Polymer/ceramic nanocomposites benefit by combining high permittivities (r) of metal oxide nanoparticles with high dielectric strength and excellent solution-processability of polymeric hosts. Simple mixing of nanoparticles and polymer generally results in poor quality materials due mainly to the agglomeration of nanoparticles and poor miscibility of nanoparticles in host materials. Surface modification of metal oxide nanoparticles with phosphonic acid-based ligands was found to afford a robust surface modification and improve the processablity and the quality of nanocomposites. The use of phosphonic-acid modified barium titanate (BaTiO₃) nanoparticles in dielectric nanocomposites dramatically improved the stability of the nanoparticle dispersion and the quality of the nanocomposites. Surface modification of BaTiO₃ nanoparticles allowed high quality nanocomposite thin films in ferroelectric polymer hosts such as poly(vinylidene fluoride-co-hexafluoropropylene) with large volume fractions (up to 50 vol. %), which exhibited a remarkable combination of a high permittvity (35 at 1 kHz) and a high breakdown strength (210 V/µm) leading to a maximum energy storage density of 6.1 J/cm³. The effect of nanoparticle volume fractions on the dielectric properties of this nanocomposite system was investigated and compared with theoretical models. At high volume fraction of nanoparticles, the porosity of the nanocomposites was found to have important role in the dielectric performance. A combined effective medium theory and finite difference simulation was used to model the dielectric properties of high volume fraction dielectric nanocomposites with porosity. These results provide a guideline to optimize the volume fractions of nanoparticles for maximum energy density. Nanocomposites based on phosphonic acid-modified BaTiO₃ nanoparticles can also be used as printable high permittivity dielectrics in organic electronics. High volume fractions (up to 37 vol. %) of phosphonic acid-modified BaTiO₃ nanoparticles dispersed in cross-linked poly(4-vinylphenol) allowed solution-processable high permittivity thin films with a large capacitance density (~50 nF/cm²) and a low leakage current (10 8 A/cm²) suitable as a gate insulator in organic field-effect transistors (OFETs). Pentacene-based OFETs using these nanocomposites showed a low threshold voltage (< -2.0 V) and a large on/off current ratio (Ion/off 104 ~ 106) due to the high capacitance density and low leakage current of the gate insulator.

<p>Microwave materials have been widely used in a variety of applications ranging from communication devices to military satellite services, and the study of materials properties at microwave frequencies and the development of functional microwave materials have always been among the most active areas in solid-state physics, materials science, and electrical and electronic engineering. In recent years, the increasing requirements for the development of high speed, high frequency circuits and systems require complete understanding of the properties of materials function at microwave frequencies.</p><p>Ferroelectric materials usually have high dielectric constants, and their dielectric properties are temperature and electric field dependent. The change in permittivity as a function of electric field is the key to a wide range of applications. Ferroelectric materials can be used in fabrication capacitors for electronic industry because of their high dielectric constants, and this is important in the trend toward miniaturization and high functionality of electronic products. The simple tunable passive component based on ferroelectric films is a varactor which can be made as a planar structure, and electrically tunable microwave integrated circuits using ferroelectric thin films can be developed. Therefore, it is very important to characterize the dielectric constant and tunability of ferroelectric thin films.</p><p>This thesis shows experimental results for growth, crystalline properties and microwave characterization of Na0.5K0.5NbO3 (NKN), AgTa0.5Nb0.5O3 (ATN), Ba0.5Sr0.5TiO3 (BST) as well as AgTaO3 (ATO), AgNbO3 (ANO) thin films. The films were grown by Pulsed Laser Deposition (PLD) and rf-magnetron sputtering of a stoichiometric, high density, ceramic NKN, ATN, BST target onto single crystal LaAlO3(LAO), Al2O3 (sapphire), and Nd:YAlO3, and amorphous glass substrates. By x-ray diffractometry, NKN, ATN, BST films on LAO substrates were found to grow epitaxially, whereas films on r-cut sapphire substrates were found to be preferentially (00l) oriented.</p><p>Coplanar waveguide interdigital capacitor (CPWIDC) structures were fabricated by standard photolithography processing and metal lift-off technique. Microwave properties of the NKN/Sapphire and ATN/Sapphire with CPW structures were characterized using on-wafer microwave measurement technique. Measurement setup is composed of network analyzer, probe station, and microwave G-S-G probes. External electric field through the connection between network analyzer and power supply was applied to measure voltage tunability. Measured S-parameter were used for the calculation of capacitance, loss tanδ, tunability and K-factor.</p><p>The NKN films interdigital capacitors with 2 μm finger gap on Nd:YAlO3 showed superior performance compared to ATN in the microwave range from 1 to 40 GHz. Within this range, the voltage tunability (40V, 200 kV/cm) was about 29%, loss tangent ∼ 0.13, K-factor = tunability/tanδ from 152% @ 10GHz to 46% @ 40GHz.</p><p>The microwave performance of ATN film CPWIDC with 2 μm finger gap on sapphire substrate in the microwave range from 1 to 40 GHz showed that frequency dispersion is about 4.3%, voltage tunability was 4.7% @ 20GHz and 200 kV/cm, loss tangent ∼ 0.068 @ 20GHz, K-factor = tunability/tanδ is ranged from 124% @ 10GHz to 35% @ 40GHz.</p><p>The BST films CPWIDC with 2μmfinger gap on Al2O3 substrate showed frequency dispersion of capacitance in the microwave range from 1 to 40 GHz about 17%, voltage tunability = 1 - C(40V)/C(0) ∼ 22.2%, loss tangent ∼ 0.137 @ 20GHz, and K-factor = tunability/tanδ from 281% @ 10GHz to 95% @ 40GHz.</p>

Les couches minces dérivées du matériau ferroélectrique BaTiO3 présentent un grand intérêt en vue de l'élaboration de composants intégrés pour la microélectronique et les télécommunications. Ainsi, des films de Ba0.6Sr0.4TiO3 (BST) possèdent une forte permittivité dont la valeur peut être modulée sous champ électrique, ce qui permet d'envisager leur utilisation dans des condensateurs aux propriétés ajustables. Cependant, le principal frein à leur intégration est l'importance de leurs pertes diélectriques. Des couches de BST déposées par pulvérisation magnétron radiofréquence ont été caractérisées d'un point de vue structural, chimique et diélectrique afin d'établir une référence. De nouvelles compositions exemptes de plomb, comme le BTZ (BaTi1-xZrxO3) et le BST substitué avec de l'étain, ont été synthétisées en vue d'abaisser les pertes. Des mesures diélectriques en température ont mis en évidence le caractère relaxeur des couches minces de BTZ riches en zirconium, et la copulvérisation a permis d'étudier l'ensemble de la solution solide BaTiO3-BaZrO3. Enfin, un nouveau type d'hétérostructures alliant le BST à une barrière diélectrique de SiO2 a permis d'atteindre des pertes très inférieures à 0.5% tout en conservant une permittivité et une accordabilité satisfaisantes.

This dissertation shows a detailed investigation on reconfigurable low profile antennas using tunable high impedance surfaces (HIS). The specific class of HIS used in this dissertation is called a frequency selective surface (FSS). This type of periodic structure is fabricated to create artificial magnetic conductors (AMCs) that exhibit properties similar to perfect magnetic conductors (PMCs). The antennas are intended for radiometric sensing applications in the biomedical field. For the particular sensing application of interest in this dissertation, the performance of the antenna sub-system is the most critical aspect of the radiometer design where characteristics such as small size, light weight, conformability, simple integration, adjustment in response to adverse environmental loading, and the ability to block external radio frequency interference to maximize the detection sensitivity are desirable. The antenna designs in this dissertation are based on broadband dipole antennas over a tunable FSS to extend the usable frequency range. The main features of these antennas are the use of an FSS that does not include via connections to ground, their low profile and potentially conformal nature, high front-to-back radiation pattern ratio, and the ability to dynamically adjust the center frequency. The reduction of interlayer wiring on the tunable FSS minimizes the fabrication complexity and facilitates the use of flexible substrates. This dissertation aims to advance the state of the art in low profile tunable planar antennas. It shows a qualitative comparison between antennas backed with different unit cell geometries. It demonstrates the feasibility to use either semiconductor or ferroelectric thin film varactor-based tunable FSS to allow adjustment in the antenna frequency in response to environment loading in the near-field. Additionally, it illustrates how the coupling between antenna and HIS, and the impact of the varactor losses affect the antenna performance and it shows solutions to compensate these adverse effects. Novel hybrid manufacturing approaches to achieve flexibility on electrically thick antennas that could be transitioned to thin-film microelectronics are also presented. The semiconductor and ferroelectric varactor-based tunable low profile antennas demonstrated tunability from 2.2 GHz to 2.65 GHz with instantaneous bandwidths greater than 50 MHz within the tuning range. The antennas had maximum thicknesses of λ/45 at the central frequency and front to back-lobe radiation ratios of approximately 15dB. They also showed impedance match improvement in the presence of a Human Core Model (HCM) phantom at close proximity distances of the order of 10-20 mm. In addition, the use of thin film ferroelectric Barium Strontium Titanate (BST) varactors in the FSS layer enabled an antenna that had smaller size, lower cost and less weight compared to the commercially available options. The challenging problems of fabricating robust flexible antennas are also addressed and novel solutions are proposed. Two different types of flexible antennas were designed and built. A series of flexible microstrip antennas with slotted grounds which demonstrated to be robust and have 42% less mass than typically used technologies (e.g., microstrip antennas fabricated on Rogers® RT6010, RT/duroid® 5880, etc.); and flexible ferroelectric based tunable low profile antennas that showed tunability from 2.42 GHz to 2.66 GHz using overlapping metallic plates instead of a continuous ground plane. The bending test results demonstrated that, by placing cuts on the ground plane or using overlapping metallic layers that resemble fish scales, it was possible to create highly conductive surfaces that were extremely flexible even when attached to other solid materials. These new approaches were used to overcome limitations commonly encountered in the design of antennas that are intended for use on non-flat surfaces. The material presented in this dissertation represents the first investigation of reconfigurable low profile antennas using tunable high impedance surfaces where the desired electromagnetic performance as well as additional relevant features such as robustness, low weight, low cost and low complexity were demonstrated.

High performance miniaturized passives are of great importance for advanced nanoelectronic packages for several applications including efficient power delivery. Low cost thin film capacitors fabricated directly on package (and/or on-chip) are an attractive approach towards realizing such devices. This thesis aims to explore fundamental frequency dependent dielectric and insulating properties of thin film high-k dielectric constant in the perovskite and perovskite-related complex oxides. Throughout this thesis, we have successfully observed the role of structure, strain and oxygen stoichiometry on the dielectric properties of thin film complex oxides, allowing a greater understanding of processing conditions and polarization mechanisms. In the first section of the thesis, we explore novel processing methods in the conventional ferroelectric, barium strontium titanate, \(Ba_{1-x}Sr_xTiO_3 (BST)\), using ultraviolet enhanced oxidation techniques in order to achieve improvements in the dielectric properties. Using this method, we also explore the growth of BST on inexpensive non-noble metals such as Ni which presents technical challenges due to the ability to oxidize at high temperatures. We observe a significant lowering of the dielectric loss while also lowering the process temperature which allows us to maintain an intimate interface between the dielectric layer and the metal electrode. The second section of this thesis explores the novel dielectric material, Lanthanum Strontium Nickelate, \(La_{2-x}Sr_xNiO_4 (LSNO)\), which exhibits a colossal dielectric response. For the first time, we report on the colossal dielectric properties of polycrystalline and epitaxial thin film LSNO. We observe a significant polarization dependence on the microstructure due to the grain/grain boundary interaction with charged carriers. We next grew epitaxial films on various insulating oxide substrates in order to decouple the grain boundary interaction. Here we observed substrate dependent dielectric properties associated with induced strain. We also observe, due to the p-type carriers in LSNO, pn junction formation when grown epitaxially on the conducting oxide degenerate n-type Nb-doped \(SrTiO_3\). Finally we explore the growth mechanism of epitaxial LSNO as a function of high oxygen content. Due to the ability for LSNO to take in interstitial oxygen, a reoriented growth is observed at a critical thickness, thereby allowing us to vary anisotropy as a function of deposition conditions. / Engineering and Applied Sciences

Various experiments on Yb₂Ti₂O₇ have shown evidence of strange magnetic behaviour at low temperatures. Specific heat measurements on powder samples of Yb₂Ti₂O₇ show evidence of a sharp peak, indicating the occurence of a first order phase transition. Meanwhile, neutron scattering, Mössbauer absorption, and μSR measurements find no evidence of long range order below the temperature of this phase transition, leaving the nature of the low temperature phase a mystery. Quantifying the magnetic interactions in this material should allow us to better understand the low temperature behaviour of this material. In this study, we fit a symmetry allowed nearest-neighbour bilinear exchange model to quasi-elastic neutron scattering data collected well above the temperature of the experimentally observed phase transition. This neutron scattering data shows evidence of rods of scattering intensity along the ⟨111⟩ crystallographic directions. Neutron scattering probes the correlations between magnetic moments in a material, so fitting an interaction model to the neutron scattering is equivalent to fitting the interactions to the magnetic correlations. These correlations are driven by the interactions between the magnetic moments, so the neutron scattering should give us direct access to the form of these interactions. Using this method we successfully identify an anisotropic nearest-neighbour bilinear exchange model that reproduces the experimentally observed quasi-elastic neutron scattering. With this model we then proceed to compute real space correlation functions, finding that the rods of neutron scattering arise from the presence of strong correlations along nearest-neighbour chains. We also compute the bulk susceptibility and local susceptibility, obtaining very good fits to experiment with no variation of the model determined from the neutron scattering. The success of these calculations provides a further independent confirmation of the success of our interaction model in describing the magnetic interactions in Yb₂Ti₂O₇. Finally, we present a brief summary of ongoing work based on our anisotropic exchange model, including mean field calculations to determine the low temperature ground state of this model and classical Monte Carlo simulations to study the phase transition present in this model. We also discuss potential further studies of this and other models.

No description available.

Als Modellsystem für Oxide mit Perowskitstruktur ist Strontiumtitanat besonders geeignet, um generalisierbare Erkenntnisse über die Auswirkungen von Defekten zu gewinnen und ausgehend davon Struktur-Eigenschafts-Korrelationen zu diskutieren. Durch den Einsatz verschiedener oberflächensensitiver Methoden lässt sich im Ausgangszustand eine erhöhte Konzentration von Liniendefekten an der Oberfläche nachweisen, die sich durch Temperaturbehandlung verkleinert. Die Defektchemie bei hohen Temperaturen wird zur Simulation der elektrischen Leitfähigkeit in Abhängigkeit vom umgebenden Sauerstoff-Partialdruck genutzt. Die Dotierung des oxidischen Halbleitermaterials ist von Eigendefekten abhängig, wobei Sauerstoff-Leerstellen Donatorniveaus bilden und Strontium-Leerstellen Akzeptorcharakter besitzen. Neben der Diffusionsbewegung dieser Eigendefekte bei hohen Temperaturen kann bei niedrigen Temperaturen ein elektrisches Feld deren Umverteilung bewirken. Damit zeigt sich die Leitfähigkeit abhängig von externen elektrischen Feldern, aber auch weitere Eigenschaften sind auf diesem Wege modifizierbar. Im Rahmen der Arbeit werden strukturelle Änderungen, Valenz-Änderungen und veränderte mechanische Eigenschaften nachgewiesen, die jeweils abhängig vom elektrischen Feld schaltbar sind. Schließlich wird das gezielte Ausnutzen struktureller Defekte für Speicherzellen, die den schaltbaren Widerstand von Metall-SrTiO3-Kontakten zur Grundlage haben, vorgestellt. Die Anwendbarkeit des oxidischen Halbleiters als resistives Speicherelement beruht wiederum auf der Kopplung von Sauerstoff-Leerstellen an das elektrische Feld. / Being a model system for oxides with pervovskite-type of structure, strontium titanate can be used to gain generalizable insights into the consequences of defects and to discuss resulting structure-property relationships. By employing different surface sensitive methods, an increased concentration of line defects is found at the surface that reduces on temperature treatment. The defect chemistry at elevated temperatures is used to simulate the electric conductivity depending on the oxygen partial pressure during annealing. Doping of the oxidic semiconductor depends on intrinsic defects, whereby oxygen vacancies form donor states and strontium vacancies have acceptor character. Beside the diffusion movement of these intrinsic defects at elevated temperatures, at low temperatures an electric field may cause their redistribution. Hence, the conductivity becomes dependent on external electric fields but also other properties can be altered in this way. Within this work, structural changes, valence changes and changing mechanical properties are shown to be switchable by the electric field. Finally, the dedicated usage of structural defects is demonstrated on memory cells that employ the switchable resistance of metal-SrTiO3 junctions. The applicability of the oxidic semiconductor as a resistive memory element is again based on the coupling between oxygen vacancies and the electric field.

This thesis presents work done on the calculation of the effects of anharmonic nuclear motion on the properties of solid materials from first principles. Such anharmonic effects can be significant in many cases. A vibrational self-consistent field (VSCF) method is used as the basis for these calculations, which is then improved and applied to a variety of solid state systems. Firstly, work done to improve the efficiency of the VSCF method is presented. The standard VSCF method involves using density functional theory (DFT) to map the Born-Oppenheimer (BO) energy surface that the nuclei move in, a computationally expensive process. It is shown that the accurate forces available in plane-wave basis DFT can be used to help map the BO surface more accurately and reduce the computational cost. This improved VSCF+f method is tested on molecular and solid hydrogen, as well as lithium and zirconium, and is found to give a speed-up of up to 40%. The VSCF method is then applied to two different systems of physical interest. It is first applied to the case of the neutral vacancy in diamond, in order to resolve a known discrepancy between harmonic ab initio calculations and experiment -- the former predict a static Jahn-Teller distortion, whilst the latter leads to a dynamic Jahn-Teller effect. By including anharmonic corrections to the energy and nuclear wavefunction, we show that the inclusion of these effects results in agreement between first-principles calculations and experiment for the first time. Lastly, the VSCF method is applied to barium titanate, a prototypical ferroelectric material which undergoes a series of phase transitions from around 400 K downwards. The nature of these phase transitions is still unclear, and understanding them is an active area of research. We describe the physics of the phase transitions of barium titanate, including both anharmonicity and the effect of polarisation caused by long wavelength vibrations, to help understand the important physics from first principles.

Esta tese investigou o efeito da taxa de resfriamento em partículas de Al2O3, Al2O3 - TiO2, e Al2TiO5 aspergidas por pistola a plasma e submetidas a diferentes taxas de resfriamento (alta: aspersão contra um substrato metálico a 100 mm de distância da pistola de plasma, e baixa: contra uma superfície de água, a 300 mm de distância). Os resultados foram avaliados por microscopia eletrônica de varredura (com EDX) e por difração de raio X para a caracterização de fases e cálculo de tamanho de cristalito por Single Line. O óxido Al2TiO5 na forma de pó quase amorfo com composição estequiométrica de tialita (tialita*) aspergido foi obtido por coprecipitação, a partir dos precursores TiCl4 e Al(NO4)3, tratado termicamente a 400, 600, 800, 900, 1000, 1200, 1300 e 1400 °C, com 6 h de patamar. Nos tratamentos térmicos com 6 horas de patamar a 800 °C e mais nitidamente a 900 °C, é identificada a formação parcial da fase tialita; desta forma, foram realizados tratamentos térmicos a 900, 1000 e 1100 °C, porém com 30 minutos de patamar. A Al2O3-a com tamanho de cristalito micrométrico foi obtida para menores taxas de resfriamento. Com o aumento da taxa de resfriamento, predominaram nanocristalitos de alumina Al2O3-g, coexistindo com fase amorfa. Já para a titânia, a fase rutilo pode ser obtida mesmo com altas taxas de resfriamento. Quando a tialita* foi submetida à alta taxa de resfriamento, levou exclusivamente à formação da fase metaestável tialita b como estrutura cristalina. No entanto, o mesmo pó, a taxas de resfriamento não tão altas, resultou na obtenção de tialita b, Al2O3-a e rutilo. Tratamentos térmicos da tialita* propiciaram a formação de tialita b, e incipientemente anatásio, com tamanho de cristalito muito pequeno (abaixo de 30 nm). À medida que a temperatura de tratamento térmico aumentou, surgiram simultaneamente as fases Al2O3-a, rutilo e tialita b. A obtenção de fases metaestáveis só foi possível quando o tamanho de cristalito era pequeno – abaixo de 100 nm, o que evidenciou a importância do número de átomos na superfície, como fator de estabilização (ou metaestabilização) de fases obtidas foras do equilíbrio. / This thesis investigated the effect of cooling rate of Al2O3, Al2O3 - TiO2 and Al2TiO5 particles plasma sprayed and subjected to different cooling rates (high: to spray against a metal substrate to 100 mm away from the plasma gun, and low: against a surface of water, 300 milimeters away). The results were evaluated by scanning electron microscope (with EDX) and X ray diffraction to characterize phases and crystallite size through Single Line. The sprayed Al2TiO5 oxide was a quasi-amorphous powder with stoichiometric composition of tialite (tialita*) obtained by co-precipitation from precursors TiCl4 and Al(NO4)3, heat treated at 400, 600, 800, 900, 1000, 1200, 1300 and 1400 °C with 6 hours of dwell. In the heat treatments with 6 hour of dwell at 800 ° C and more explicitly at 900 °C, is identified partial formation of tialite phase; then, heat treatments were performed at 900, 1000 and 1100 ° C, but with 30 minutes of dwell. Basically, a-Al2O3 with micrometer crystallite size was obtained for smaller cooling rates. By increasing the cooling rate, there were predominantly g-Al2O3 nanocrystallites coexisting with amorphous phase. However, for the titania, the rutile phase could be obtained even with high cooling rates. When tialita* was subjected to high cooling rate, exclusively, metastable b tialite was observed as crystalline phase. However, the same powder, with cooling rates not so high, resulted in b tialite, a-Al2O3 and rutile. Heat treatments of tialita* provided the formation of b tialite, and incipiently anatase with crystallite size very small (below 30 nm). As the heating treatment temperature was increased, there were simultaneously a-Al2O3, rutile and b tialite phases. Metastable phases were obtained only when the crystallite size was small - less than 100 nm. This highlighted the importance of the number of atoms on the surface as a stabilizing factor (or metastabilization) to produce phases out of equilibrium.