Zinc oxide (ZnO), as a Ⅱ-Ⅵ compound semiconductor with a wide direct band gap, has attracted great attention from the worldwide researchers for its potential application in the fields of spintronics and optoelectronics. At present research about the defects in ZnO and ZnO-based materials is still far from complete. The deep level defects in melted grown ZnO single crystal induced by helium ions implantation and electron irradiation, as well as their thermal evolution, were studied in this research using the technique of deep level transient spectroscopy (DLTS) and photoluminescence (PL). DLTS results indicated that, besides E3 (????~0.28 ????) trap which was widely observed in the as-grown ZnO samples, the deep level with ????~0.92 ???? was also indentified in the helium-implanted ZnO samples, which was introduced by the ion implantation and tentatively assigned to be the oxygen vacancy (VO). This deep level was removed after 350 oC annealing in argon gas. Annealing at 350 oC also brought along a new deep level with ????~0.66???? into helium-implanted samples which could be annealed out by 650 oC annealing in argon gas. The electron irradiation induced a deep level with ????~0.59 ???? into ZnO, which was probably associated with the singly charged state of VO. This deep level also tended to be removed at 350 oC annealing in argon gas. The PL spectra revealed that both helium implantation and electron irradiation could improve the bound-exciton peak. Helium implantation also introduced defects emission at 1.90 eV , which was the red luminescence band, into the ZnO single crystal materials. This red luminescence band peak might be associated with DAP recombination. Electron irradiation might restrain the green luminescence in ZnO single crystal. The fine structures could disappear as the measurement temperature increased, leaving the green luminescence band only. / published_or_final_version / Physics / Doctoral / Doctor of Philosophy

Zinc oxide surfaces have been of considerable interest because of their favorable properties, such as high electron mobility, good transparency, large electronic breakdown field and wide bandgap. Knowing the surface structure of ZnO is the key to better understand the above phenomena and to further develop its applications. In this thesis, the Patterson Function was evaluated by inversion of LEED I-V spectra at multiple incident angles to determine the surface structure of the ZnO(0001) polar surface. The sample was prepared by degassing and then 15 cycles of argon sputtering and annealing. The experimental LEED I-V spectra from multiple incident angles were taken from the sample. After processing the data by a macro program in OPTIMAS and a Matlab program, a clean Patterson Function map showing the inter-atomic pair distances was obtained. It was then compared with the simulated Patterson Function map of the proposed 1×1 bare surface model. As a result, the spots positions in the simulated Patterson Function map matched well with that of the experimental Patterson Function map. On the other hand, the LEED I-V curve fitting work was done by the surface science group of City University of Hong Kong. Six models were proposed by them and normal incidence theoretical LEED I-V spectra were calculated to fit with the experimental LEED I-V curves provided by us. Among the six models 2×2 Zn point defect model was fitted to be the best model with the R-factor 0.244. We also compared the multiple scattering simulated Patterson Function map of 2×2 Zn point defect model with the experimental one to verify the validity of the model. As a result, the model fit the experimental data. So we conclude that in general 1×1 model support the order part, and 2×2 top layer Zn defect model best fits the random missing part. / published_or_final_version / Physics / Master / Master of Philosophy

The observation of ferromagnetism of (Ga,Mn)As by Ohno in 1998 has inspired great interest in diluted magnetic semiconductors (DMS). DMS’s features combining ferromagnetism and semiconducting make them of great potential for conceptual spintronic devices, which is a promising field of research for the emerging electronics. The practical application of DMS requires a Curie temperature well above room temperature and an intrinsic ferromagnetism. There are several types of DMS materials. The typical ones are transition-metal (TM) doped GaAs, GaN and ZnO. The TM-doped ZnO has drawn particular attention due to the observation of room temperature ferromagnetism in this system including cobalt-doped ZnO.But the origin of ferromagnetic TM-doped ZnO is still unknown after a decade’s theoretical and experimental effort on this material. In this thesis, we do the magnetic circular dichroism(MCD) and Hall measurement of high quality Cobalt-doped ZnO thin films grown by molecular beam epitaxy (MBE). Room temperature ferromagnetism is observed in these samples. Combining the data from MCD and Hall measurement, we attribute the room temperature ferromagnetism in this system to the impurity band of the doped Cobalt cations. / published_or_final_version / Physics / Master / Master of Philosophy

Understanding the relationship between the structure of materials and their properties allows for the development of new applications and technologies. Here the relationship between local structure and optical properties in several binary oxide glass systems containing zinc oxide was examined, in particular the relationship between structure, applied stress and induced birefringence in a glass. The empirical model introduced by Zwanziger and co-workers posits a negative correlation between the ratio of the bond length to coordination number in a glass and the induced birefringence; zinc oxide in this model is predicted to be exactly at the threshold between positive and negative birefringence and is thus of particular interest to investigate. XAFS and Raman spectroscopy were used to determine local structure while the Sénarmont compensator method, Abbe refractometry and spectroscopic ellipsometry were used to measure optical properties.

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The optical properties of zinc oxide crystals and thin films prepared by different methods are investigated. Single crystal zinc oxide samples prepared by melt and hydrothermal growth techniques were obtained. The influence of polarity and growth method on the optical properties were studied and correlated with their electronic properties. Thin films prepared by molecular beam epitaxy (MBE) and sputtering were studied and the influence of growth conditions and post growth treatment on the optical properties of the films was investigated. The photo-luminescence (PL) of bulk zinc oxide was examined at high resolution. Line widths of less than 0.1 meV were observed. More than a dozen different transitions in the near band edge region (NBE 360-380 nm) were noted, several of which displayed a separation of <0.5 meV which goes some way to illustrating the complexity of the system. Attempts were made, with some success, to reconcile the two main competing identification systems of the NBE transitions and explanations for some of the discrepancies are provided. The controversial deep level transitions in the visible part of the spectrum are fit with 3 Gaussians and their identities discussed with relation to the available literature. The presence of copper impurities was detected in annealed films and a model to explain their behaviour under annealing conditions is hypothesised. Films grown by MBE here at the University of Canterbury are shown to have PL line widths of as little as 2.2 meV, the ratio of active oxygen species in the growth chamber during deposition is shown to effect the optical quality of the films. It is shown that annealing can improve the optical quality of the films and various other methods of influencing the films properties are discussed. Reactive, magnetron, direct current sputtering is shown to be the optimal method of growth for maximising both optical and piezo-electric properties. Optimum annealing temperatures were found at 900 and 1100 ℃ with a local minimum at 1000 ℃. X-ray diffraction, atomic force and scanning electron microscopy measurements in addition to optical PL measurements show the influence of annealing on the polycrystalline sputtered ZnO films. Films grown on glass, silicon, sapphire and quartz were shown to display similar behaviour under annealing conditions. It was found that zinc oxide based devices were liable to be chemically unstable at temperatures above 1100 ℃. The piezo electric properties of the films were examined and attempts were made to prepare a zinc oxide film optimised for both optical quality and piezoelectric properties for possible future applications of a hybrid opto-mechanical coupled devices.

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

The subject of this thesis is microwave assisted rapid growth of ZnO nanoparticles from an aqueous solution using different zinc precursors and heating powers, and characterization of these by scanning electron microscopy, atomic force microscopy and optical microscopy. The goal of the experiment performed was to study the effect of the heating power of the microwave oven as well as that of the zinc precursor used on the morphology and size of the grown particles. ZnO nanoparticles has many interesting possible applications in a wide range of areas, such as LED-technology, medicine, antibacterial applications, solar cells and more. Also, there is still a lot of knowledge missing concerning the growth mechanisms and properties of ZnO on the nano-scale. These two facts give good reasons to continue the research and investigations of nano-ZnO. Being able to use the microwave assisted growth method in large scale is highly interesting as it is relatively cheap, safe and easy compared to other presently used methods, so there are good reasons to learn more about this technique as well. In this project it was found that both the heating power and the zinc precursor used had significant effects on the morphology and size of the grown ZnO nanocrystals, and also that adding a zinc seed layer to the surface of the substrate before growth made a big difference in some cases.

At present, one of the key challenges in the light-emitting diode (LED) packaging technology is light extraction due to the difference in index of refraction between LED chip and air. Silicone nanocomposites have been extensively researched for applications in LED encapsulant to reduce such difference in refractive index. It is well-known that silicone is desirable for LED encapsulant because of its optical transparency and photothermal resistance. However, not much has been accomplished to leverage the elastic properties of silicone for enabling a stretchable LED encapsulant. In this work, I aim to investigate the stretch ability of silicone/zinc oxide (ZnO) nanocomposites for LED packaging. Wurtzite ZnO nanoparticles were prepared in colloids and subjected to silane treatment. Effects of both ex situ and in situ silane treatment on the final mechanical and optical properties of the silicone/ZnO nanocomposites were examined. Silicone/ZnO nanocomposites exhibit significantly more compliant stress-strain behavior than silicone control. In particular, silicone/silane-treated ZnO nanocomposites show more serrated stress-strain curves. They also embrace higher transmittance than silicone/unmodified ZnO nanocomposites, indicating an improvement in the dispersion of the nanoparticles. It was found that the silicone/5% silane-treated ZnO nanocomposite prepared by an in situ method was able to deform over a range of up to 160%. The film made of this unique silicone/ZnO nanocomposite (~40 microns thick) exhibits transmittance >70% throughout the visible range.

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.