedades de viscosidade e de condutividade elétrica das soluções preparadas para eletrofiação. Avaliou-se a modificação da morfologia do material pelo uso de vários solventes em diferentes concentrações. Uma morfologia mais uniforme das membranas contendo fibras eletrofiadas foi obtida com o sistema de solventes tetra-hidrofurano (THF) e dimetilformamida (DMF), na proporção de 50:50. A avaliação da morfologia e da distribuição da fase dispersa inorgânica nas membranas foi efetuada utilizando-se microscopia ótica (MO) e microscopia eletrônica de varredura (MEV), e a formação de fibras com diâmetros na faixa de 250 a 800 nanômetros foi observada. As fases dispersas apresentaram-se distribuídas na membrana, sem a presença de regiões de aglomeração. A presença de prata ou de óxido de zinco nas membranas eletrofiadas foi confirmada através da espectroscopia de energia dispersiva de raios- X (EDS) e por difratometria de raios-X. As propriedades bactericidas das membranas compósitas de TPU/ZnO e TPU/Ag foram avaliadas e estabelecidas em testes com as bactérias S. aureus e K. pneumoniae. O teste de citotoxicidade das membranas de TPU foi executado e numa avaliação inicial foi observada a sua biocompatibilidade. / The aim of this study is to develop nanostructured polyurethane composite membranes which have antibacterial properties, high porosity and high air permeability, suitable for medical applications. Membranes of thermoplastic polyurethane (TPU) having silver and zinc oxide particles as additives were prepared by electrospinning. The impact of the solvents nature on the electrospinning process was studied. The best results were obtained using a mixture of tetrahydrofuran (THF) and dimethylformamide (DMF), at 50:50 ratio. Viscosity and electrical conductivity of the solutions were measured. Morphology of the membranes formed by the fibers was verified using optical microscopy and scanning electron microscopy, and fibers presenting diameters from 250 to 800 nanometers were observed. The presence of silver and zinc oxide particles in the membranes was confirmed using energy dispersive X-ray spectrometry and wide angle X-ray diffractometry. Antibacterial properties of the membranes were evaluated by testing its activity against suspensions of S. aureus and K. pneumoniae. Additionally, cytotoxicity tests were performed for initial evaluation of the biocompatibility of the TPU membranes having silver as additive.

Nesta dissertação, estuda-se a reação de carboxilação de metano com CO2 para a produção de ácidos e acetatos. Esses dois gases contribuem para a intensificação do efeito estufa, relacionado aos problemas ambientais enfrentados atualmente. Dessa forma, o aproveitamento dessas fontes para a produção de compostos de alto valor agregado é de grande interesse. Para isso, um catalisador com óxido de zinco suportado em grafeno foi sintetizado e caracterizado a partir de diferentes técnicas, com o objetivo de se avaliar as propriedades morfológicas, texturais e estruturais do catalisador, bem como a sua estabilidade térmica e redutibilidade. O desempenho do catalisador foi avaliado na reação de metano com CO2 e O2 em testes de reação superficial com temperatura programada, com a formação de gases como CO, H2 e H2O, e em testes a partir da técnica de Espectroscopia no Infravermelho, com o estudo da interação dos gases metano e CO2 com o catalisador, assim como dos mecanismos que levam à formação dos gases observados e das evidências que indicam o processo de formação de ácido ou acetatos na superfície do catalisador. / The present study is dedicated to the carboxilation reaction of methane with CO2 for acid and acetates production. These two gases contribute to the intensification of the greenhouse effect, related to the environmental problems currently faced. Thus, the use of these sources for the production of compounds with high added value is of large interest. In this study, a zinc oxide catalyst supported on graphene was synthesized and characterized using different techniques, with the objective of evaluating the morphological, textural and structural properties of the catalyst, as well as its thermal stability and reducibility. The catalyst performance was evaluated in the reaction of methane with CO2 and O2 in tests of the surface reaction at programmed temperature, with the formation of gases such as CO, H2 and H2O, and in tests using Infrared Spectroscopy technique, for the study of the interaction of methane and CO2 with the catalyst, as well as for studying the mechanisms that lead to the formation of the gases observed, and the evidence that indicates the process of formation of acids or acetates on the catalyst surface.

Nos últimos anos no Brasil, instituições como o Instituto Nacional de Câncer José Alencar Gomes da Silva e o Ministério da Saúde, reportaram o aumento de casos de câncer de pele. O câncer de pele é uma das doenças mais comuns a nível mundial e pode estar relacionado à exposição à radiação ultravioleta (UV). O objetivo do presente trabalho foi realizar a funcionalização de tecidos sarja 100% algodão com nanopartículas (NPs) de óxido de zinco (ZnO), as quais possuem propriedades para aplicação como protetor solar, melhorando desta forma as características de proteção à radiação UV do algodão. As NPs de ZnO foram sintetizadas pelo processo de precipitação, empregando nitrato de zinco hexahidratado (Zn(NO3)2.6H2O) e hidróxido de sódio (NaOH). A síntese in situ das NPs de ZnO sobre os tecidos foi realizada por meio do processo de esgotamento, usando o equipamento de tingimento têxtil HT (High Temperature). Para este processo foram utilizadas diferentes concentrações de Zn(NO3)2.6H2O (2, 5, 8 e 10% sobre a massa do tecido) e NaOH (0,7; 1,6; 2,5 e 3,0 g/L), respectivamente. A avaliação do fator de proteção UV (FPU) e os testes de resistência à lavagem dos tecidos foram realizados segundo normas as AATCC 183:2004 e AATCC 61:1996, respectivamente. Foram promovidas também aplicações de resinas têxteis comerciais sobre os tecidos funcionalizados e determinação das propriedades físicas. Além disso, foram realizadas caracterizações de vibração molecular, estruturais e morfológicas das NPs de ZnO e para os tecidos funcionalizados foram efetuadas caracterizações estruturais, morfológicas e térmicas. Os resultados mostraram que tanto as NPs de ZnO como as sintetizadas in situ sobre os tecidos apresentaram estrutura cristalina hexagonal wurtzite. As NPs de ZnO mostraram uma morfologia de estrela com pontas muito protuberantes enquanto que as NPs sintetizadas no tecido apresentaram morfologia similar, mas com pontas pequenas. Para todas as concentrações de nitrato de zinco estudadas, antes e após as 20 lavagens, o FPU dos tecidos funcionalizados com NPs de ZnO tiveram categoria de proteção UV entre boa e excelente / In Brazil, institutions such as the José Alencar Gomes da Silva National Cancer Institute (INCA) and the Brazilian Ministry of Health reported increase and appearance of new types of cancer in recent years. Skin cancer is the most common type of disease worldwide and generally might be related to the exposure of the skin to ultraviolet (UV) radiation generated by the sun. The objective of this work was to perform the functionalization of 100% cotton woven fabrics with zinc oxide (ZnO) nanoparticles (NPs), which has interesting properties for applications as solar protector, thus improving the protection characteristics of cotton against UV radiation. ZnO NPs were synthesized by the precipitation process using zinc nitrate hexahydrate (Zn(NO3)2.6H2O) and sodium hydroxide (NaOH). In situ synthesis of ZnO NPs onto the fabric was carried out via exhaust dyeing method, using the textile High Temperature (HT) dyeing machine. For this process, different concentrations of Zn(NO3)2.6H2O (2, 5, 8 and 10% on the weight of fabric) and NaOH (0.7, 1.6, 2.5 and 3.0 g/L) were used. The evaluation of UV protection factor (UPF) and wash durability tests were performed according to AATCC 183:2004 and AATCC 61:1996 standards, respectively. Commercial textile resins applications onto functionalized fabrics and determination of physical properties were also performed. In addition, molecular, structural and morphological characterizations of ZnO NPs were carried out and structural, morphological and thermal analyzes were performed for functionalized fabric. The results showed that both ZnO NPs and those in situ synthesized onto the fabric, exhibited wurtzite hexagonal crystalline structure. The ZnO NPs displayed a star-like morphology with very pronounce tips, while the NPs onto the fabric had a similar morphology but with small tips. For all concentrations of zinc nitrate studied, before and after 20 cycles washing, the UPF of cotton fabrics functionalized with ZnO NPs had an UV-protection category between good to excellent

O objetivo do presente trabalho foi avaliar a resposta tecidual em 48 pré- molares (96 raízes) de cães, após obturação dos canais radiculares com diferentes materiais. Os dentes foram submetidos à biopulpectomia, ao preparo biomecânico e divididos em oito grupos, onde os canais radiculares foram obturados com os seguintes materiais: Grupos I e V pasta Calen® espessada com óxido de zinco; Grupos II e VI cimento EndoREZ; Grupos III e VII cimento Sealapex®, e Grupos IV e VIII cimento de óxido de zinco e eugenol. Decorridos os períodos de 30 e 90 dias, os animais foram mortos, as peças removidas e submetidas ao processamento histológico. A avaliação histopatológica foi baseada nos seguintes parâmetros: intensidade do infiltrado inflamatório, espessura do ligamento periodontal, reabsorção do tecido ósseo, limte de obturação e presença ou ausência de selamento apical. Os resultados foram submetidos à análise estatística pelo teste não paramétrico de Kruskal-Wallis, com nível de significância de 5%. Com base nos resultados obtidos e considerando as condições específicas deste trabalho, pôde-se concluir que a pasta Calen® espessada com óxido de zinco foi o material que apresentou a melhor resposta tecidual, seguida pelos cimentos Sealapex® e óxido de zinco e eugenol. O cimento EndoREZ apresentou resposta tecidual desfavorável . / The objective of the present work was evaluate the tissue response in 48 premolars( 96 roots), of dogs teeth, after pulpectomy, with different roots canals filling materials. The teeth were submitted to the biomechanical preparation and divided in eigth groups, where the canals were filled with following materials: Groups I and V - Calen® paste thickened with zinc oxide; Groups II and VI - EndoREZ sealer; Groups III and VII - Sealapex® sealer; and Groups IV and VIII Zinc oxide and eugenol cement. After periods of 30 and 90 days, the animals were killed, the pieces reduced and submitted to the histological processing. The histopathological evaluation was based on the following parameters: intensity of the inflammatory infiltrate, thickness of the periodontal ligament, bone resorption,filling limit and presence or absence of sealed apical. The results were submitted to the statistical analysis by the non parametric test of Kruskal-Wallis, with significance level was 5%. Based on the results obtained in histopathological analysis and methodologies employed in the present work, it may be conclued that: Calen® paste thickened with zinc oxide was the material that showed the better tissue response, following by Sealapex® sealer and zinc oxide and eugenol cement. EndoREZ sealer showed tissue response unfavorable.