The goals of this thesis were to synthesize nanocrystalline Zn, to study the mechanical properties of bulk nanocrystalline Zn and try to reveal the deformation mechanisms in nanocrystalline materials. Nanocrystalline Zn powder has been synthesized by a cryomilling method. The average grain size decreased exponentially with the cryomilling time and reached a minimum average grain size of around 17nm. Large numbers of small grains (2~6nm) have been found in the very early stages of cryomilling. Dynamic recrystallization (DRX) was used to explain the observed phenomena. Differential scanning calorimetry (DSC), x-ray diffraction and transmission electron microscopy (TEM) were used to study the structural changes and grain size distribution with milling time and subsequent annealing. Maxima in both stored enthalpy (for the low temperature DSC peak) and lattice strain on the Zn basal planes were observed at the same milling time. Dislocation density on the basal planes is proposed as a major source for lattice strain and the measured stored enthalpy. The released enthalpy that might be due to grain growth is very small. These cryomilled nanocrystalline Zn powders were consolidated into disks with a density of nearly theoretical density by uniaxial compression at room temperature. Cyclic variation of microhardness with milling time has been observed in cryomilled nanocrystalline Zn. Evidence from transmission electron microscopy (TEM) and high resolution transmission electron microscopy (HRTEM) suggests that the variation of dislocation density and grain size distributions determine the hardness behavior. A model, based on a kinetic reaction-rate model for cyclic amorphous-to-crystalline phase transformations observed during ball milling, simulates the experimental results very well. The model confirms the effect of DRX on modulated cyclic variation of microhardness. Dislocation strain hardening and recrystallization effects are superposed linearly with the intrinsic grain.

This book is a printed edition of the Special Issue "Zinc Oxide Nanostructures: Synthesis and Characterization" that was published in Materials

This dissertation, "Synthesis and Characterization of Nanostructured Metallic Zinc and Zinc Oxide" by Amol, Muley, was obtained from The University of Hong Kong (Pokfulam, Hong Kong) and is being sold pursuant to Creative Commons: Attribution 3.0 Hong Kong License. The content of this dissertation has not been altered in any way. We have altered the formatting in order to facilitate the ease of printing and reading of the dissertation. All rights not granted by the above license are retained by the author. Abstract: Abstract of thesis entitled Synthesis and characterization of nanostructured metallic Zinc and Zinc oxide submitted by Amol Muley B.Eng (VNIT, Nagpur) for the degree of Master of Philosophy at The University of Hong Kong in June 2007 In 1965, Gordan Moore predicted the future of integrated circuits technology when he stated that every two years the number of transistors per square inch on integrated circuits would double. This prediction has become a reality, but sustaining this exponential size decrease is a big challenge for the future of IC technology, requiring extensive research into new materials and new processes in order to advance in nanoscale IC technology. In the last few years research has been conducted to fabricate technologically useful nanostructured semi-conducting materials like silicon, gallium arsenide, gallium nitride and zinc oxide. ZnO has been recognized as a promising material, with potential applications in fields such as optoelectronics, laser diodes and field effect transistors. In this study two different approaches, top-down (AFM oxidation lithography) and bottom-up (thermal evaporation) were used to synthesize nanostructured ZnO. The first part of the study demonstrates the local oxidation of metallic zinc induced by a conducting atomic force microscopy (AFM) tip. The effect of factors such as bias voltage, pulse duration and scan speed on the oxidation rate were examined. The oxide growth rate was found to increase linearly with the logarithm of the bias voltage at a constant pulse duration, and to decrease with the oxide height at a constant bias voltage. Increasing the scan speed has the same effect as reducing the pulse duration. The oxidation rate was also found to rise with the relative humidity at a constant temperature, and to drop with temperature at constant far-field humidity. The drop of the oxidation rate with temperature is thought to be due to the localized evaporation of the moisture content from the sample-tip gap region at elevated temperatures. Another potential application of ZnO, the Schottky diode, is also demonstrated. The second part of the study deals with the fabrication of highly facetted, hexagonal-shaped metallic Zn nanocrystals. These nanocrystals were synthesized by a simple catalyst-free thermal evaporation technique on a Si (001) substrate using Zn pellets as the source material. The Zn nanocrystals were characterized by scanning electron microscopy, X-ray diffraction, transmission electron microscopy and energy dispersive X-ray spectroscopy. The nanocrystals of a size range 100-200 nm were {10 10} found to be highly facetted along {0001} and planes. The possibility of the presence of a thin ZnO layer on the surface of the as-deposited Zn nanocrystals was revealed by SAD analyses. This was further confirmed by exposing the Zn nanocrystals to air, which led to the formation of an epitaxial Zn-ZnO core-shell having a similar crystallographic orientation. (414 words) DOI: 10.5353/th_b3910153 Subjects: Zinc oxide Nanocrystals Nanostructured materials - Design and construction