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The dramatic expansion of the electronics industry over the past 40 years has been based on the progressive reduction in size of the silicon-based semiconductor components of integrated circuits. The miniaturisation of semi-conductor circuits cannot, however, continue indefinitely, and we are rapidly approaching the stage where quantum effects will prevent further dramatic improvements in computer performance using existing technology. As a result, the field of molecular electronics, which seeks to identify and develop much smaller molecular analogues of the transistors that make up integrated circuits, has expanded rapidly over the past few years. Recent studies suggested that extended metal atom chains (EMAC) may have many potential applications in molecular electronics, but it is clear that this potential can only be realised if we establish a link between the fundamental electronic properties of these systems and the transport of electrons. For this reason the ultimate goal of this thesis is to relate the electronic structure of extended metal chains to their electron transport properties. We address the problem using non-equilibrium Green’s function, in conjugation with density functional theory. In the results sections of this thesis we present calculations on tricobalt, trichromium and trinickel chains. Our data suggested that in the trimetal chains, the dominant electron transport channel is the σ manifold, while the π systems establish the contact with the electrodes. The implication of this is that even when the highly polarized π channels are strongly rehybridised by the applied electric field, current flow is not affected. In the trichromium systems we find that the distortion of the chain away from the symmetric equilibrium structure does not perturb the current flow but rather enhances it. Our rather counter intuitive conclusion is therefore that ‘broken wires’ (highly unsymmetric) are more efficient conductors than their symmetric counterparts. We have performed calculation on longer penta- and heptacobalt structures chains to establish the extent to which longer structures attenuate the conductance. Our calculations show significant oscillations of the conductance due to development of a one-dimensional band structure about the Fermi level. The evolution of the electron transport properties in cobalt chains with different length is a complex one, but it is clear that narrowing the band gap in longer chains makes it increasingly likely that the Fermi level will be in resonance with one or more of the orbitals of the extended metal atom chain.

A state-of-the-art gas electron diffraction (GED) apparatus has been reassembled in the school of chemistry at the University of Edinburgh. This combines molecularbeam and telefocus-electron-gun technologies and the alignment of the electron beam produced by the latter has been discussed. A new custom-made CCD detector has also been installed and electron diffraction patterns for a few small molecules have been recorded. In analogy to the rotating sector in a conventional GED apparatus, the new camera contains an optical filter and a procedure for its calibration is outlined and followed step by step to produce an estimate of the filter transmittance. The data have been shown to be of less than ideal quality and the probable root of the problem is discussed. GED refinements of two pairs of compounds (arachno-6,9-decaboranes, and a covalent sulfonate and thiosulfonate) are presented, using data collected with the conventional Edinburgh GED apparatus.

International Telemetering Conference Proceedings / October 26-29, 1992 / Town and Country Hotel and Convention Center, San Diego, California / The ionosphere is a critical link in the earth's environment for space-based navigation, communications and surveillance systems. Signals sent down by the GPS satellites can provide an excellent means of studying the complex physical and chemical processes that take place there. GPS uses two frequencies to ascertain signal delays passing through the ionosphere. These are measured as errors and used to correct position solutions. Since this process is a means of measuring columns of Total Electron Content (TEC), multiple top-soundings from the GPS constellation could provide significant detail of the ionospheric pattern and possibly lead to enhancement of predictions for selectable areas and sites. This paper addresses transforming the GPS propagation delays (errors) into TEC and providing TEC contours on a PC-style workstation in real and integrated time and discusses a worldwide ionospheric network monitoring system.

Random Access Memory (RRAM) has emerged as a leading candidate for nonvolatile memory storage. RRAM devices typically consist of a metal/insulator/metal (MIM) structure and exhibit switching of the device resistivity state (low-to-high, highto- low) by application of electrical bias. It is now widely accepted that shunting and rupturing of local conductive paths (filaments) directly determines the resistance state. The size and composition of these filaments are very much an open question, but are usually attributed to high local concentrations of oxygen vacancies. Although there has been a huge body of research conducted in this field, the fundamental nature of the conductive path and basic switching/failure mechanisms are still under debate. This is largely due to a lack of structural analysis of existing filament size and composition in actual devices. Since the non-volatile nature and device reliability issues (i.e. retention and endurance) are directly related to the irreversible structural transformations in the device, microstructural characterization is essential for eventual commercialization of RRAM. In this study, I investigated oxygen vacancy defect dynamics under electric filed essential for resistive switching and aim to identify size, location, and chemical nature of the conductive filaments in RRAM devices by using a variety of devices and materials characterization methods: in situ transmission electron microscopy (TEM), highresolution TEM (HRTEM), scanning TEM (STEM)-electron energy loss spectroscopy (EELS), electron holography, rapid thermal annealing (RTA), transient thermometry, and electro-thermal simulation. I adopt an in situ electrical biasing TEM technique to study microstructural changes occurring during resistive switching using a model TiO2-based RRAM device, and confirmed the device is switchable inside of the TEM column. I observed extension and contraction of {011} and {121}-type Wadsley defects, crystallographic shear faults, associated with resistive switching. More specifically, emission and adsorption of oxygen vacancies under different polarity of electrical biases at the fault bounding dislocations were identified. The motion of Wadsley defects was used to track oxygen vacancy migration under electric field. Also, the microstructural changes that occur when the device experiences low electric field (~104 V/cm) was reported, akin to read disturb. Crossbar type RRAM device stacks consisting of TiN/a-HfAlOx/Hf/TiN were investigated to estimate filament size, filament temperature, and its chemical footprint using HRTEM, transient thermometry and numerical simulation. In each of the switched devices, a single crystallite ~ 8-16 nm in size embedded in an amorphous HfAlOx matrix was found. The HfAlOx crystallization temperature (Tc) of 850 K was determined by combining RTA and HRTEM imaging. In parallel, the filament size has been determined by transient thermometry. The temperature profile extracted from these measurements suggested that the peak filament temperature was > 1500 K at the center, with the hot zone (T > Tc = 850 K) extending to a radius of 7 nm around the filament. These results were consistent with the HRTEM observations of the crystallite size. The potential filament location (crystallite) in the switching devices was analyzed by STEM-EELS and identification of the filament chemical nature identification has been attempted.