A literature review on the topic of ferroic and multiferroic solid solutions of BaTiO3, SrTiO3 and EuTiO3 forms the first part of this master thesis. The second part describes the experimental preparation and evaluation of the properties of samples of europium strontium titanates - EuxSr1-xTiO3. First, the high temperature solid state synthesis was carried out and relative density and open porosity of the sintered samples were evaluated. The sintered samples showed open porosity higher than 10%. The reasons for this behavior were evaluated and described from the point of view of experimental conditions and thermodynamical calculations. Finally, electric and dielectric properties of selected samples were measured. These results show that these samples are insulators and their residual conductivity is caused probably by oxygen vacancies, arising from the synthesis in a strongly reducing atmosphere of pure hydrogen.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第17985号 / 工博第3814号 / 新制||工||1584(附属図書館) / 80829 / 京都大学大学院工学研究科電子工学専攻 / (主査)教授 川上 養一, 教授 藤田 静雄, 准教授 浅野 卓 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

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The development of nanoscale heterostructure photocatalysts for the effective, direct utilization of visible light (400-750 nm, ~44% of solar spectrum) to drive important chemical conversions is a prime research area in the field of photocatalysis. Particles at nanoscale dimensions have a large surface area-to-volume ratio, expose a high number of active surface sites, and exhibit unique electronic properties (different from bulk) that are beneficial for improving the overall catalytic activity. However, the advantages of size reduction are often overshadowed by the low optical absorption (as absorption power  size3) and colloidal instability (extensive aggregation) of particles at the nanoscale. In this dissertation, we demonstrate a strategy to improve the colloidal stability and enhance the optical absorption of nano-sized semiconductor and metal nanoparticles (NPs) that exhibit weak visible light absorption. The colloidal, free-standing NPs are placed on transparent, dielectric silica nanospheres (SiOx NSs) that act as optical antenna supports, forming SiOx/NP composite nanostructures. The spherical morphology of SiOx enables scattering resonances (Fabry Perot or Whispering Gallery Modes) which enhances the local electric field on or near the surface of the NS. The NPs placed on the surface of SiOx NS interact with the locally enhanced electric field and exhibit improved optical absorption. By varying the size of the SiOx NS, the resonance wavelengths and the intensity of the local electric field enhancement can be tuned, offering the ability of such structures to effectively utilize a wide range of energies in the visible region. Composite nanostructures comprised of various classes of nanomaterials such as metal-doped semiconductor, plasmonic, and non-plasmonic metal NPs were investigated to perform the desirable solar-to-chemical transformations. First, we employed SiOx-loaded silver-doped silver chloride (SiOx/AgCl(Ag)) photocatalyst to investigate the role of metal-induced gap states in AgCl, a wide bandgap semiconductor. SiOx/AgCl(Ag) exhibit high catalytic performance and photostability after 10 cycles of the probe reaction, methylene blue (MB) degradation under visible light irradiation. The results indicate that the visible light absorption due to metal-induced gap states can be further improved by employing the SiOx NSs as supports that act as optical nanoantenna. We then studied the influence of NP size on the catalytic activity to understand the effect of size in promoting the generation and transfer of hot electrons to surface adsorbates. Our findings indicate that upon employing Ag NPs of different particle size (<10 nm and >10 nm) and normalizing for the optical absorption and moles of surface Ag atoms, the efficient generation and transfer of photoexcited hot electrons is favored in the small-sized Ag NPs (size <10 nm) than bigger Ag NPs. Next, we investigated the selective partial hydrogenation of nitroarene to N-aryl hydroxylamine using SiOx-loaded platinum (SiOx/Pt) photocatalysts. We found that change in the surface electronic structure of the small Pt NPs (size <5 nm) due to light illumination and surface modification (by adding suitable organic ligands), minimize the adsorption of the electron-rich hydroxylamine molecules and minimize their complete conversion to aniline, resulting in high N-hydroxylamine selectivity. Overall, our work shows that well-controlled composite nanostructures comprising of active catalyst loaded on dielectric SiOx NS supports that act as optical nanoantenna are a promising class of photocatalysts for driving photon-to-chemical transformations with high activity and product selectivity. / Chemistry

The desire to incorporate multiple frequency bands of operation into personal communication devices has led to much research on reducing the size of antennas while maintaining adequate performance. GPS is one such application, where dual frequency operation, bandwidth and circular polarization pose major challenges when using traditional miniaturization techniques. Various loading methods have been studied to reduce the resonant frequency of the antenna – high permittivity dielectric loading, slot loading and cavity loading – while examining their effects on bandwidth and gain. The objective of this thesis is to provide guidelines on what is achievable using these miniaturization methods and insight into how to implement them effectively.

Wide bandgap (WBG) devices and power electronic converters (PEC) that enable the dynamic control of energy and high-power density designs inevitably contain defects including sharp edges, triple points, and cavities, which result in local electric field enhancements. The intensified local electric stresses cause either immediate dielectric breakdown or partial discharge (PD) that erodes electrical insulators and accelerates device aging. With the goal of addressing these dielectric challenges emerging in power-dense applications, this dissertation focuses on 1) modeling the dielectric characteristics of supercritical fluids (SCFs), which is a new dielectric medium with high dielectric strength and high cooling capability; and 2) establishing the optimal fabrication conditions of electrets, which is a new dielectric solution that neutralizes locally enhanced electric fields. In this dissertation, the dielectric breakdown characteristics of SCFs are modeled as a function of pressure based on the electron scattering cross section data of clusters that vary in size as a function of temperature and pressure around the critical point. The modeled breakdown electric field is compared with the experimental breakdown measurements of supercritical fluids, which show close agreement. In addition, electrets are fabricated based on the triode-corona charging method and their PD mitigation performance is evaluated through a series of PD experiments. Electrets are fabricated under various charging conditions, including charging voltage, duration, polarity, and temperature with the goal of identifying the optimal condition that leads to effective PD mitigation. The PD mitigation performance of electrets fabricated based on these charging conditions is further assessed by investigating the impact of various power electronics voltage characteristics, including dv/dt, polarity, switching frequency, and duty cycle. Electret based electric field neutralization approach is further utilized in increasing the critical flashover voltage associated with the surface flashover voltage. Moreover, due to the high mechanical strength of epoxy composites at cryogenic temperatures, in this dissertation, epoxy-based electrets are fabricated as a solution to PD in high temperature superconducting cables. The experimental demonstrations conducted with electret in this dissertation is dedicated for the establishing the electret based electric field neutralization approach as a dielectric solution for the dielectric challenges in power electronics driven systems.

Scaling of electronic circuits from micro- to nanometer size determined the incredible development in computer technology in the last decades. In charge storage capacitors that are the largest components in dynamic random access memories (DRAM), dielectrics with higher permittivity (high-k) were needed to replace SiO2. Therefore ZrO2 has been introduced in the capacitor stack to allow sufficient capacitance in decreasing structure sizes. To improve the capacitance density per cell area, approaches with three dimensional structures were developed in device fabrication. To further enable scaling for future generations, significant efforts to replace ZrO2 as high-k dielectric have been undertaken since the 1990s. In calculations, CaTiO3 has been identified as a potential replacement to allow a significant capacitance improvement. This material exhibits a significantly higher permittivity and a sufficient band gap. The scope of this thesis is therefore the preparation and detailed physical and electrical characterization of ultrathin CaTiO3 layers. The complete capacitor stacks including CaTiO3 have been prepared under ultrahigh vacuum to minimize the influence of adsorbents or contaminants at the interfaces. Various electrodes are evaluated regarding temperature stability and chemical reactance to achieve crystalline CaTiO3. An optimal electrode was found to be a stack consisting of Pt on TiN. Physical experiments confirm the excellent band gap of 4.0-4.2 eV for ultrathin CaTiO3 layers. Growth studies to achieve crystalline CaTiO3 indicate a reduction of crystallization temperature from 640°C on SiO2 to 550°C on Pt. This reduction has been investigated in detail in transmission electron microscopy measurements, revealing a local and partial epitaxial growth of (111) CaTiO3 on top of (111) Pt surfaces. This preferential growth is beneficial to the electrical performance with an increased relative permittivity of 55 with the advantage of a low leakage current comparable to that in amorphous CaTiO3 layers. A detailed electrical analysis of capacitors with amorphous and crystalline CaTiO3 reveals a relative permittivity of 30 for amorphous and an excellent value of 105 for fully crystalline CaTiO3. The permittivity exhibits a quadratic dependence with applied electric field. Crystalline CaTiO3 shows a 1-3% drop in capacitance density and permittivity at a bias voltage of 1V, which is significantly lower compared to all results for SrTiO3 capacitors measured elsewhere. A capacitance equivalent thickness (CET) below 1.0 nm with current densities 1×10−8 A/cm2 have been achieved on carbon electrodes. Finally, CETs of about 0.5 nm with leakage currents of 1 × 10−7 A/cm2 on top of Pt/TiN fulfill the 2016 DRAM requirements following the ITRS road map of 2012. / Die Verkleinerung von elektronischen Bauelementen hin zu nanometerkleinen Strukturen beschreibt die unglaubliche Entwicklung der Computertechnologie in den letzten Jahrzehnten. In Ladungsspeicherkondensatoren, den größten Komponenten in Arbeitsspeichern, wurden dafür Dielektrika benötigt, die eine deutlich höhere Permittivität als SiO2 besitzen. ZrO2 wurde als geeignetes Dielektrikum eingeführt, um eine ausreichende Kapazität bei kleiner werdenen Strukturen sicherzustellen. Zur weiteren Verbesserung der Kapazitätsdichte pro Zellfläche konnten 3D Strukturen in die Chipherstellung integriert werden. Seit den 1990ern wurden parallel bedeutende Anstrengungen unternommen, um ZrO2 als Dielektrikum durch Materialien mit noch höherer Permittivität zu ersetzen. Nach Berechnungen stellt nun CaTiO3 eine mögliche Alternative dar, die eine weitere Verbesserung der Kapazität ermöglicht. Das Material besitzt eine deutlich höhere Permittivität und eine ausreichend große Bandlücke. Diese Arbeit beschäftigt sich deshalb mit Herstellung und detaillierter physikalischer und elektrischer Charakterisierung von extrem dünnen CaTiO3 Schichten. Zusätzlich wurden diverse Elektroden bezüglich ihrer Temperaturstabilität und der chemischen Stabilität untersucht, um kristallines CaTiO3 zu herhalten. Als eine optimale Elektrode stellte sich Pt auf TiN heraus. Physikalische Experimente an extrem dünnen CaTiO3 Schichten bestätigen die Bandlücke von 4,0-4,2 eV. Wachstumsuntersuchungen an kristallinem CaTiO3 zeigen eine Reduktion der Kristallisationstemperatur von 640°C auf SiO2 zu 550°C auf Pt. Diese Reduktion wurde detailliert mittels Transmissionselektronenmikroskopie untersucht. Es konnte für einige Schichten ein partielles lokales epitaktischesWachstum von (111) CaTiO3 auf (111) Pt gemessen werden. Dieses Vorzugswachstum ist vorteilhaft für die elektrischen Eigenschaften durch eine gesteigerte Permittivität von 55 bei gleichzeitig geringem Leckstrom vergleichbar zu amorphen Schichten. Eine genaue elektrische Analyse von Kondensatoren mit amorphen und kristallinem CaTiO3 ergibt eine Permittivität von 30 für amorphe und bis zu 105 für kristalline CaTiO3 Schichten. Die Permittivität zeigt eine quadratische Abhängigheit von der angelegten Spannung. Kristallines CaTiO3 zeigt einen 1-3% Abfall der Permittivität bei 1V, der wesentlich geringer ausfällt als vergleichbare Werte für SrTiO3. Eine zu SiO2 vergleichbare Schichtdicke (CET) von unter 1,0 nm mit Stromdichten von 1×10−8 A/cm2 wurde auf Kohlenstoffsubstraten erreicht. Mit Werten von 0,5 nm bei Leckstromdichten von 1×10−7 A/cm2 auf Pt/TiN Elektroden erfüllen die CaTiO3 Kondensatoren die Anforderungen der ITRS Strategiepläne für Arbeitsspeicher ab 2016.

A numerical study has been performed to investigate the mechanics of the turbulent wake of a circular cylinder that is controlled by a plasma actuator. The numerical investigation implements a straightforward moving wall boundary condition to model the actuator's effects on the flow. Validations of the moving wall for this simulation are set forth with the understanding that the moving wall can model the plasma actuator bulk flow effects at a distance downstream and not in a region near or on the plasma actuator. The moving wall boundary condition is then applied to a circular cylinder at a Reynolds number of 8,000. At this unsteady transitional flow regime, a large eddy simulation solver is utilized to resolve flow features. The moving walls are placed at the top and bottom ninety degree points of the cylinder and alternately activated at a frequency to produce lock-in behavior. Investigation into the flowfield mechanics reveals that a harmonic frequency of the forced frequency occurs from the creation of sub-vortices from the instantaneous starting and stopping of the moving-wall actuators. With the forcing frequency close to the natural shedding frequency it is found that the aerodynamic drag increases due to the moving wall creating an average low pressure region on to the downstream side of the cylinder. It is also found that drag can be reduced when the forcing frequency is closer to half the natural shedding frequency. This happens because of a decrease in the average pressure on the downstream side of the cylinder.