GaN-based light emitting diodes (LEDs) face several challenges if the technology is to make a significant impact on the solid state lighting market. The two most pressing of these challenges are cost and efficiency. The development of alternative substrate technologies shows promise toward addressing both of these challenges, as both GaN-based device technology and the associated metalorganic chemical vapor deposition (MOCVD) technology are already relatively mature. Zinc oxide (ZnO) and silicon (Si) are among the most promising alternative substrates for GaN epitaxy. This work focuses on the development of MOCVD growth processes to yield high quality GaN-based materials and devices on ZnO and Si. ZnO, because of its similar lattice constant and thermal expansion coefficient, is a promising substrate for growth of low defect-density GaN. The major hurdles for GaN growth on ZnO are the instability of ZnO in a hydrogen atmosphere and out-diffusion of zinc and oxygen from the substrate. A process was developed for the MOCVD growth of wurtzite GaN and InxGa1-xN on ZnO, and the structural and optical properties of these films were studied. High zinc and oxygen concentrations remained an issue, however, and the diffusion of zinc and oxygen into the subsequent GaN layer was studied more closely. Silicon is the most promising material for the development of an inexpensive, large-area substrate technology. The challenge in GaN growth on Si is the tensile strain induced by the lattice and thermal mismatch between GaN and Si. A thin atomic layer deposition (ALD)-grown Al2O3 interlayer was employed to relieve strain while also simplifying the growth process. While some strain was still observed, the oxide interlayer leads to an improvement in thin film quality and a reduction in both crack density and screw dislocation density in the GaN films. A comparison of GaN-based LEDs grown on sapphire and Al2O3/Si shows similar performance characteristics for both devices. IQE of the devices on silicon is ~32%, compared to ~37% on sapphire. These results show great promise toward an inexpensive, large-area, silicon-based substrate technology for MOCVD growth of GaN-based optoelectronic devices.

In this study, photoemission spectroscopy (PES) was used to investigate the electronic properties of nanocrystalline titanium dioxide (TiO2), zinc oxide (ZnO), and cadmium selenide (CdSe). Electrospray deposition technique enabled the preparation of thin films in vacuum from a dispersion prepared outside the vacuum chamber. This method also allowed the step-wise formation of interfaces and the monitoring of the evolution of the electronic structure with intermittent PES characterization. The work function of nanocrystalline TiO2 and ZnO was measured with ultraviolet photoemission spectroscopy (UPS) and low-intensity x-ray photoemission spectroscopy (LIXPS). Measurements on environmentally contaminated surfaces revealed an instantaneous and permanent work function decrease of 0.3-0.5 eV upon exposure to ultraviolet radiation during a UPS measurement. The work function reduction is likely to be related to the formation of a surface dipole caused by the photo-chemical hydroxylation of surface defects. This phenomenon was further investigated with regard to its influence on the electronic structure of the indium tin oxide (ITO)/TiO2 interface found in dye-sensitized solar cells. The experiments suggest that UV radiation can cause a small but significant change of the charge injection barriers at the interface. The determined band line-ups revealed electron injection barriers of ~0.3-0.5 eV, while UV radiation caused an increase of about 0.15 eV. This might have the potential to further impede electron transfer to the ITO electrode and affect the performance of solar cell device. Another type of photovoltaic cell using nanocrystalline material is a heterojunction bulk solar cell. Conversion efficiencies of such devices are currently only about 3% due to the inefficient charge separation at interfaces formed by blending organic and inorganic material. An approach to improve efficiencies in such devices is the use of covalently bonded conductive polymer/inorganic hybrid nanocrystals. In this study a prototypical model system was investigated with PES with the aim to develop a measurement protocol that allows the determination of electronic properties for such hybrid materials. The comparison of the relative core-level binding energies of the organics-functionalized CdSe nanocrystal compared to the ligand-free CdSe nanocrystal and the arylselenophosphate ligand material enabled the determination of the electronic structure at the interface. Core-level measurements support the hypothesis that the Se functionality of the organic ligand coordinates to the Cd sites on the nanopthesis surface.

In order to properly evaluate the ecological and human health risks of ZnO Manufactured nanomaterials (MNMs) released to the environment, it is critical to understand the likely transformation products in the wastewater treatment process and in soils receiving biosolids. To address this critical knowledge gap, we examined the transformation reactions of 30 nm ZnO MNMs in single component and multi-component systems, with phosphate and natural organic matter (NOM). We also assessed the influence of nano ZnO transformation on the bioavailability, and toxicity of ZnO transformation products to Triticum aestivum. The data revealed that ZnO MNMs react with phosphate at concentrations expected in wastewater and transform into two distinct morphological/structural phases. A micron scale crystalline zinc phosphate phase (hopeite), and a nano-sized phase that likely consists of a ZnO core with a Zn3(PO4)2 rich shell. Presence of NOM reduces particle aggregation and enhances stability, regardless of the sequence of ligands addition in the aging scenarios. The presence of phosphate and NOM also altered the bioavailability and reduced the toxicity of the ZnO MNMs to Triticum aestivum.

Heterojunctions of n-ZnO/p-Si solar cells were fabricated by RF sputtering ZnO:Al onto boron-doped (100) silicon (Si) substrates. Zinc Oxide (ZnO) films were also deposited onto soda lime glass for electrical measurements. Sheet resistance measurements were performed with a four-point-probe on the glass samples. Values for samples evacuated for 14 hours prior to deposition increased from 7.9 to 10.17 and 11.5 O/□ for 40 W, 120 and 160 W in RF power respectively. In contrast, those evacuated for 2 hours started with a higher value of 22.5 O/□, and decreased down to 7.6 and 5.8 O/□. Vacuum annealing was performed for both the glass and the Si samples. Current-voltage measurements were performed on the ZnO/Si junctions in the dark and under illumination. Parameters such as open-circuit voltage, Voc; short-circuit current, Isc; fill factor, FF; and efficiency, eta were determined. A maximum efficiency of 0.25% among all samples was produced, with an I sc of 2.16 mA, Voc of 0.31V and a FF of 0.37. This was a sample fabricated at an RF power of 80 W. Efficiency was found to decline with vacuum annealing. Furthermore, interfacial state density calculated based on capacitance-voltage measurements showed an increase in the value with vacuum annealing. The results found suggest that the interface states may be due to an interdiffusion of atoms, possibly those of Zn into the Si surface. The Electron Beam Induced Current (EBIC) method was used to determine diffusion length to be at a value ∼40--80 mum and therefore a minority carrier lifetime calculated of 3 musec. It was also used to determine the surface recombination velocity (SRV) of the fractured surface of the Si bulk from the fabricated solar cells. An SRV of ∼500 cm/sec was determined from the fractured Si surface, at a point located at 30 and 20 mum away from the junction interface.

The object of this thesis research was to develop and characterize a new type of acoustic biosensor - a ZnO-based laterally excited thickness shear mode (TSM) resonator in a solidly mounted configuration. The first specific aim of the research was to develop the theoretical underpinnings of the acoustic wave propagation in ZnO. Theoretical calculations were carried out by solving the piezoelectrically stiffened Christoffel equation to elucidate the acoustic modes that are excited through lateral excitation of a ZnO stack. A finite element model was developed to confirm the calculations and investigate the electric field orientation and density for various electrode configurations. A proof of concept study was also carried out using a Quartz Crystal Microbalance device to investigate the application of thickness shear mode resonators to cancer biomarker detection in complex media. The results helped to provide a firm foundation for the design of new gravimetric sensors with enhanced capabilities. The second specific aim was to design and fabricate arrays of multiple laterally excited TSM devices and fully characterize their electrical properties. The solidly mounted resonator configuration was developed for the ZnO-based devices through theoretical calculations and experimentation. A functional mirror comprised of W and SiO2 was implemented in development of the TSM resonators. The devices were fabricated and tested for values of interest such as Q, and electromechanical coupling (K2) as well as their ability to operate in liquids. The third specific aim was to investigate the optimal surface chemistry scheme for linking the antibody layer to the ZnO device surface. Crosslinking schemes involving organosilane molecules and a phosphonic acid were compared for immobilizing antibodies to the surface of the ZnO. Results indicate that the thiol-terminated organosilane provides high antibody surface coverage and uniformity and is an excellent candidate for planar ZnO functionalization. The fourth and final specific aim was to investigate the sensitivity of the acoustic immunosensors to potential diagnostic biomarkers. Initial tests were performed in buffer spiked with varying concentrations of the purified target antigen to develop a dose-response curve for the detection of mesothelin-rFc. Subsequent tests were carried out in prostate cancer cell line conditioned medium for the detection of PSA. The results of the experiments establish the operation of the devices in complex media, and indicate that the acoustic sensors are sensitive enough for the detection of biomolecular targets at clinically relevant concentrations.

Understanding the fundamentals of the growth of nanostructures is key to controlling their size and morphology. This thesis investigated the supersaturation effect as well as other effects on the growth of two one-dimensional nanomaterials - Magnesium hydroxide sulfate hydrate(MHSH) nanobelt and ZnO nanorod. It was found that the supersaturation for the growth of 1D nanomaterial had to be controlled at low level and it could be controlled through sparingly soluble carbonate salts. To examine the supersaturation effect on one-dimensional nanostructure growth, this study developed a quantitative kinetic model was developed to describe the one-dimensional nanostructure growth. The qualitative investigation and the quantitative model should provide more insight to the processes and some guide-lines for one-dimensional nanostructure growth in the future. This thesis also examines other factors such as agitation and temperature. Some other process parameters can have a significant effect on the growth process. The Zn(NO3)2 and HMT system was used as a model system to demonstrate that agitation had dramatic effects on the final morphology of the nanostructure. Spherical morphology could be obtained through mixing the reaction solution. The building blocks of the nanospheres were similar to those forming the nanorods. Thus, the spherical morphology was believed to result from the breakdown of the free diffusion of building blocks to the growing nanocrystal surface.

The entire thesis text is included in the research.pdf file; the official abstract appears in the short.pdf file; a non-technical public abstract appears in the public.pdf file. Title from PDF of title page (University of Missouri--Columbia, viewed on March 23, 2010). Thesis advisor: Dr. Mengshi Lin. Includes bibliographical references.

Orientador: José Roberto Cury Saad / Banca: Victor Humberto Orbegoso Flores / Banca: Luiz Alberto Plácido Penna / Banca: Leonor de Castro Monteiro Loffredo / Banca: Welingtom Dinelli / Resumo: O objetivo deste estudo foi avaliar o efeito de cimentos provisórios e de métodos de limpeza dentinária na resistência de união de restaurações indiretas em resina à dentina. Foram selecionados 21 terceiros molares recém extraídos e isentos de cárie. A parte da coroa dental correspondente ao esmalte foi removida expondo-se toda superfície dentinária. Os dentes foram divididos aleatoriamente em sete grupos experimentais de acordo com o cimento provisório e o método de limpeza dentinária utilizado: (G1-controle) não recebeu restauração provisória nem limpeza dentinária; (G2) cimentação provisória com Life e limpeza com pasta de pedra-pomes; (G3) cimentação provisória com Life (Kerr) e limpeza com jato abrasivo; (G4) nenhum procedimento de limpeza foi executado após cimentação com Life; (G5) cimentação provisória com Temp Bond e limpeza com pasta de pedra-pomes; (G6) cimentação provisória com Temp Bond (Kerr) e limpeza com jato abrasivo e (G7) nenhum procedimento de limpeza foi executado após cimentação com Temp Bond. Após uma semana de armazenamento em água, restaurações de Solidex (Shofu) foram cimentadas com adesivo Single Bond (3M ESPE) e cimento Rely X ARC (3M ESPE). Todos os produtos foram manipulados de acordo com as instruções do fabricante. Os dentes foram seccionados obtendo-se espécimes de 1,0 mm2 para realização de teste de microtração. Os valores obtidos foram submetidos à análise de variância e teste de Tukey. Os resultados indicaram que o grupo contaminado com hidróxido de cálcio sem realização da limpeza dentinária apresentou os menores valores de resistência e foi estatisticamente diferente do grupo onde não houve contaminação. Qualquer dos cimentos e métodos de limpeza utilizados obteve as maiores médias de resistência, porém sem diferenças significativas entre elas. / Abstract: The purpose of this study was to evaluate the effect of provisional cements and dentin cleaning methods on the adhesion of resin bonded indirect restorations. Flat dentin surfaces were produced cutting extracted human molars. The teeth were divided randomly in seven experimental groups according with the provisional cement and the used dentin cleaning method: (G1- control) no provisional restoration and no dentin cleaning; (G2) pumice-water slurry cleaning after cementation with Life (Kerr); (G3) aluminum oxide sandblasting after cementation with Life; (G4) no cleaning procedure after Life cementation; (G5) pumice-water slurry cleaning after cementation with Temp Bond (Kerr); (G6) aluminum oxide sandblasting after cementation with Temp Bond and (G7) no cleaning procedure after Temp Bond cementation. After one week of storing in water, Solidex indirect restorations (Shofu) were cemented with Single Bond adhesive system (3M ESPE) and Rely X ARC cement (3M ESPE). All products were handled according with manufacturer's instructions. The teeth were sectioned resulting in adhesion area of 1,0 mm2 specimens for microtencile tests. The resulted values were submitted to variance analysis and Tukey's test. These values indicated the group which was contaminated with calcium hydroxide cement and had no dentin cleaning presented the lowest bond strength and was statistically different from the group with no contamination. Any of the used cements and cleaning methods got the highest means of bond strength, but with no relevant differences among them. With these results can be concluded that, after the treatment with provisional cements, the absence of dentin cleaning implies in lower bond strength values. / Doutor

Orientador: Angela Cristina Cilense Zuanon / Resumo: Avaliou-se a dureza superficial, rugosidade, porosidade, resistência a compressão, atividade antibiofilme, atividade metabólica do biofilme (XTT) e observou-se a aderência e formação do biofilme em microscopia eletrônica de varredura (MEV) de um cimento de ionômero de vidro (CIV) de alta viscosidade (Ketac Molar Easy Mix), associado a nanopartículas de óxido de zinco (NPZnO) a 2% ou ao diacetato de clorexidina (CLX) nas concentrações de 0,5%, 1% e 2%. Como grupo controle utilizou-se o próprio CIV. Para os testes físicos, mecânicos e atividade antibiofilme foram confeccionados 10 corpos de prova por grupo, para o teste de XTT e MEV, foram utilizados 5 e 2 corpos de prova por grupo respectivamente. A atividade antibiofilme foi avaliada para biofilme monoespécie de Streptococus mutans, no período de incubação de 1, 7, 14 e 21 dias. Realizou-se contagem das unidades formadoras de colônia por mililitro (UFC/mL) e a atividade metabólica do biofilme, assim como a observação em MEV foram avaliadas nos os períodos de 1 e 7 dias . Os dados foram analisados estatisticamente e atenderam quanto à normalidade e a homogeneidade de variâncias. Realizou-se análise paramétrica de variância (ANOVA) para verificar diferença estatística seguida pelo teste de Tukey. Todos os testes foram realizados com um nível de significância de 5%. Avaliação qualitativa em MEV foi realizada para a observação da aderência e formação de biofilme. No teste de dureza superficial todos os grupos apresentaram diminui... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: It was evaluated the surface hardness, roughness, porosity, compressive strength, antibiofilm activity, metabolic activity of the biofilm (XTT) and the adherence and formation of the biofilm in Scanning Electron Microscopy (SEM) of a glass ionomer cement (GIC) of high viscosity (Ketac Molar Easy Mix), associated with 2% zinc oxide (NPZnO) nanoparticles or chlorhexidine diacetate (CLX) at concentrations of 0.5%, 1% and 2%. As a control group, the GIC itself was used. For the physical, mechanical and antibiofilm activity tests, 10 specimens were prepared per group, for the XTT and MEV test, 5 and 2 specimens were used per group, respectively. The antibiofilm activity was evaluated for monospecific biofilm of Streptococus mutans, during the incubation period of 1, 7, 14 and 21 days. The colony forming units were counted per milliliter (CFU / mL) and the metabolic activity of the biofilm, as well as the SEM observation, were evaluated in the 1 and 7 day periods. The data were analyzed statistically and attended to the normality and homogeneity of variances. We performed a parametric analysis of variance (ANOVA) to verify statistical difference followed by the Tukey test. All tests were performed with a significance level of 5%. Qualitative evaluation in SEM was performed for the observation of adhesion and biofilm formation. In the superficial hardness test, all groups showed decreased values, being the lowest values of the CLX groups. For the surface roughness, only the group wi... (Complete abstract click electronic access below) / Doutor

O trauma dental é uma das principais causas da reabsorção radicular. A reabsorção radicular é uma perda patológica progressiva da dentina e do cemento em um dente permanente, que pode ocorrer dentro do dente, ou na superfície externa do dente. Uma proposta de pasta obturadora densa, composta por Ca(OH)2, gel de clorexidina 2% (CHX) e óxido de zinco (ZnO) vem sendo utilizada como protocolo para dentes com reabsorção radicular. Apesar das propriedades do Ca(OH)2, CHX e ZnO serem amplamente estudadas de forma individual, há pouca informação na literatura sobre o mecanismo de ação da associação entre Ca (OH)2, CHX e ZnO. Portanto, o objetivo do estudo foi avaliar propriedades biológicas e físico-químicas desta associação. Neste estudo foram analisadas as propriedas de: atividade antimicrobiana, radiopacidade, escoamento, liberação de ions cálcio, avaliação de pH, citotoxicidade, bioatividade e proliferação celular a partir de pastas intracanais, como segue: Natrosol; Natrosol + ZnO; Natrosol + Ca(OH)2; Natrosol + ZnO + Ca(OH)2; 2% CHX; 2% CHX + ZnO; 2% CHX + Ca(OH)2; 2% CHX + ZnO + Ca(OH)2. Todos os ensaios foram realizados em triplicatas. Foi realizada uma análise estatística descritiva e inferencial. Os dados foram analisados estatísticamente, seguindo o teste de normalidade (teste de Shapiro-Wilk). A análise estatística foi realizada com o software GraphPad Prism 7 (GraphPad Software Inc., La Jolla, CA, EUA), com um nível de significância de 5%. O efeito antimicrobiano das pastas contra E. faecalis dependia da presença de CHX. Os halos de inibição mais elevados para C. albicans foram associados com Ca(OH)2 + CHX. Apenas as pastas com ZnO demonstraram uma radiopacidade superior a 3 mm Al, o Ca(OH)2 reduziu a radiopacidade das pastas contendo ZnO. As pastas que não continham Ca(OH)2 não liberaram ions de cálcio. Existe uma tendência para aumentar o pH até 14 dias. Os grupos com CHX apresentaram maior escoamento do que o natrosol quando misturados apenas com Ca(OH)2 ou ZnO. O teste de proliferação celular mostrou o fechamento contínuo da ferida de acordo com o tempo em todos os grupos avaliados, com exceção da CHX. Todos os grupos que continham Ca(OH)2 apresentaram maior formação de nódulos mineralizados de acordo com o tempo e uma atividade enzimática aumentada, exceto para o grupo CHX. Todos os grupos que continham Natrosol na sua composição apresentaram resultados acima ou próximos da linha de controle para a citotoxicidade. O grupo CHX apresentou uma taxa de viabilidade inferior a 50%, mas quando acompanhado de Ca(OH)2 ou ZnO mostrou taxas de viabilidade semelhantes às da linha de controle. Concluiu-se que a pasta obturadora composta por CHX + ZnO + Ca(OH)2 demonstrou efeitos biológicos favoráveis, como bioatividade, citotoxicidade e proliferação celular e mostrou a liberação de Ca+, alto pH, atividade antimicrobiana principalmente devido à presença de CHX e Ca(OH)2. / Dental trauma is a major cause of root resorption. Root resorption is a pathological progressive loss of dentine and cementum in a permanent tooth, that can occur inside/internal the tooth, or on the external surface of the tooth. A proposal of dense filling paste, composed of Ca (OH) 2, chlorhexidine gel 2% (CHX) and zinc oxide (ZnO) has been used as a protocol for teeth with root resorption. Despite the properties of Ca(OH)2, CHX and ZnO have been extensively studied, there is little information on the literature regarding the mechanism of action on the association among Ca(OH)2, 2% CHX and ZnO. Therefore, the aim of the study was to test biological and physicochemical properties by this filling paste. In this study the properties of antimicrobial activity, radiopacity, flow, calcium ions release, pH evaluation, cytotoxicity, bioactivity and cell proliferation from intracanal pastes were analyzed as follows: Natrosol; Natrosol + ZnO; Natrosol + Ca(OH)2; Natrosol + ZnO + Ca(OH)2; 2% CHX; 2% CHX + ZnO; 2% CHX + Ca(OH)2; 2% CHX + ZnO + Ca(OH)2. All assays were performed in triplicate. A descriptive and inferential statistical analysis was performed. The data were statistical analyzed, following the normality test (Shapiro-Wilk test). Statistical analysis was carried out with the software GraphPad Prism 7 (GraphPad Software Inc., La Jolla, CA, USA), at a 5% level of significance. Antimicrobial effect of the pastes against E. faecalis depended on the presence of CHX. The highest inhibition haloes for Candida albicans were associated with Ca(OH)2 + CHX. Only pastes with ZnO demonstrated radiopacity higher than 3 mm Al, Ca(OH)2 reduced the radiopacity of the pastes containing ZnO. Pastes that did not contain Ca(OH)2 had no calcium ion release. There is a tendency to increase the pH up to 14 days.The groups with CHX had greater fluidity than natrosol when mixed only with Ca(OH)2 or ZnO. Cell proliferation showed continuous closure of the wound according to time in all evaluated groups, except for 2% CHX. All groups containing Ca(OH)2 showed increased mineralized nodules formation according to the time and an increased enzyme activity except for group 2% CHX. All groups containing Natrosol in their composition showed results above or near the control line to cytotoxicity. CHX group exhibited a viability rate lower than 50% but when containing Ca(OH)2 or ZnO showed viability rates similar to the control line. It was concluded that the filling paste formed by CHX + ZnO + Ca(OH)2 demonstrated favorable biological effects such as bioactivity, cytotoxicity and cellular proliferation and showed release of Ca, high pH, antimicrobial activity mainly due to the presence of CHX and Ca(OH)2.