The temperature dependence of the band structure of ZnO has been studied on epitaxial films and bulk crystals with the methods of temperature dependent photoluminescence, photoconductivity, reflectivity and transmission spectroscopy. A major question investigated was the intriguing detail that could be resolved in band edge photoconductivity spectra of both high quality ZnO bulk crystals as well as epitaxial films. The connection of these spectral details in photoconductivity to the excitonic band structure of ZnO was made by comparison to the other spectroscopic methods which have a better understood relation to the semiconductor band structure. Photoluminescence spectroscopy enabled us to get a direct and reliable feedback about the energy fine structure of emitting levels in ZnO. Comparison of the emitting levels of epitaxial films with the emitting levels of high quality bulk material allowed the identification of dominating defect structures and impurities in the epitaxial films. The investigation of the effect of annealing on these emission lines finally allowed us to get a better understanding of the effects of annealing on the crystal and electric structure of epitaxially grown heterostructural films and allowed the determination of the optimum temperature range to be used for improved crystal quality. It has been investigated if temperature dependent reflectivity can serve as a simple tool for the examination of the temperature dependence of the band structure of ZnO. The appeal of reflectivity is its enhanced sensitivity only to free excitonic transitions. This proved a valuable simplification compared to the methods of photoluminescence and photoconductivity: Photoluminescence is limited by phonon-broadening of the multitude of emission levels in the band gap region of ZnO, and photoconductivity has a multitude of processes that are potentially contributing to its spectra, making the identification of their relation to the band structure less reliable. Therefore the applicability of reflectivity for the deduction of the temperature dependence of the band structure has been investigated, by measuring the temperature dependence of the energy positions of the characteristic reflectivity features, with particular focus on the effect of phonon broadening and interaction of close lying resonator levels. The investigation of the temperature dependence of photoconductive centres was enabled through the resulting possibility of directly relating the purely excitonic reflectivity spectra to the complex features in photoconductivity. The temperature dependent evolution of the spectra obtained by photoconductivity then revealed that there are at least two types of photoconductive processes that have to be distinguished: features in photoconductivity that are directly related to the band structure proved to be distinguishable from slow defect related processes in terms of their response speed. For the samples of bulk ZnO as well as epitaxial films, the peaks in photoconductivity only had a meaningful position in regard to the band structure for the cases of spectra that are dominated by fast processes. The spectra dominated by slow processes showed a meaningful temperature dependence of respective dips in the spectra. The strong response of fast photoconductive levels in bulk ZnO allowed us to directly observe the A- and B-free excitons by photoconductivity. Additional fine structure could be observed that is likely to be related to the narrow photo emission lines of neutral as well as ionized donor bound excitons and the upper polariton branch of the A-free exciton. These findings agree with the temperature dependence of related Anti-Stokes phonon replica levels that allow a first estimate of the activation energies of the zero-phonon lines. The energy and temperature dependent lateral transport properties of ZnO are expected to be of importance in ZnO device technology

High energy particle irradiation inevitably generates defects in solids in the form of collision cascades. The ballistic formation and thermalization of cascades occur rapidly and are believed to be reasonably well understood. However, knowledge of the evolution of defects after damage cascade thermalization, referred to as dynamic annealing, is quite limited. Unraveling the mechanisms associated with dynamic annealing is crucial since such processes play an important role in the formation of stable post-irradiation disorder in ion-beam-processed semiconductors and determines the “radiation tolerance” of many nuclear materials. The purpose of this dissertation is to further our understanding of the processes involved in dynamic annealing. In order to achieve this, two main tasks are undertaken. First, the effects of dynamic annealing are investigated in ZnO, a technologically relevant material that exhibits very high dynamic defect annealing at room temperature. Such high dynamic annealing leads to unusual defect accumulation in heavy ion bombarded ZnO. Through this work, the puzzling features that were observed more than a decade ago in ion-channeling spectra have finally been explained. We show that the presence of a polar surface substantially alters damage accumulation. Non-polar surface terminations of ZnO are shown to exhibit enhanced dynamic annealing compared to polar surface terminated ZnO. Additionally, we demonstrate one method to reduce radiation damage in polar surface terminated ZnO by means of a surface modification. These results advance our efforts in the long-sought-after goal of understanding complex radiation damage processes in ceramics. Second, a pulsed-ion-beam method is developed and demonstrated in the case of Si as a prototypical non-metallic target. Such a method is shown to be a novel experimental technique for direct extraction of dynamic annealing parameters. The relaxation times and effective diffusion lengths of mobile defects during the dynamic annealing process play a vital role in damage accumulation. We demonstrate that these parameters dominate the formation of stable post-irradiation disorder. In Si, a defect lifetime of ∼ 6 ms and a characteristic defect diffusion length of ∼ 30 nm are measured. These results should nucleate future pulsed-beam studies of dynamic defect interaction processes in technologically relevant materials. In particular, understanding length- and time-scales of defect interactions are essential for extending laboratory findings to nuclear material lifetimes and to the time-scales of geological storage of nuclear waste.

In this thesis, high temperature vapor deposition method has been extensively used to synthesize nanomaterials. One of the as-synthesized nanostructures is superlattice-structured nanohelix, which is made of two types of alternating and periodically distributed long crystal strips. The manipulation of the nanohelix showed super-elasticity and special fracture mechanism. The other widely studied nanomaterial is vertically aligned ZnO nanowire array, which is epitaxially grown on GaN and SiC substrates. Several manipulation methods such as e-beam lithography (EBL), dielectrophoresis, and in situ direct manipulation, have been developed, so that the mechanical and electrical properties of a single nanowire can be characterized, which provide essential references for fabricating bridged nanowire based devices. Specifically, an improved atomic force microscope (AFM) based method has been developed to accurately measure the elastic modulus of bridged ZnO nanowires. Bridged nanostructure is an extremely important configuration in planar MEMS/NEMS devices and this new approach provides insights to the importance of boundary conditions. Novel physical and statistical models have been firstly developed to obtain better estimate of elastic modulus. For electrical properties of bridged nanowires, it is found that the direct contact of ZnO nanowire and Au electrodes displays a back-to-back Schottky behavior. Self-assembled monolayer (SAM) can improve the mechanical contact and increase the conductance. These devices with Schottky contacts show much better UV sensing performance than the ones with Ohmic contacts. Barrier height change is believed to play an important role in a lot of sensors. A thermionic emission-diffusion model is deduced to successfully explain the current change in a strain sensor. This thesis clearly exhibits the unique properties of ZnO nanomaterials and provides deeper understanding to methodologies as well as the phenomena. With further exploration, ZnO nanomaterials should be able to better understood and utilized, and come close to the next step of commercialization.

CoordenaÃÃo de AperfeiÃoamento de Pessoal de NÃvel Superior / Com o rÃpido crescimento de tecnologias sem fio, a indÃstria de telecomunicaÃÃes tem buscado constantemente materiais que possuam excelentes caracterÃsticas dielÃtricas para ser à base de novos dispositivos. Devido a essa demanda sempre crescente, pesquisas em busca de novos e melhores materiais cerÃmicos tÃm ocupado cada vez mais lugar de destaque no interesse da comunidade cientÃfica mundial. O uso de materiais cerÃmicos em busca de materiais fluorescentes tambÃm vem recebendo destaque, jà que materiais desse tipo apresentam diversas aplicaÃÃes, tais como lasers; diodo emissor de luz (LED); como fonte de luz sensores; estocagem de dados Ãticos e atà mesmo na Ãrea mÃdica. Neste trabalho foram estudados as propriedades da matriz cerÃmica LaNbO4 (LNO) modificada pela adiÃÃo de ZnO e tambÃm pela dopagem com Ãons terras-raras Ãrbio; itÃrbio e tÃlio. As amostras de LNO e dopadas foram obtidas atravÃs do mÃtodo reacional do estado sÃlido utilizando Ãxidos precursores seguido de tratamento tÃrmico, enquanto as amostras com ZnO foram obtidas atravÃs da adiÃÃo de determinada quantidade de massa deste sobre o LNO. Os resultados de difraÃÃo de Raios-X e espectroscopia Raman confirmaram a obtenÃÃo da fase cerÃmica LNO e os valores das propriedades dielÃtricas desse material foram prÃximos da literatura. A simulaÃÃo numÃrica realizada para o LNO apresentou bom valor de ganho e alta eficiÃncia, mostrando que esse material pode atuar como DRA. Quanto à adiÃÃo de ZnO, a difraÃÃo de Raios-X mostrou que praticamente nÃo houve mudanÃas no padrÃo de difraÃÃo da fase LNO. Jà com relaÃÃo Ãs propriedades dielÃtricas foi observado que essa adiÃÃo causou aumento nos valores de permissividade e tangente de perda de forma nÃo linear com o aumento da concentraÃÃo de zinco. Nos sistemas contendo Ãons terras-raras a difraÃÃo Raios-X e espectroscopia Raman indicaram que os Ãons dopantes entraram na estrutura cristalina da fase LNO. Na fluorescÃncia foram observadas bandas na regiÃo do verde e vermelho para as amostras com Er3+ e Yb3+, referentes Ãs transiÃÃes dos orbitais 4f do Er3+. Enquanto que para o sistema com Er3+, Yb3+ e Tm3+ foram observadas bandas nas regiÃes do ultra-violeta; azul; verde; vermelho e infravermelho originadas das transiÃÃes dos orbitais 4f do Er3+ e 4f do Tm3+. / With the rapid growth of wireless technologies, the telecommunications industry has constantly searching materials having excellent dielectric characteristics to be based on new devices. Due to this ever increasing demand, research for new and improved ceramic materials have occupied prominent place in the interest of the scientific community worldwide. The use of ceramic materials in search of fluorescent materials also has received attention, since such materials have several applications, such as lasers; light emitting diode (LED); as a source of light sensors; optical data storage and even in the medical field. In this work were studied the properties of LaNbO4 (LNO) matrix modified by adding of ZnO and also by doping with rare-earth ions erbium; ytterbium and thulium. The pure and doped LaNO4 samples were obtained by solid state reaction method using oxide precursor followed by heat treatment, while samples with ZnO was obtained by adding of determined quantity of latter on the LNO. The results of x-ray diffraction and Raman spectroscopy confirmed the formation of the ceramic phase LNO and the values of the dielectric properties obtained of this material were close to the values of the literature. The numerical simulation realized for LNO presented good gain value and a high efficiency, showing that this material can act as a DRA. About the addition of zinc, the x-ray diffraction showed that practically not occured significant changes in the diffraction pattern of LNO phase, being that regarding the dielectric properties was observed that the addition caused increase in the values of the permittivity and loss tangent nonlinearly with the increasing of the concentration of zinc. In the systems containing rare-earth ions the X-ray diffraction and Raman spectroscopy indicated that the dopant ions entered on the crystalline lattice of LNO phase. In the fluorescence were observed bands in the green and red region for the system with Er3+ and Yb3+ , concerning the transitions between the 4f orbitals of Er3+ . While for the system with Er3+ , Yb3+ and Tm3+ were observed bands in the ultraviolet region; blue; green; red and infrared originated of transitions that occur in the 4f orbitals of Er3 + and in the 4f orbitals of Tm3+.

Made available in DSpace on 2014-06-12T15:50:29Z (GMT). No. of bitstreams: 2 arquivo5735_1.pdf: 4705023 bytes, checksum: 7a0fe2d5c4f63775a5324627a3b0e8aa (MD5) license.txt: 1748 bytes, checksum: 8a4605be74aa9ea9d79846c1fba20a33 (MD5) Previous issue date: 2010 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Nos dias atuais, a busca pelo uso racional da água é um dos grandes desafios para se alcançar um desenvolvimento sustentável. O desenvolvimento de estratégias para promover o tratamento adequado da água sem gerar desperdício vem sendo um dos pontos de maior interesse na comunidade científica. Diversas alternativas vêm sendo estudadas, entre elas, a degradação de poluentes orgânicos, como corantes, por sistemas fotocatalíticos. Nestes processos, semicondutores inorgânicos (TiO2, ZnO, etc) são usados como catalisadores para promover a degradação/oxidação destes poluente, através da irradiação com luz ultravioleta. Apesar dos processos fotocatalíticos serem bem estabelecidos, o papel desempenhado pelo catalisador e a influência de suas propriedades nestes processos ainda são assuntos abertos. Neste trabalho foi investigada a influência de várias características do semicondutor (ZnO) no processo fotocatalítico. A maioria destas características estão relacionadas ao método de síntese, e o principal objetivo deste trabalho é entender melhor como eles estão conectados, visando a obtenção de partículas fotocatalíticas com alto desempenho. Assim, nanopartículas de ZnO foram inicialmente preparadas através de método de precipitação homogênea. A influência de parâmetros sintéticos como a natureza do precursor de Zn2+, a concentração e o efeito de tratamentos térmicos sobre a evolução das partículas e a atividade fotocatalítica (relacionada com a degradação do corante Rodamina-B) foi investigada. Foi observado que a cristalinidade das partículas e a presença de resíduos orgânicos são mais relevantes na atividade fotocatalítica do que parâmetros como tamanho de partícula e área de superfície, indicando que o uso de nanopartículas como estratégia para melhorar a eficiência do processo não se constitui em uma regra. Além disso, foi observado que resíduos orgânicos apresentam um efeito tipo pinning que previne a coalescência e crescimento das partículas, embora iniba a fotoatividade. Visando comprovar estas conclusões, outra série de amostras foi preparada pelo método de Pechini e o efeito de precursor de Zn2+ e o tratamento térmico também foram investigados. Ficou provado que a cristalinidade e os resíduos orgânicos desempenham um papel crucial nas propriedades fotocatalíticas e que a natureza química do precursor também é um fator determinante, bem como a rota sintética usada. Finalmente, foi investigada a possibilidade de melhorar a atividade superficial com a dopagem das partículas de ZnO com cobalto ou manganês. Estas amostras foram preparadas através de método de precipitação, empregando as condições ótimas alcançadas na primeira parte do trabalho. No entanto, não foi observada uma correlação clara entre a dopagem e eficiência fotocatalítica devido à dopagem

Please read the abstract in the front of the document. / Dissertation (MSc)--University of Pretoria, 2009. / Physics / unrestricted

Emerging transparent conducting and semiconducting oxide (TCO) and (TSO) materials have achieved success in display markets. Due to their excellent electrical performance, TSOs have been chosen to enhance the performance of traditional displays and to evaluate their application in future transparent and flexible displays. This dissertation is devoted to the study ZnO-based thin film transistors (TFTs) using multilayer dielectrics and channel layers. Using multilayers to engineer transistor parameters is a new approach. By changing the thickness, composition, and sequence of the layers, transistor performance can be optimized. In one example, Al2O3/Ta2O5 bilayer gate dielectrics, grown by atomic layer deposition at low temperature were developed. The approach combined high dielectric constant of Ta2O5 and the excellent interface quality of Al2O3/ZnO, resulting in enhanced device performance. Using zinc oxide (ZnO)/hafnium oxide (HfO2) multilayer stack as a TFT channel with tunable layer thicknesses resulted in significant improvement in TFT stability. Atomic layer deposited SnO2 was developed as a gate electrode to replace ITO in thin film transistors and circuits. The SnO2 films deposited at 200 °C show low electrical resistivity of ~3.1×10-3 Ohm-cm with the high transparency of ~93%. TFT fabricated with SnO2 gate show excellent transistor properties. Using results from the above experiments, we have developed a novel process in which thin film transistors (TFTs) are fabricated using one binary oxide for all transistor layers (gate, source/drain, semiconductor channel, and dielectric). In our new process, by simply changing the flow ratio of two chemical precursors, C8H24HfN4 and (C2H5)2Zn, in an ALD system, the electronic properties of the binary oxide HZO were controlled from conducting, to semiconducting, to insulating. A complete study of HZO thin films deposited by (ALD) was performed. The use of the multi-layer (HfO2/ZnO) channel layer plays a key role in improving the bias stability of the devices. The low processing temperature of all materials at 160 °C is an advantage for the fabrication of fully transparent and flexible devices. After precise device engineering, including growth temperature, gate dielectric, electrodes (S/D&G) and semiconductor thickness, TFT with excellent device performance are obtained.

The main objective of the research was the fabrication and characterization of MOS/MIS capacitors with ZnO as the insulating layer. Comparison with the already well known behavior of MOS/MIS capacitors with SiO2 as insulator was used to facilitate determination of the ZnO characteristics. Moreover, thermal annealing of the samples led to increased understanding of the role of defects on the dielectric properties of the ZnO layers in the MOS/MIS devices. Hall-effect transport measurements and x-ray diffraction (XRD) spectroscopy are used to analyze the structure and electronic surface characteristics of the ZnO insulator. Capacitance-voltage (C-V) measurements are used to understand the effect of surface interface charges and fixed oxide charges in the MOS/MIS (metal-oxide (insulator)-semiconductor) capacitor. The results of the Hall-effect measurement will reveal several things; the sheet resistance, carrier concentration, and mobility as well as confirm the type of silicon used. The optical spectrophotometry measurement confirmed the band gap of 3.2 eV for ZnO. The x-ray diffraction data confirmed a (002) orientation polycrystalline wurtzite ZnO structure. Initial capacitance-voltage measurement of SiO2 and ZnO revealed that the capacitance was larger for SiO2 than for ZnO. This study also explores the impact of thermal annealing on the performance of the ZnO capacitors. Hall-effect measurements are used to evaluate the influence of thermal annealing on the resistivity, carrier concentration and mobility as a function of annealing temperature. ZnO is an n-type semiconductor; this n-type conductivity is due to deviations from the stoichiometry as a result of oxygen vacancies and interstitial zinc. After ZnO samples were annealed at different temperatures, the Hall-effect measurements were performed. After thermal annealing, the mobility increased significantly by two orders of magnitude, but both the carrier concentration and the sheet density decreased. A threshold voltage (turn-on) of -1V was observed for the ZnO sample annealed at 980oC. ZnO is very versatile material with the potential for use in field effect transistors, solar cells, sensors, surface acoustic wave devices and photodiodes due to the high conductivity and high transmittance in the visible part of the spectrum. ZnO as an insulator works through analytical solutions, but not necessarily through this investigation. The difference in oxide thickness during rf magentron sputtering change the capacitance for ZnO making it lower. For n-type substrates it appears that the capacitance after annealing was higher than the capacitance before annealing. After annealing, a stretched out capacitance-voltage curve indicates the presence of trapped oxide charges and an unsmoothed surface. A high resistivity material could be used for some devices. However, typically low resistivity materials are used. After ZnO samples were annealed (unetched) at different temperatures, the Hall-effect were performed and the mobility increased significantly by two orders of magnitude, but the sheet density decreased along with the carrier concentration. The only sample that appears to come to a high frequency C-V in equilibrium is the ZnO sample annealed at 980oC. The depletion region was distinguishable and the transition point (threshold voltage) was found to be at -1 V.

No description available.

No description available.