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Zn(_x)Co(_2-x)GeO(_4) materials were prepared and the variation in structure with composition was investigated using XED, SEM and EDX analysis. Limited series of solid solution were identified at both ends of the compositional range. D C electrical measurements were carried out to characterize the variation in the resistivity of the materials with humidity. Resistivities of the order of 10(^8) Ω m were observed in dry conditions, decreasing by 4 to 5 orders of magnitude with increasing humidity. Resistivity was not found to vary greatly with composition. Resistivity was temperature dependent, increasing by 1 to 2 orders of magnitude for a 70 C decrease in temperature. A C impedance measurements were performed to gain an understanding of the mechanism of the humidity dependent conductivity. At low frequencies impedance was found to be independent of frequency and humidity dependent. At high frequencies impedance was found to be inversely proportional to frequency and independent of humidity. The break point frequency was also humidity dependent and an increase in the impedance indicated inductive-type behaviour. Complex plane representation of the impedance gave a distorted semicircle at high frequencies and a low frequency tail. At high humidities the tail appears as a straight line, inclined at approximately 45 . At medium levels of humidity a distinctive loop is apparent at the intersection between the semicircle and the tail, corresponding to the inductive behaviour indicated at the break point frequency. The impedance response was modelled by an equivalent circuit consisting of various ideal and constant phase (dispersive) elements. The proposed mechanism of humidity-dependent conductivity is due to chemisorption and physisorption of water vapour from the atmosphere at the surface of the material, It is suggested that conduction occurs by hopping of protons between cheraisorbed hydroxyl groups at low humidities, by diffusion of H(_3)O(^+) ions between the hydroxyl groups at intermediate humidities and by hopping of protons between physisorbed H(_3)O(^+) ions (Grotthus Chain reaction) at high humidities.

This thesis addresses the issue of a potential future microelectronics technology, namely the possibility of utilising the optical properties of nanocrystalline silicon for optoelectronic circuits. The subject is subdivided into three chapters. Chapter 1 is an introduction. It formulates the oncoming problem for microelectronic development, explains the basics of Integrated Optoelectronics, introduces porous silicon as a new light-emitting material and gives a brief review of other competing light-emitting material systems currently under investigation. Examples of existing porous silicon devices are given. Chapter 2 reviews the basic physics relevant to the subject of this thesis and informs on the present situation in this field of research, including both experimental and theoretical knowledge gained up-to-date. The chapter provides the necessary background for correct interpretation of the results reported in Chapter 3 and for a realistic decision on the direction for future work. Chapter 3 describes my own experimental and computational results within the framework of the subject, obtained at De Montfort University. These include: onestep preparation of laterally structured porous silicon with photoluminescence and microscopy characterisation, Raman spectroscopy of porous silicon, a polarisation study of the photoluminescence from porous silicon, computer simulations of the conductivity of two-component media and of laser focused atomic deposition for nanostructure fabrication. Thus, this thesis makes a dual contribution to the chosen field: it summarises the present knowledge on the possibility of utilising optical properties of nanocrystalline silicon in silicon-based electronics, and it reports new results within the framework of the subject. The main conclusion is that due to its promising optoelectronic properties nanocrystalline silicon remains a prospective competitor for the cheapest and fastest microelectronics of the next century.

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This thesis concerns the formation, sintering and humidity dependent electrical behaviour of the spinel ceramic material nickel germanate, Ni(_2)Ge0(_4).Ni(_2)Ge0(_4) has been prepared via the solid state reaction between NiO and GeO(_2) over a range of temperatures, and characterised using a number of techniques. The sintering behaviour of pressed pellets of Ni(_2)Ge0(_4) has also been investigated, together with a characterisation of the microstructure of the sintered bodies. Substitutional doping of Ni(_2)GeO(_4) with Li as a replacement for Ni is found to promote a high degree of shrinkage in the sintering process, probably due to the formation of a liquid phase. XRD revealed that even when 10 % of the Ni atoms were replaced with Li, no change in the crystal structure could be detected. A C. impedance spectroscopy of Ni(_2)Ge0(_4) samples was used to investigate the humidity sensitivity of this material. Equivalent circuit analysis, based on a network of resistors and constant phase elements, shows that the humidity sensitivity is due to conduction in a surface layer of water, in agreement with the models currently popular in the Uterature. Measurement of the water adsorption isotherm of Ni(_2)Ge0(_4) in pellet form indicates that a single monolayer of water is formed at around 20 %R(_H), with an approximately linear increase in water layer thickness up to around 80 %R(_H), after which capillary condensation causes a large increase in the volume of adsorbed water. The information gained on the thickness of this layer of water has been correlated with the resistance of the layer measured by impedance spectroscopy, and subsequently used to provide evidence for a model of the humidity sensitive conduction. The conduction in the surface layer is thought to be due to dissociation of the water, where the amount of dissociation is exponentially dependent on the humidity.