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The interaction between light and matter is usually modeled by approximating the material under study as a continuum. The magnitude of the material's polarization in the presence of an electric field is dependent on the atomic response via the well-known Lorentz-Lorentz relation. These continuous medium models can be used to see many light-matter effects including non-linear interactions.The goal of this thesis is to adapt and use novel computational methods to explore the microscopic origins of non-linear optical effects. The Microscopic Particle-in-Cell (MicPIC) technique, initially developed to model the laser-driven dynamics of strongly-coupled plasmas, is extended to study the non-linear scattering of light by a collection of dipoles in the atomic limit. In this thesis, we find that in one-dimensional chains of individual scatterers there are apparent boundary effects and the generation of even harmonics that do not appear in continuous media calculations.These finite structures of dipoles also exhibit a lower average response from each at odd harmonic frequencies of the driving light frequency.These results are in contradiction with the commonly used Lorentz-Lorenz relation, derived for a dipole in a 3D material with infinite volume, and suggest that MicPIC is more appropriate for calculations of nanostructures than models using the Lorentz-Lorenz relation.

The problem of electromagnetic wave propagation across the junction of two similar planar dielectric waveguides is analysed, within the Kirchhoff approximation, by expanding the field into transverse variations of all possible modes. It is proven that the expansion can represent any solution for any planar dielectric waveguide. The spectral function is introduced into the representation, and this helps resolve some of the theoretical problems in passing from the limit of closed waveguides to open waveguides. Using the spectral function and the Gel'fand-Levitan integral equation some new exact solutions to novel dielectric planar waveguides can be found. Examples of waveguiding by total internal reflection or by Bragg reflection (which are physically very different processes) can be generated by changing a single parameter in the formulation. Usually the representation for an open dielectric waveguide requires the matrix spectral function. However the Gel'fand-Levitan reconstruction is defined for scalar spectral functions. A technique for constructing the spectral matrix and the scattering solutions from two spectral functions is demonstrated. This technique uses a variational formulation of a scattering experiment. The connection between a dielectric structure and the characteristics of propagation on it is obscure. However the connection between these characteristics and the spectral function is much clearer. It is sometimes possible to make predictions about the properties of the waveguide by looking at its spectral function only. Since the connection between the spectral function and the dielectric structure is well established by inverse spectral theory, introducing the spectral function has been of help in establishing the desired connection between the dielectric structure and the characteristics of propagation on it. Such considerations suggest one of the above waveguides is sensitive to small perturbations and could be used as an electro-optic modulator. Detailed calculations confirm the hypothesis. / Applied Science, Faculty of / Electrical and Computer Engineering, Department of / Graduate

Ca(1-x)Nd2x/3TiO3 and MgTiO3-Ca0.61Nd0.26TiO3 composite ceramics were prepared by the mixed oxide route and characterised in terms of their structure, microstructure and properties. Ceramics sintered at 1450-1500oC achieved better than 95% of the theoretical density. X-Ray diffraction (XRD) revealed that Ca(1-x)Nd2x/3TiO3 ceramics were single phase for all compositions. For x ≤ 0.39 the structure was Pbnm with lattice parameters of a = b = √2ac and c = 2ac and a tilt system of a-a-c+. Compositions with x ≥ 0.48 could be better described by a C2/m structure with lattice parameters of a = b = c = 2ac. Scanning electron microscopy (SEM) revealed that the ceramics had grain sizes in the 5-70 μm range with abnormal grain growth for Nd3+ rich compositions. Images revealed that the twin domains in CaTiO3 were needle shaped and on addition of Nd3+ the domain morphology becomes more complex. The needle domain morphology returns for Ca0.43Nd0.38TiO3. High resolution electron microscopy (HAADF-STEM and electron diffraction) was used to probe cation-vacancy ordering (CVO) in the lattice. It was found that there was no CVO for x < 0.48 whilst at x = 0.48 there was evidence of a transition to a short range CVO. A transition to long range ordering is almost complete for the Ca0.1Nd0.6TiO3. The structural characteristics of Ca(1-x)Nd2x/3TiO3 ceramics as a function of temperature were investigated using in-situ XRD and Raman spectroscopy. All compositions were found to have the same structure across the entire temperature range. The Raman spectroscopy as a function of temperature indicated a possible transition with similar characteristics to a Curie temperature in a ferroelectric ceramic. The transition temperature was dependent on the cation ordering with the ceramics with greatest degree of disorder having the lowest transition temperature. The microwave dielectric properties of the samples were measured by a cavity resonance method in the 2-4GHz range. The relative permittivity (εr) was found to decrease from 180 for CaTiO3 to approximately 80 for Ca0.1Nd0.6TiO3 with an exponential dependence between the composition and the property. The temperature coefficient of resonant frequency (τf) ranged from +770ppmK-1 for CaTiO3 to +200ppmK-1 for Ca0.1Nd0.6TiO3. The Q x f for CaTiO3 was found to be 6000GHz and this increased to a maximum of 13000GHz for Ca0.7Nd0.2TiO3. After the Ca0.7Nd0.2TiO3 composition, the Q x f decreased to approximately 1100GHz for Ca0.1Nd0.6TiO3. The εr and τf were found to be mainly dependent on the composition of the ceramics whilst the Q x f value was more complex being dependent on the width of the twin domains in the grains. CaTiO3 samples fabricated by spark plasma sintering at 1150oC and above achieved better than 95% of the theoretical density. XRD revealed only a single phase with an orthorhombic Pbnm structure at room temperature and a tilt system of a-a-c+. SEM confirmed that the samples were single phase with grain size between 500nm-5μm. Transmission electron microscopy (TEM) of specimens sintered at 1150oC showed evidence of both (011) and (112) type domains. The τf of the ceramics was shown to be dependent on the volume of the unit cell, in agreement with the Bosman-Havinga equations. The ceramic sintered at 1150oC showed improvement in the Q x f value compared to samples prepared by conventional sintering. The structure, microstructure and properties of composite ceramics based on the MgTiO3-Ca0.61Nd0.26TiO3 system were investigated. Optimum properties were achieved at a composition of 0.8MgTiO3-0.2Ca0.61Nd0.26TiO3 with τf = -0.1ppmK-1, Q x f of 39000GHz and εr of 25.4. XRD revealed the presence of 3 phases including Ca0.61Nd0.26TiO3, MgTiO3 and MgTi2O5. The grain size of the ceramics was typically 5μm. The Q x f value was sensitive to the cooling rate and these changes could be related to changes in the vibrational properties of the lattice through changes in the lattice parameters.

This thesis reports the first detailed study of the stoichiometry control mechanisms and physical properties of ZnO films deposited by dc planar magnetron sputtering of a Zn target in a reactive Ar/0₂ atmosphere. Control of film stoichiometry was achieved using a subsidiary rf discharge at the substrate and a reactive gas baffle surrounding the target. The reactive gas baffle was shown to enhance film oxidation by decreasing the metal flux to the substrate and increasing the oxygen partial pressure near the substrate. Rutherford backscattering analysis of film stoichiometry demonstrated that the effect of the rf discharge was to increase the O/Zn composition ratio. This oxidation was shown to occur through preferential resputtering and preferential evaporation of excess Zn and by activation and ion plating of oxygen species. Resputtering and evaporation rates were found to be enhanced above that expected for bulk Zn, due to the weak bonding of surface adatoms during film growth. Conducting ZnO films produced at various values of the rf-induced substrate bias voltage were characterized for electrical, optical and structural properties using Hall probe,. X-ray diffraction, electron microscope, and visible and infrared spectroscopy techniques. Films deposited at low substrate bias (0 to -50V) were found to have a large Zn excess (15%) resulting in low electron mobilities (1 cm²/Vs), high resistivities (10⁻² Ωcm) and were strongly absorbing in the visible. Films deposited at high substrate bias were nearly stoichiometric, optically transparent and had high electron mobilities (15 cm²/Vs) resulting in low resistivity (10⁻³ Ωcm). The optical properties of transparent conducting films for wavelengths 0.4 to 20 /im were modelled by the Drude theory of free electrons using measured electrical transport properties. The original goal of this work, to develop a heat mirror coating suitable for manufacture, was achieved by bias sputter deposition of ZnO onto uncooled polyester sheet at deposition rates approaching 75 nm/min. The best heat mirror films had a transmission to solar energy of 75% and an 85% reflection of 300 K blackbody radiation. / Science, Faculty of / Physics and Astronomy, Department of / Graduate

ZnO has generated interest for flexible electronics/optoelectronic applications including transparent thin film transistors (TFTs). For this application, low temperature processes that simultaneously yield good electrical conductivity and optical transparency and that are compatible with flexible substrates such as plastic, are of paramount significance. Further, gate oxides are a critical component of TFTs, and must exhibit low leakage currents and self-healing breakdown in order to ensure optimal TFTs switching performance and reliability. Thus, the objective of this work was twofold: (1) develop an understanding of the processing-structure-property relationships of ZnO and high-κ BaTa2O6 and Al2O3 (2) understand the electronic defect structure of BaTa2O6 /ZnO and Al2O3/ZnO interfaces and develop insight to how such interfaces may impact the switching characteristics (speed and switching power) of TFTs featuring these materials. Of the ZnO films grown by atomic layer deposition (ALD), pulsed laser deposition (PLD) and magnetron sputtering at 100-200 °C, the latter method exhibited the best combination of n-type electrical conductivity and optical transparency. These determinations were made using a combination of photoluminescence, photoluminescence excitation, absorption edge and Hall measurements. Metal-insulator-semiconductor devices were then fabricated with sputtered ZnO and high-κ BaTa2O6 and Al2O3 and the interfaces of high-κ BaTa2O6 and Al2O3 with ZnO were analyzed using frequency dependent C-V and G-V measurements. The insulator films were deposited at room temperature by magnetron sputtering using optimized processing conditions. Although the Al2O3 films exhibited a lower breakdown strength and catastrophic breakdown behavior compared to BaTa2O6/ZnO interface, the Al2O3/ZnO interface was characterized by more than an order of magnitude smaller density of interface traps and interface trapped charge. The BaTa2O6 films in addition were characterized by a significantly higher concentration of fixed oxide charge. The transition from accumulation to inversion in the Al2O3 MIS structure was considerably sharper, and occurred at less than one tenth of the voltage required for the same transition in the BaTa2O6 case. The frequency dispersion effects were also noticeably more severe in the BaTa2O6 structures. XPS results suggest that acceptor-like structural defects associated with oxygen vacancies in the non-stoichiometric BaTa2O6 films are responsible for the extensive electrical trapping and poor high frequency response. The Al2O3 films were essentially stoichiometric. The results indicate that amorphous Al2O3 is better suited than BaTa2O6 as a gate oxide for transparent thin film transistor applications where low temperature processing is a prerequisite, assuming of course that the operation voltage of such devices is lower than the breakdown voltage. Also, the operation power for the devices with amorphous Al2O3 is lower than the case for devices with BaTa2O6 due to the smaller fixed oxide charges and interface trap density.

Increasing demand for high-density memories has necessitated the search for new materials with higher dielectric constants to satisfy the minimum charge storage density requirements. Several materials such as Ta₂O₅, BST¹, BBT² are being investigated to replace the currently used Si based oxide/nitride dielectrics. Among the materials under investigation, Ta₂O₅ is one of the most promising, especially from the fab compatibility point of view. Ta₂O₅ thin films offer a six-fold increase in dielectric constant compared to conventional dielectrics. However, the significant improvement in dielectric constant is offset by higher leakage currents compared to conventional dielectrics. Improvement in both, dielectric and insulating properties is required for the successful integration of Ta₂O₅ thin films into devices. In the current research work, it was demonstrated that by chemically modifying the tantalum pentoxide matrix, significant improvements in its electrical properties can be achieved which would enable the fabrication of a reliable high-density memory device. In the present work, the effects of Al addition on Ta₂O₅ thin films were systematically studied. The structural and electrical properties of these chemically modified thin films were investigated in detail to establish their potential for device applications. The effects on dielectric and insulating characteristics due to incorporation of Al in Ta₂O₅ matrix were studied in capacitor configuration. A metallorganic solution decomposition (MOSD) technique was used to deposit thin films onto Pt coated Si(100) substrates. The capacitors were fabricated by sputter depositing Pt electrodes on the top surface of the films. The dielectric and insulating properties of pure and modified Ta₂O₅ thin films and their dependence on film composition, processing temperature, and the thickness were discussed and an attempt was made to provide theoretical understanding for the experimental observations. The dielectric and insulating properties of Ta₂O₅ were found to be significantly modified by addition of Al. It was observed that Al addition has decreased the leakage currents approximately by an order of magnitude and improved thermal and bias stability characteristics of Ta₂O₅ capacitors. For example, the leakage currents in crystalline pure Ta₂O₅ thin films were found to be 4.5 x 10⁷ A/cm² in a 1MV/cm dc field which decreased to 3.4 x 10⁸ A/cm² for 10% Al modified Ta₂O₅ thin films. A typical dielectric constant of 42.5 was obtained for 10% Al modified Ta₂O₅ thin films. This is significantly higher compared to the commonly reported dielectric constant of 25 to 35 for Ta₂O₅ thin films. This enhancement was attributed to strong (100) orientation exhibited by both pure and modified Ta₂O₅ thin films. The high dielectric constant, low dielectric loss, low leakage currents and low temperature coefficient of capacitance suggest the suitability of Al modified Ta₂O₅ as a capacitor dielectric for future generation DRAM applications. ¹Barium strontium titanate, ²Barium bismuth tantalate / Master of Science

Light absorption in metal catalyst nanoparticles can excite charge carriers to generate hot electron (and complimentary hot holes) with energy higher than the Fermi level. When hot electrons possess energy high enough, they exhibit a high tendency to inject into antibonding orbitals of adsorbates on the photoexcited metal nanoparticles, weakening the corresponding chemical bonds to promote chemical reactions with accelerated reaction kinetics and improved selectivity. Such hot-carrier chemistry has been reported on plasmonic metal nanoparticles, such as silver and gold, which exhibit strong surface plasmon resonances (SPRs) and strong light absorption. However, these metal nanoparticles are not suitable catalysts because their affinity toward interesting molecules is limited. In contrast, most transition metals, such as platinum-group metals and early transition metals, are industrially essential catalysts, but light absorption power in metal nanoparticles is low due to the absence of SPRs in the visible spectral range. Therefore, it is intriguing to explore the potential of hot-carrier catalytic chemistry on photoexcited non-plasmonic metal nanoparticles. Upon the absorption of the same optical power, metal nanoparticles with a small size usually exhibit a high probability of hot electron production and high efficiency of injecting hot electrons into adsorbates. It is challenging to have strong light absorption power and operation stability of the catalyst metal nanoparticles with small sizes. In this thesis, dielectric light antenna, i.e., spherical silica nanoparticles with strong surface scattering resonances near their surfaces, is introduced to support the metal catalyst nanoparticles, enabling improved light absorption power in the metal nanoparticles and operation stability. This thesis focuses on ultrafine rhodium (Rh) nanoparticles (with sizes ranging from 1.7 nm to 4.2 nm) that are widely used as thermal catalysts in many important industry reactions, especially for oxygen-containing species conversion, an oxyphilic feature of Rh nanoparticles. Firstly, this dissertation conducted a comparative study to investigate the influence of silica geometry, nanospheres, and rodlike nanoparticles on the light absorption of Rh nanoparticles. Both silica substrates enhanced the light absorption of loaded Rh nanoparticles due to elongated light scattering paths (random scattering) and enhanced electromagnetic field intensity (resonant scattering). However, silica nanospheres support both resonant scattering and random light scattering modes, exhibiting a higher Rh absorption than the usage of rodlike silica nanoparticles. The light resonant scattering modes on highly symmetrical silica nanospheres enable producing "hot spots" with a much higher electromagnetic field intensity than incident light intensity. This study then investigated the effect of silica geometries on photocatalytic performance. The CO2 hydrogenation was studied as a model reaction. The Rh/silica nanosphere system exhibited a faster photocatalytic kinetic than the case of rodlike silica nanoparticles. It is possibly due to the enhanced light power density around the silica nanospheres. The results give a promise of expanding Rh nanoparticles from thermo-catalysis to photocatalysis. Secondly, this dissertation moves onto accelerating aerobic oxidation of primary alcohols to aldehydes, which was benefited from activated oxygen molecules by hot electron injection. This study found that photoexcited Rh nanoparticles enabled accelerating the alcohol oxidation kinetics by four times at a light power intensity of 0.4 W cm-2, accompanied by a reduced activation energy of 21 kJ mol-1. The derived Langmuir-Hinshelwood rate equation was used to fit the oxygen partial pressure results. Photo-illumination promotes the cleavage of associatively adsorbed oxygen molecules into adsorbed oxygen atoms, reducing the energy barrier. Besides, the silica-supported Rh nanoparticles exhibited a higher photocatalytic performance because of the good colloidal stability and enhanced light absorption of small-sized Rh particles. This part of the dissertation shows the possibility of hot-electron mediated reaction pathways towards a desirable kinetic of alcohol oxidation. Thirdly, it will be meaningful to use the abstracted protons from cheap alcohol sources to reduce other organic molecules rather than dangerous hydrogen gas. This dissertation then investigated the possibility of using an isopropanol solvent as a hydrogen source to reduce nitrobenzene and the feasibility of enhancing the selectivity of the reaction with the light illumination. The results showed that the isopropanol was spontaneously oxidized, producing acetone. Light illumination onto Rh particles selectively enhanced the coupling of reduced nitrobenzene intermediates to produce azoxybenzene. The selectivity of nitrobenzene and production rates gradually increased with a higher number of light photons. Photo-illumination promotes both aniline and azoxybenzene production rates. Hot electrons on Rh particles possibly enabled activating nitrobenzene molecules and increasing concentrations of reduced nitrobenzene intermediates. It resulted in a higher possibility of condensation product and azoxybenzene selectivity, which could not be obtained by elevating temperature without light illumination. This part of the work demonstrated the feasibility of hot electrons from Rh nanoparticles to tune the reaction selectivity in a liquid phase. Lastly, it is challenging to modulate the selectivity of CH4 from CO2 hydrogenation because of the competitive CO production. This dissertation moves towards enhancing both kinetic rates and selectivity of CH4 for gaseous CO2 hydrogenation by photoexcited Rh nanoparticles. Light illumination onto Rh/silica nanosphere particles resulted in the selectivity of CH4 over 99% in contrast to ~70% under dark conditions at 330 oC and with an absorbed light power intensity of 1.5 W cm-2. The activation energy of CH4 production and CO2 consumption gradually decreased with higher light power intensity because of the transient injection of hot electrons into adsorbates to activate intermediates. Increasing operating temperature and light power intensity synergistically enhanced the reaction kinetics. Besides, a middle-sized Rh nanoparticle showed a better photocatalytic performance than that of the largest-sized Rh nanoparticles because of the balance in hot-electron production efficiency and intrinsic catalytic performance. Partial pressure dependence and in situ infrared characterizations showed that the critical stable intermediates for CH4 production should be hydrogenated CO2 species (HCOO* COOH*) and hydrogenated CO* species (carbonyl hydride or HxCO*). The light illumination exclusively enhanced the dissociation of CO2 and CO* without apparent influence on CO* desorption. Under high reaction temperature, light illumination preferred a faster CO* conversion than CO2 dissociation, leading to high CH4 selectivity. This result was also supported by higher methanation rates of CO gas under light illumination. The infrared result showed a reduced stretching frequency of CO*, which supported the possibility of the electron from Rh back-donating into antibonding orbitals of strongly adsorbed CO* species. However, hot electrons from silver nanoparticles with a weak COOH* or CO* adsorption could not efficiently activate carbon-species and could not promote CO2 hydrogenation kinetics. This dissertation offers an avenue of enhancing light absorption of small-sized Rh nanoparticles and expanding its usage from thermal catalysis to photocatalysis for driving oxidation and reduction reactions. The reactants share a common feature containing oxygen elements, a strong affinity with rhodium metal for efficient hot electron injection. We studied the light power intensity and temperature-dependence, showing the accelerated reaction kinetics by hot electron-driven pathways. Photo-excited rhodium nanoparticles were believed to promote the cleavage of chemical bonds O-O, N-O, and C-O to drive chemical transformations. The findings offer insights into developing the scope of non-plasmonic metal nanoparticles in photocatalytic reactions for industrial applications. / Chemistry

Dielectric properties play an influential role in the development of medical devices. Understanding the behavior of these properties and how they respond to external stimuli, such as heat, over an extended frequency has yet to be researched. The focus of this study is to examine the impact of temperature on dielectric properties from 500 MHz to 10 GHz in order to better match the antenna properties of medical applications to the dielectric properties of biological tissue in question; more specifically, microwave ablation, microwave hyperthermia, and thermal modeling of brown adipose tissue’s metabolic processes. The dielectric properties of biological tissue samples from porcine lung, liver, heart, skin, fat, and muscle as well as brown adipose tissue and white adipose tissue from rat have been tested. These results have then been used to develop medical applications involving microwave antennas.

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