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Metal oxide thin films are dynamic materials that have revolutionised the nature of semiconductor and electronic thin film devices. Recently, progress has stagnated in some aspects due to the increasingly complex deposition apparatus required, and the dearth of suitable precursor complexes of certain ???difficult??? metals. This thesis seeks to address both of these issues. The application of a precursor complex, Mg6(O2CNEt2)12 to the SSCVD of MgO thin films delivered the highest quality films ever reported with this technique. The resultant films were found to be of purely (111) orientation. Due to the nature of the precursor, the chemical reactions occurring at the surface during SSCVD growth result in a high growth rate, low flux environment and films of (111) orientation have been achieved without the amorphous underlayer. This finding has important implications for buffer layers in perovskite thin film devices. The unprecedented precursor chemistry has been used as a basis for the extremely high quality material produced, along with the unusual, yet beneficial structural morphology it possesses. A new range of barium complexes with single encapsulating ligands have been prepared for use in chemical vapour deposition (CVD) of BaTiO3 thin films. A novel pathway to an unprecedented class of barium carbamates is reported, and also new dianionic bis ??-ketoesterates and their barium, strontium, and calcium analogues were synthesised. High resolution mass spectrometry showed the barium bis ??-ketoesterate derivatives to be monomeric, and preliminary testing indicated some volatility in these species. Insights were gained into the likely successful pathways to building a volatile heterobimetallic precursor complex containing an alkaline earth metal. The knowledge of intimate mixing in heterobimetallic precursor complexes was extended by some novel chemistry to develop the first mixed Zn/Mg carbamato cluster complexes. These complexes were found to be excellent SSCVD precursors for ZnxMg1-xO thin films. Thin films were deposited with these precursors and exhibited a single preferred orientation, with a constant amount of magnesium throughout the bulk of the films. Investigation of the light emission properties of the films revealed significant improvements in the structural order commensurate with the incorporation of magnesium, and the formation of the ZnxMg1-xO alloy.

The deformation mechanisms and contact response of TiN-based thin films deposited onto a soft substrate using a physical vapour deposition (PVD) technique is still an area of both technological importance and considerable discussion. These coatings are commonly applied to various kinds of steel cutting tools, creating surfaces with enhanced tribological properties. However, no extensive systematic study of the deformation mechanisms in these thin film systems has been performed to date. In the present study, the effect of the coating microstructure, indenter geometry, coating thickness and substrate hardness on the deformation mechanisms in both TiN and TiAlN coatings of varying thickness deposited onto ductile steel substrates has been investigated using a combination of nanoindentation and microstructural analysis, including focused ion beam (FIB) milling and transmission electron microscopy (TEM). Different modes of cracking, such as columnar and transverse cracking, as well as shear steps at the coating/substrate interface, were observed. The microstructure of the TiN coatings was found to be very important in controlling their modes of deformation. Thicker coatings were seen to contain more equiaxed grains, so less columnar shearing occurred and inclined cracks were found to be a more dominant fracture type in the thicker coating. Also, it was found that soft substrates absorbed most of the energy from indentation by plastic deformation. It was found that both the TiN and TiAlN/TiN dual-layer coatings exhibited broadly similar mechanisms of deformation. The epitaxial interface between the TiAlN and TiN in the dual-layer coating did not appear to affect the deformation behaviour. As a further investigation of the overall deformation behaviour for the coating/substrate systems studied, a DualBeam FIB was used to generate three dimensional images of the indented regions which provided additional information on the crack morphology. For the first time, a systematic study of the deformation behaviour of TiN and TiAlN coatings upon indentation has been carried out. FIB milling was demonstrated to be a highly appropriate technique for characterization of the deformation behaviour of these coatings, allowing detailed, high resolution microstructural investigations to be performed in both two and three dimensions.

Metal oxide thin films are dynamic materials that have revolutionised the nature of semiconductor and electronic thin film devices. Recently, progress has stagnated in some aspects due to the increasingly complex deposition apparatus required, and the dearth of suitable precursor complexes of certain ???difficult??? metals. This thesis seeks to address both of these issues. The application of a precursor complex, Mg6(O2CNEt2)12 to the SSCVD of MgO thin films delivered the highest quality films ever reported with this technique. The resultant films were found to be of purely (111) orientation. Due to the nature of the precursor, the chemical reactions occurring at the surface during SSCVD growth result in a high growth rate, low flux environment and films of (111) orientation have been achieved without the amorphous underlayer. This finding has important implications for buffer layers in perovskite thin film devices. The unprecedented precursor chemistry has been used as a basis for the extremely high quality material produced, along with the unusual, yet beneficial structural morphology it possesses. A new range of barium complexes with single encapsulating ligands have been prepared for use in chemical vapour deposition (CVD) of BaTiO3 thin films. A novel pathway to an unprecedented class of barium carbamates is reported, and also new dianionic bis ??-ketoesterates and their barium, strontium, and calcium analogues were synthesised. High resolution mass spectrometry showed the barium bis ??-ketoesterate derivatives to be monomeric, and preliminary testing indicated some volatility in these species. Insights were gained into the likely successful pathways to building a volatile heterobimetallic precursor complex containing an alkaline earth metal. The knowledge of intimate mixing in heterobimetallic precursor complexes was extended by some novel chemistry to develop the first mixed Zn/Mg carbamato cluster complexes. These complexes were found to be excellent SSCVD precursors for ZnxMg1-xO thin films. Thin films were deposited with these precursors and exhibited a single preferred orientation, with a constant amount of magnesium throughout the bulk of the films. Investigation of the light emission properties of the films revealed significant improvements in the structural order commensurate with the incorporation of magnesium, and the formation of the ZnxMg1-xO alloy.

Metal oxide thin films are dynamic materials that have revolutionised the nature of semiconductor and electronic thin film devices. Recently, progress has stagnated in some aspects due to the increasingly complex deposition apparatus required, and the dearth of suitable precursor complexes of certain ???difficult??? metals. This thesis seeks to address both of these issues. The application of a precursor complex, Mg6(O2CNEt2)12 to the SSCVD of MgO thin films delivered the highest quality films ever reported with this technique. The resultant films were found to be of purely (111) orientation. Due to the nature of the precursor, the chemical reactions occurring at the surface during SSCVD growth result in a high growth rate, low flux environment and films of (111) orientation have been achieved without the amorphous underlayer. This finding has important implications for buffer layers in perovskite thin film devices. The unprecedented precursor chemistry has been used as a basis for the extremely high quality material produced, along with the unusual, yet beneficial structural morphology it possesses. A new range of barium complexes with single encapsulating ligands have been prepared for use in chemical vapour deposition (CVD) of BaTiO3 thin films. A novel pathway to an unprecedented class of barium carbamates is reported, and also new dianionic bis ??-ketoesterates and their barium, strontium, and calcium analogues were synthesised. High resolution mass spectrometry showed the barium bis ??-ketoesterate derivatives to be monomeric, and preliminary testing indicated some volatility in these species. Insights were gained into the likely successful pathways to building a volatile heterobimetallic precursor complex containing an alkaline earth metal. The knowledge of intimate mixing in heterobimetallic precursor complexes was extended by some novel chemistry to develop the first mixed Zn/Mg carbamato cluster complexes. These complexes were found to be excellent SSCVD precursors for ZnxMg1-xO thin films. Thin films were deposited with these precursors and exhibited a single preferred orientation, with a constant amount of magnesium throughout the bulk of the films. Investigation of the light emission properties of the films revealed significant improvements in the structural order commensurate with the incorporation of magnesium, and the formation of the ZnxMg1-xO alloy.

A study of the effect of catalyst properties on the synthesis of carbon nanotubes (CNTs) is done in this thesis. Three different metal alloy catalysts, Fe/Ti, Ni/Ti, Co/Ti, have been studied. Various atomic concentrations and thicknesses were cosputter deposited on clean Si wafers using AJA Orion 4 RF Magnetron sputter deposition tool at 5mtorr and 17��C, and the films were characterized using a scanning electron microscope, Energy-dispersive X-ray spectroscopy. All the alloys have been annealed at 650��C and 3 torr in an argon atmosphere at 100 SCCM, followed by ammonia gas plasma etch at different powers at 3 torr and 50 SCCM NH��� flow in a modified parallel plate RF chemical vapor deposition tool for 1 minute. The influence of plasma power, thickness of catalyst and concentration of Ti the secondary metal in the alloy composition, on the surface morphology of the catalyst are investigated by characterizing them with atomic force microscopy. The study has shown that the surface roughness is affected by Ti concentration, thickness and plasma power. The 35 W power NH��� plasma produced rougher surfaces when compared to the 75 W NH��� plasma. The result is interpreted as follows: ion bombardment leads to greater etching of the catalyst surface. Thus, plasma power must be optimized for catalyst thin film and etch time. The study has provided an in depth analysis and understanding of the various factors that influence catalyst surface morphology which can be applied into further study for optimizing parameters for synthesis of single walled CNTs. Following this, a study on catalysts for CNT synthesis was performed using Plasma enhanced chemical vapor deposition and characterized by scanning electron microscope. CNTs were synthesized on Ni, Ni-Ti, Co, Co-Ti and Fe catalyst. Ni, Ni-Ti catalyst produced forest like vertically aligned CNTs whereas Co, Co-Ti produced vertically aligned free standing CNTs. The growth was dense and uniform across the substrate. Initial growth runs on Fe, Fe-Ti alloy did not produce any CNTs until catalyst was restructured with a thicker Ti under layer after an investigation using Secondary ion mass spectrometry of suspected Fe catalyst poisoning due to reaction with Si substrate. A room temperature run was carried out on annealed and plasma etched Ni catalyst and no CNTs were produced indicating the importance of substrate temperature of CNTs. A deeper understanding of factors of influence on CNTs such as catalyst types, structure/morphology, and substrate temperature has been achieved with this study. / Graduation date: 2013

This research is aimed at synthesizing millimeter-scale carbon nanotube arrays (CNTA) by conventional chemical vapor deposition (CCVD) and water-assisted chemical vapor deposition (WACVD) methods, and exploring their application as catalyst supports for electrochemical supercapacitors. The growth mechanism and growth kinetics of CNTA under different conditions were systematically investigated to understand the relationship among physical characteristics of catalyst particles, growth parameters, and carbon nanotube (CNT) structures within CNTAs. Multiwalled CNT (MWCNT) array growth demonstrates lengthening and thickening stages in CCVD and WACVD. In CCVD, the lengthening and thickening were found to be competitive. By investigating catalyst particles after different pretreatment conditions, it has been found that inter-particle spacing plays a significant role in influencing CNTA height, CNT diameter and wall number. In WACVD, a long linear lengthening stage has been found. CNT wall number remains constant and catalysts preserve the activity in this stage, while MWCNTs thicken substantially and catalysts deactivate following the previously proposed radioactive decay model in the thickening stage of WACVD. Water was also shown to preserve the catalyst activity by significantly inhibiting catalyst-induced and gas phase-induced thickening processes in WACVD. Mn3O4 nanoparticles were successfully deposited and uniformly distributed within millimeter-long CNTAs by dip-casting method from non-aqueous solutions. After modification with Mn3O4 nanoparticles, CNTAs have been changed from hydrophobic to hydrophilic without their alignment and integrity being destroyed. The hydrophilic Mn3O4/CNTA composite electrodes present ideal capacitive behavior with high reversibility. This opens up a new route of utilizing ultra-long CNTAs, based on which a scalable and cost-effective method was developed to fabricate composite electrodes using millimeter-long CNTAs. To improve the performance of the composites, -MnO2 nanorods were anodically pulse-electrodeposited within hydrophilic 0.5 mm-thick Mn3O4 decorated CNTAs. The maximum gravimetric capacitance for the MnO2 nanorods/CNTA composite electrode was found to be 185 F/g, and that for -MnO2 nanorods was determined to be 221 F/g. After electrodeposition, the area-normalized capacitance and volumetric capacitance values were increased by a factor of 3, and an extremely high area-normalized capacitance of 1.80 F/cm2 was also achieved for the MnO2 nanorods/CNTA composite. / Materials Engineering

Over the course of the past several decades the benefits of redeveloping brownfields have been widely recognized. Actions have been taken to foster sustainable redevelopment of brownfields by government, policy makers and stakeholders across the world. However, redevelopments encounter great challenges and risks related to environmental and non-environmental issues. In this work, we intend to build a comprehensive and practical framework to evaluate the hydrogeological and financial risks involved during redevelopment and to ensure developers reserve sufficient capital to cover unexpected future costs within the guarantee period. Punitive damages, which contribute to these costs, are in this thesis solely associated with the cost of repossessing a house within a development should the indoor air concentration of TCE exceed the regulatory limit at a later time. The uncertainties associated with brownfield remediation have been among the barriers to brownfield redevelopment. This is mainly caused by the lack of knowledge about a site’s environmental condition. In order to alleviate uncertainties and to better understand the contaminant transport process in the subsurface, numerical simulations have been conducted to investigate the role of controlling parameters in determining the fate and transport of volatile organic compounds originating from a NAPL source zone located below the water table in the subsurface. In the first part of this thesis, the numerical model CompFlow Bio is used on a hypothesized three-dimensional problem geometry where multiple residential dwellings are built. The simulations indicate that uncertainty in the simulated indoor air concentration is sensitive to heterogeneity in the permeability structure of a stratigraphically continuous aquifer with uncertainty defined as the probability of exceeding a regulatory limit. Houses which are laterally offset from the groundwater plume are less affected by vapour intrusion due to limited transverse horizontal flux of TCE within the groundwater plume in agreement with the ASTM (2008) guidance. Within this uncertainty framework, we show that the Johnson and Ettinger (1991) model generates overly-conservative results and contributes to the exclusion zone being much further away from the groundwater plume relative to either CompFlow Bio or ASTM (2008). The probability of failure (or the probability of exceedence of the regulatory limit) is defined and calculated for further study. Due to uncertainties resulting from parameter estimation and model prediction, a methodology is introduced to incorporate field measurements into the initial estimates from the numerical model in order to improve prediction accuracy. The principle idea of this methodology is to combine the geostatistical tool kriging with the statistical data assimilation method Kalman filter to evaluate the worth and effectiveness of data in a quantitative way in order to select an optimal sampling scenario. This methodology is also used to infer whether one of the houses located adjacent to affected houses has indoor air problems based on the measurements subject to the observation that the affected house is monitored and has problems and developers have liability if a problem occurs. In this part of the study, different sampling scenarios are set up in terms of permeability (1 – 80 boreholes) and soil gas concentration (2, 4 and 7 samples) and three metrics are defined and computed as a criterion for comparison. Financing brownfield redevelopment is often viewed as a major barrier to the development process mainly due to risks and liabilities associated with brownfields. The common way of managing the risk is to transfer it to insurers by purchasing insurance coverage. This work provides two different strategies to price the risk, which is equivalent to an insurance premium. It is intended to give an instructive insight into project planning and feasibility studies during the decision-making process of a brownfield project. The two strategies of risk capital valuation are an actuarial premium calculation principle and a martingale premium calculation principle accounting for the hydrogeological and financial uncertainties faced in a project. The data used for valuation are the posterior estimates of data assimilation obtained from the results of different sampling scenarios. The cost-benefit-risk analysis is employed as a basis to construct the objective function in order to find the least cost among sampling scenarios for the project. As a result, it shows that drilling seven boreholes to extract permeability data and taking soil gas samplings in four locations or seven locations alternatively give the minimum total cost. Sensitivity analysis of some influential parameters (the safety loading factors and the possible methods to calculate the probability of failure) is performed to determine their roles of importance in the risk capital valuation. This framework can be applied to provide guidance for other risk-based environmental projects.