Thesis (M.E.E.)--University of Delaware, 2006. / Principal faculty advisors: Olufemi Olowolafe, Dept. of Electrical and Computer Engineering and Robert L. Opila, Dept. of Materials Science. Includes bibliographical references.

Thesis (M. Phil.)--University of Hong Kong, 2006. / Title proper from title frame. Also available in printed format.

Thesis (Ph. D.)--Materials Science and Engineering, Georgia Institute of Technology, 2008. / Peter J. Hesketh, Committee Member ; Zhong Lin Wang, Committee Chair ; C.P. Wong, Committee Member ; Robert L. Snyder, Committee Member ; Christopher Summers, Committee Member.

In this dissertation, Zinc oxide (ZnO) nanorods grown by a two-step chemical bath deposition method on Si substrate is characterized. Research was conducted on ZnO nanorods for the understanding of their optical properties at room temperature (RT), with the emphasis on the visible luminescence. To this end, controlled thermal treatments of as-grown ZnO nanorods were conducted under different conditions, such as annealing time and environment, at atmospheric pressure. Results related to the following studies are reported: an investigation of the structure of ZnO nanorods, an analysis of the chemical composition of the surface, an investigation of the surface stoichiometry of the rods, and a study of defect-related photoluminescence of ZnO nanorods upon thermal treatment in different ambients.To achieve this, the samples were investigated by Scanning Electron Microscopy (SEM), X-ray Diffraction (XRD), Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS), X-ray Photoelectron Spectroscopy (XPS), Auger Electron Spectroscopy (AES) and room temperature (RT) photoluminescence Spectroscopy (PL). As-grown ZnO nanorods exhibit a hexagonal shape and have the wurtzite structure; they have, respectively, an average length and diameter of ~900 nm and ~50 nm, and most of the rods are perpendicular to the substrate. The main extrinsic species found in as-grown nanostructures are C, H, F, S, and Cl. ToF-SIMS and XPS confirmed the presence of H related-defects, and the oxygen 1 S XPS peak at 531.5 eV is therefore assigned to oxygen bound to H-related defects. Based on stoichiometry studies, it is found that the near surface regions of as-grown ZnO nanorods (2 to 10 monolayers) are rich in Zn. The RT luminescence of as-grown ZnO nanorods exhibits a near band edge emission centered at ~379.5 nm and deep level emission extending from ~450 nm to ~850 nm. When these nanorods are thermally treated at high temperatures (>850 oC), it is found that even though their crystalline quality is preserved, their morphology is significantly affected, regardless of annealing ambient. Furthermore, in the near surface regions of annealed ZnO nanorods it is found that the Zn/O stoichiometric ratios deviate from unity. Specifically, oxygen vacancies form within the first 100 nm from the sample surface. Further from the surface, the material is deficient in Zn. It is deduced from XPS and AES that the ambient affects the activation rate of intrinsic defects. Furthermore, the only extrinsic defects that are affected by thermal treatment are found to be H-related defects. At high annealing temperatures (300 oC to ~700 oC), H-related defects are removed, and this removal process is found to affect significantly the RT luminescence properties of ZnO nanorods. Specifically, hydrogen passivates vacancy-related defects, depending on the thermal treatment. PL spectroscopy is used to follow this passivation effect as a function of annealing temperature, which causes an initial quenching followed by an enhancement of the green and the red luminescence, regardless of the ambient. Finally, the green luminescence that arises following annealing above ~800 oC is assigned to Zn vacancy-related defects, while the red luminescence that dominates the visible band of ZnO nanorods upon annealing between 400 oC and 600 oC is suggested to be due to oxygen vacancy-related defects.

MgxZn1-xO has emerged as a material of great technological importance. Having a direct energy band gap that is tunable throughout much of the ultraviolet (UV) region of the spectrum from the near-UV (~370 nm) to the deep-UV (~176 nm), this compound is of interest for a variety of optoelectronic devices operating in this part of the electromagnetic spectrum. MgxZn1-xO offers advantages over the more mature compound semiconductor AlGaN which stem mainly from the unusually high exciton binding energy (60 meV in ZnO). In this study the growth of ZnO and MgxZn1-xO thin films using metal organic chemical vapour deposition (MOCVD) is systematically investigated. The films are mainly grown on c-Al2O3 and Si (100) and characterized using various techniques, such as photoluminescence (PL), x-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and auger electron spectroscopy (AES). The optical and the structural properties are essentially inspected in order to improve their quality. In this thesis the optimisation of ZnO grown using oxygen gas as a new oxidant in our reactor is investigated. The growth temperature and VI/II ratio are varied in order to find optimum parameters giving high quality layers. The effects of Si (100), Si (111), c- and r-sapphire, glass, GaAs and ZnO substrates on the optical, structural and morphological properties of ZnO thin films grown with tert-butanol (TBOH) is examined. Similar morphologies are observed for all substrates, with the films comprising hexagonal columns having cone shaped ends. The photoluminescence spectra are similar, but the various transitions have different relative intensities. It is clear that the different substrates influence neither the orientation of the films, nor the surface morphology, significantly. The photoluminescence hints at larger stacking fault densities in films grown on silicon and glass, however, as evidenced by stronger basal plane stacking fault-related luminescence at ~3.319 eV in the relevant low temperature photoluminescence spectra. The morphology changes with Mg incorporation, from hexagonal columnar structures to cubic faceted columns. From PL, the full with at half maximum is found to gradually increase with Mg content due to alloy broadening. The deep level emission (DLE) is observed to shift with Mg content. By changing the Mg content, the band gap of MgxZn1-xO film is tuned by ~450 meV, which provides an excellent opportunity for band gap engineering for optoelectronic applications. The c-lattice constant of ZnO (5.205 Å) decreases by only 0.6% when the Mg content reaches x=0.39. The introduction of Mg into ZnO is shown to increase the relative PL intensity of stacking fault-related transitions (at 3.314 eV for ZnO). This becomes the dominant near band edge emission. Using TEM a thin Mg rich layer is observed at the interface between the film and the Si or Al2O3. Temperature dependent PL measurements on layers with low Mg concentration (x=0.05 and 0.1) show that the main bound exciton peak exhibits an “s-shaped” temperature dependence, characteristic of localization in a disordered alloy. The origin of the PL line broadening of MgxZn1-xO (x≤0.04) is also analyzed with respect to alloy broadening, taking into account a random cation distribution and alloy clustering. The influence of various MOCVD growth parameters such as growth temperature and VI/II ratio is studied. Varying the temperature from 280 ˚C to 580 ˚C reveals strong morphological changes and optical degradation of the films. Low (<280 ˚C) and high (>580 ˚C) growth temperatures reduce the Mg incorporation. High VI/II ratios also decrease the Mg incorporation, as evidenced by the red-shift of the donor bound exciton (D°X) line. This is ascribed to a stronger premature reaction between (MeCp)2Mg and the oxidant or a preferential heterogeneous interaction between the Mg and oxygen species on the growth front. For both oxidizing agents (O2 and TBOH), the growth at 420 ˚C and a VI-II ratio of 60 on c-Al2O3 gave optimal quality layers in terms of their optical and structural quality. A comparison of films grown using TBOH and O2 gas as oxidizing agent shows no major difference in terms of Mg incorporation. The effect of annealing, the inclusion of a buffer layer and the influence of growth rate on the properties MgxZn1-xO thin films are also reported.

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