A superconducting microwave cavity has been designed to test advanced materials for use in the accelerating structures contained within linear colliders. The electromagnetic design of this cavity produces surface magnetic fields on the sample wafer exceeding the critical limit of Niobium. The ability of this cavity to push up to 4 times the critical field provides, for the first time, a short sample method to reproducibly test these thin films to their ultimate limit. In order for this Wafer Test cavity to function appropriately, the large sapphire at the heart of the cavity must have specific inherent qualities. A second cavity was constructed to test these parameters: dielectric constant, loss tangent, and heat capacity. Several tests were performed and consistent values were obtained. The consequences of these measurements were then applied to the Wafer Cavity, and its performance was evaluated for different power inputs. The Q_0 of the cavity could be as low as 10^7 because of the sapphire heating, therefore removing the ability to measure nano-resistances. However, with additional measurements in a less complex environment, such as the Wafer Test Cavity, the Q_0 could be higher than 10^9.

The (BMN) bulk materials were sintered at 1050°C, 1100°C, 1150°C, 1200°C by the conventional ceramic process, and their microstructure and dielectric properties were investigated by Scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy, Transmission electron microscopy (TEM) (including the X-ray energy dispersive spectrometry EDS and high resolution transmission electron microscopy HRTEM) and dielectric impedance analyzer. We systematically investigated the structure, dielectric properties and voltage tunable property of the ceramics prepared at different sintering temperatures. The XRD patterns demonstrated that the synthesized BMN solid solutions had cubic phase pyrochlore-type structure when sintered at 1050°C or higher, and the lattice parameter (a) of the unit cell in BMN solid solution was calculated to be about 10.56Å. The vibrational peaks observed in the Raman spectra of BMN solid solutions also confirmed the cubic phase pyrochlore-type structure of the synthesized BMN. According to the Scanning Electron Microscope (SEM) images, the grain size increased with increasing sintering temperature. Additionally, it was shown that the densities of the BMN ceramic tablets vary with sintering temperature. The calculated theoretical density for the BMN ceramic tablets sintered at different temperatures is about 6.7521 . The density of the respective measured tablets is usually amounting more than 91% and 5 approaching a maximum value of 96.5% for sintering temperature of 1150°C. The microstructure was investigated by using Scanning Transmission Electron Microscope (STEM), X-ray diffraction (XRD). Combined with the results obtained from the STEM and XRD, the impact of sintering temperature on the macroscopic and microscopic structure was discussed. The relative dielectric constant ( ) and dielectric loss ( ) of the BMN solid solutions were measured to be 161-200 and (at room temperature and 100Hz-1MHz), respectively. The BMN solid solutions have relative high dielectric constant and low dielectric loss. With increasing sintering temperature, the dielectric constant showed the maximum at 1150°C. The leakage current of BMN ceramic material is extraordinary small. When the voltage and thickness of the BMN capacitor are 4000V and 300um, the leakage current amounts only about 0.13-0.65 . The excellent physical and electrical properties make BMN thin films promising for potential tunable capacitor applications.

The performance of modern high frequency components and electronic systems are often limited by the properties of the materials from which they are made. Over the past decade, there has been an increased emphasis on the development of new, high performance dielectrics for use in high frequency systems. The development of these materials requires novel broadband characterization, instrumentation, and extraction techniques, from which models can be formulated. For this project several types of dielectric sheets were characterized at terahertz (THz) frequencies using quasi-optical (free-space) techniques. These measurement systems included a Fourier Transform Spectrometer (FTS, scalar), a Time Domain Spectrometer (TDS, vector), a Scalar Network Analyzer (SNA), and a THz Vector Network Analyzer (VNA). Using these instruments the THz spectral characteristics of dielectric samples were obtained. Polarization based anisotropy was observed in many of the materials measured using vector systems. The TDS was the most informative and flexible instrument for dielectric characterization at THz frequencies. To our knowledge, this is the first such comprehensive study to be performed. Anisotropy effects within materials that do not come into play at microwave frequencies (e.g. ~10 GHz) were found, in many cases, to increase measured losses at THz frequencies by up to an order of magnitude. The frequency dependent properties obtained during the course of this study included loss tangent, permittivity (index of refraction), and dielectric constant. The results were largely consistent between all the different systems and correlated closely to manufacturer specifications over a wide frequency range (325 GHz-1.5 THz). Anisotropic behavior was observed for some of the materials. Non-destructive evaluation and testing (NDE/NDT) techniques were used throughout. A precision test fixture was developed to accomplish these measurements. Time delay, insertion loss, and S-parameters were measured directly, from which loss tangent, index of refraction, and permittivity was extracted. The test materials were low-loss dielectric slabs ranging in thickness from 1-60 mils. The substrate sheets were PTFE, fiberglass, and epoxy-ceramic composite substrates. The other group was polyethylene plastic sheets (LDPE/HDPE/UMHW) and 3D printer Photopolymers. The results were verified by using several online THz spectral databases and compared to manufacturer data sheets. Permittivity and loss of some of the test samples varied as a function of polarization angle. 0 - 90 degrees of rotation were tested (i.e., H-V, and 45 degrees polarization). Inter-molecular scattering in the composite materials raised the loss considerably. This effect was verified. Standard, well documented, material types were selected for the project for best comparison. These techniques can also be applied to analyze newer substances such as nanodielectrics.

abstract: The mechanism of loss in high performance microwave dielectrics with complex perovskite structure, including Ba(Zn1/3Ta2/3)O3, Ba(Cd1/3Ta2/3)O3, ZrTiO4-ZnNb2O6, Ba(Zn1/3Nb2/3)O3, and BaTi4O9-BaZn2Ti4O11, has been investigated. We studied materials synthesized in our own lab and from commercial vendors. Then the measured loss tangent was correlated to the optical, structural, and electrical properties of the material. To accurately and quantitatively determine the microwave loss and Electron Paramagnetic Resonance (EPR) spectra as a function of temperature and magnetic field, we developed parallel plate resonator (PPR) and dielectric resonator (DR) techniques. Our studies found a marked increase in the loss at low temperatures is found in materials containing transition metal with unpaired d-electrons as a result of resonant spin excitations in isolated atoms (light doping) or exchange coupled clusters (moderate to high doping) ; a mechanism that differs from the usual suspects. The loss tangent can be drastically reduced by applying static magnetic fields. Our measurements also show that this mechanism significantly contributes to room temperature loss, but does not dominate. In order to study the electronic structure of these materials, we grew single crystal thin film dielectrics for spectroscopic studies, including angular resolved photoemission spectroscopy (ARPES) experiment. We have synthesized stoichiometric Ba(Cd1/3Ta2/3)O3 [BCT] (100) dielectric thin films on MgO (100) substrates using Pulsed Laser Deposition. Over 99% of the BCT film was found to be epitaxial when grown with an elevated substrate temperature of 635 C, an enhanced oxygen pressures of 53 Pa and a Cd-enriched BCT target with a 1 mol BCT: 1.5 mol CdO composition. Analysis of ultra violet optical absorption results indicate that BCT has a bandgap of 4.9 eV. / Dissertation/Thesis / Ph.D. Materials Science and Engineering 2013

Abstract This work presents a method for the fabrication of Li₂MoO₄ ceramics at room-temperature based on utilizing a small amount of water with Li₂MoO₄ powder. The densification of the ceramic takes place during pressing. Thus the shape and size of the final ceramic compact can easily be managed by controlling the mould dimensions and the amount of material. Post-processing at 120 °C is applied to remove residual water from the compact. This post-processing temperature can be chosen to be suitable to the other materials integrated, such as the substrate or electrodes, as long as the post-processing time is adequate to remove the residual water. The dielectric properties (relative permittivity of 5.1 and a loss tangent value of 0.00035 at 9.6 GHz) after optimization of the powder particle size, sample pressing pressure, and post-processing time were similar to those achieved for Li₂MoO₄ ceramics fabricated by sintering at 540 °C. The dielectric properties of Li₂MoO₄ ceramics were also modified using composite methods. For example, an addition of 10 volume-% of BaTiO₃ increased the relative permittivity from 6.4 to 9.7 and the loss tangent value from 0.0006 to 0.011 at 1 GHz. To investigate the thermal dependence of the permittivity, different amounts of rutile TiO₂ were incorporated into a Li₂MoO₄ ceramic matrix fabricated with the method described in this work. As the amount of TiO₂ increased from 10 to 30 volume-%, the thermal coefficient of permittivity decreased from 180 ppm/°C to -170 ppm/°C. The low processing temperature made the fabrication approach introduced here feasible for silver electrode integration without the formation of extra phases, which were observed in sintered samples with similar compositions in another study. A patch antenna was realized utilizing a Li₂MoO₄ ceramic disk fabricated by the room-temperature method. The antenna operating at ~4 GHz showed reasonably good performance. A relative humidity of 80% lowered the resonant frequency by 3.25% from the initial value, and reduced the total and radiation efficiencies of the antenna by ~2 dB. The changes were slowly reversible. Use of a silicone conformal coating reduced the shift of the resonant frequency to 1.26% from the initial value and also reduced the effect on efficiencies to ~1 dB. The use of the coating also speeded up the reversibility of the changes when the humidity was decreased. / Tiivistelmä Tässä työssä esitellään menetelmä, jolla Li₂MoO₄-keraameja voidaan valmistaa huoneenlämpötilassa. Menetelmä hyödyntää pientä määrää Li₂MoO₄-vesiliuosta ja sen kiteytymistä. Keraami tiivistyy kappaletta puristettaessa, joten sen koko ja muoto ovat sama kuin muotilla riippuen vain keraamin määrästä. Kappaleeseen jäänyt vesi poistetaan lämpökäsittelyllä yleensä 120 celsiusasteessa. Jälkikäsittelylämpötila voidaan valita muiden integroitavien materiaalien mukaan, kuten alusta- tai elektrodimateriaalin, kunhan jälkikäsittelyaikaa muokataan vastaavasti, jotta kaikki vesi poistuu. Optimoimalla Li₂MoO₄-jauheen partikkelikokoa, puristuspainetta ja jälkikäsittelyaikaa saavutettiin samankaltaiset dielektriset ominaisuudet taajuudella 9,6 GHz (suhteellinen permittiivisyys 5,1 ja häviötangentti 0,00035) kuin Li₂MoO₄-keraameilla, jotka on sintrattu 540 celsiusasteessa. Li₂MoO₄-keraamien dielektrisiä ominaisuuksia muokattiin myös lisäaineilla. Esimerkiksi 10 tilavuus-% BaTiO₃-jauhetta kasvatti suhteellista permittiivisyyttä taajuudella 1 GHz arvosta 6,4 arvoon 9,7 ja häviötangenttia arvosta 0,0006 arvoon 0,011. Myös eri määriä TiO₂-jauhetta (rutiili) lisättiin Li₂MoO₄-matriisiin permittiivisyyden lämpötilariippuvuuden tutkimiseksi. TiO₂-jauheen määrän kasvaessa 10 tilavuusprosentista 30 tilavuusprosenttiin laski permittiivisyyden lämpötilariippuvuus arvosta 180 ppm/°C arvoon -170 ppm/°C. Matalan käsittelylämpötilan ansiosta työssä esitelty valmistusmenetelmä soveltui käytettäväksi hopeaelektrodien kanssa. Aiemman tutkimuksen mukaan nämä komposiittimateriaalit muodostivat ei-toivottuja faaseja sintrattaessa hopean kanssa. Menetelmällä valmistettua Li₂MoO₄-keraamikiekkoa käytettiin mikroliuska-antennin valmistuksessa. Taajuudella 4 GHz toimivan antennin suorituskyky oli suunnitellun kaltainen. 80 prosentin suhteellinen ilmankosteus laski resonanssitaajuutta 3,25 % alkuperäisestä arvosta ja vähensi antennin kokonais- ja säteilytehokkuutta noin 2 dB. Muutokset palautuivat hitaasti. Silikonisuojalakan käyttö vähensi taajuuden laskua 1,26 prosenttiin alkuperäisestä arvosta ja tehokkuudet laskivat vain noin 1 dB. Suojalakan käyttö nopeutti muutosten palautuvuutta ilmankosteuden laskiessa.

Les travaux de thèse sont axés sur le développement de nouvelles techniques de caractérisation basées sur la variation de la réponse d’un résonateur, réponse modifiée par les propriétés diélectriques ou métalliques d’un matériau sous test. La première méthode utilise la microscopie microonde en champ proche pour la caractérisation résonante et non destructive de matériaux diélectriques dans la bande ISM (2,45 GHz).Celle-ci permet de déterminer les propriétés électromagnétiques (permittivité relative, tangente de pertes) des échantillons diélectriques solides de faible volumepar rapport à la longueur d’onde de mesure, et cela sans aucun traitement préalable. La connaissance de ces paramètres est essentielle pour fournir des informations critiques nécessaires pour la conception, la modélisation et la fabrication de circuits microondes. Une deuxième approche vise l’étude et le développement d’un nouveau capteur à base de céramique, économique, sensible, et pouvant s’intégrer dans un système sans fil pour la détection et la caractérisation du degré de corrosion. Ces nouveaux capteurs fournissent des informations sur l'état de l'équipement opérationnel d’une structure cible afin d'assurer la sécurité de cette dernière et par conséquent celle de leurs utilisateurs. Pour ces deux axes d’études, des simulations sur des logiciels de calcul électromagnétique ont été effectuées puis validées par des mesures expérimentales. / This Ph. D thesis focuses on the development of new characterization techniques of dielectric and metallic materials in the ISM band (2.45 GHz). The first proposed method is based on non-destructive near field microave microscopy. This technique allows the determination of the electromagnetic properties (permittivity, loss tangent) of solid dielectric samples of small volume without prior treatment. The knowledge of these parameters is essential to provide critical information needed for accurately designing, modeling and manufacturing microwave circuits. A second study focuses on the development of a new, ceramic based, sensitive and economic sensor that can be integrated in a wireless system for the detection and characterization of the corrosion evolution. These new sensors provide information about the state of the operational equipment of the target structure in order to ensure the safety of these structures and therefore that of their users. In these two studies, simulations on electromagnetic calculation software have been performed and validated by experimental measurements.

京都大学 / 新制・課程博士 / 博士(農学) / 甲第25326号 / 農博第2592号 / 新制||農||1105(附属図書館) / 京都大学大学院農学研究科森林科学専攻 / (主査)准教授 簗瀬 佳之, 教授 矢野 浩之, 教授 仲村 匡司, 教授 村田 功二 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DGAM

The increasing number of power electronic devices in medium voltage networks lead to a harmonic distortion of the voltage waveforms in electrical systems. Medium frequency components up to several kHz are superimposed on the fundamental grid voltage. The distorted voltage waveforms stresses the insulation systems due to the additional current and hence additional dielectric losses. The heat generated from dielectric losses is suspected to be an accelerator to insulation ageing below partial discharge inception. Therefore, the systematic assessment of the losses and their correct quantification is crucial to designing reliable insulation systems with a high lifetime. The investigation of losses under nonsinusoidal and distorted voltage waveforms is not trivial and has been subject to little research to date, compared to investigations at 50 or 60 Hz. In this paper, several approaches of quantifying dielectric losses under multifrequent voltage waveforms are presented and compared. The losses of cast resin specimens are quantified with a test setup using a reference measurement method. The loss computation algorithms range from previously utilised Extrapolation and Superposition approaches to a direct power measurement technique. The results presented in this contribution show that the different measurement procedures provide considerably different outcomes for which possible explanations are given. The presented data indicates that realistic field strength conditions should be ensured in order to quantify the losses under distorted voltage waveformes correctly.

abstract: Microwave properties of low-loss commercial dielectric materials are optimized by adding transition-metal dopants or alloying agents (i.e. Ni, Co, Mn) to tune the temperature coefficient of resonant frequency (τf) to zero. This occurs as a result of the temperature dependence of dielectric constant offsetting the thermal expansion. At cryogenic temperatures, the microwave loss in these dielectric materials is dominated by electron paramagnetic resonance (EPR) loss, which results from the spin-excitations of d-shell electron spins in exchange-coupled clusters. We show that the origin of the observed magnetically-induced shifts in the dielectric resonator frequency originates from the same mechanism, as described by the Kramers-Kronig relations. The temperature coefficient of resonator frequency, τf, is related to three material parameters according to the equation, τf = - (½ τε + ½ τµ + αL), where τε, τµ, and αL are the temperature coefficient of dielectric constant, magnetic permeability, and lattice constant, respectively. Each of these parameters for dielectric materials of interest are measured experimentally. These results, in combination with density functional simulations, developed a much improved understanding of the fundamental mechanisms responsible for τf. The same experimental methods have been used to characterize in-situ the physical nature and concentration of performance-degrading point defects in the dielectrics of superconducting planar microwave resonators. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2016

Abstract The main objective of this thesis was to research and develop a sensitive characterization method for dielectric powdery substances which could be utilized in various industrial and research fields. With modern electromagnetic simulation tools and the presented experimental measurements, the characterization of dielectric powders using an indirectly coupled open-ended coaxial cavity resonator operating in TEM mode at 4.5 GHz was found to have potential. The modelling and the experimental measurement results of commonly used dielectric powders revealed that, from the nine classical mixing rules, it was possible to derive reliable inclusion permittivity values when using the properties of the perturbed resonator and the Bruggeman symmetric and the Looyenga mixing theories. In addition, the determination accuracy of the inclusion permittivity was found to be greatly improved with the correction factor included into the previously presented permittivity equation of the quarter wave coaxial resonator. Determination of the dielectric losses was found to be reliable when using the differences between the perturbed and unperturbed resonator and the general mixing model equation. The sensitivity of the characterization method was researched with both humidity exposed and surfactant treated modified SiO2, Al2O3 and ZrO2 powders. Experimental results showed that the effect of adsorbed water on the particles was most pronounced when measuring the dielectric losses of the inclusions. Furthermore, a clear correlation with the theory of the general mixing model was found. Thus, in addition to the changed dielectric properties between dry and humidity exposed powders, it was also possible to determine the moisture content with reasonable accuracy. This correlated well with the traditional, mass based, determination. Stearic acid coating of the particles induced only a small change in inclusion permittivity but a notable change in dielectric losses. Unlike the cases with the larger particle sized SiO2 and Al2O3, the dielectric loss of ZrO2 inclusions, with stearic acid coating, was decreased significantly from 6.2 × 10-3 to 3.8 × 10-3. When characterizing magnesium and calcium titanate composite powders, with CaTiO3 molar ratios of 0.0, 0.02, 0.05 and 0.1, the method was found to have good sensitivity and accuracy. Additions of CaTiO3 exhibited a clear increase in net inclusion permittivities from 13.4 up to 14.9 and in dielectric loss tangents from 7.1 × 10-3 up to 8.5 × 10-3. In addition, a good correlation was found in the theoretical determination of the CaTiO3 molar ratios using the resonator measurement results and the general mixing model. The characterization method was proved to be capable of measuring the dielectric properties and detecting even very slight changes in the powders. Thus, the method could be utilized in various types of powdery material characterization, for example, in the analysis and quality control of different composite powders. / Tiivistelmä Väitöstyön päätavoitteena oli tutkia ja kehittää herkkä jauhemaisten eristemateriaalien karakterisointimenetelmä, jota voitaisiin hyödyntää usealla teollisuuden ja tutkimuksen alueella. Hyödyntäen nykyaikaisia sähkömagnetiikan simulointityökaluja sekä kokeellisia mittauksia, havaittiin TEM -moodissa 4,5 GHz taajuudella toimivan avoimen epäsuorasti kytketyn koaksiaalionteloresonaattorin soveltuvan karakterisoimaan eristejauheita. Sähkömagneettinenmallinnus yhdessä yleisesti käytettyjen eristejauheiden kokeellisten mittausten kanssa osoitti, että partikkelin permittiivisyysarvot voitiin johtaa luotettavasti. Tällöin käytettiin näytemateriaalilla täytetyn resonaattorin ominaisuuksia, sekä yhdeksästä vertaillusta klassisesta sekoitusyhtälöstä Bruggeman symmetristä ja Looyengan sekoitusteorioita. Tämän lisäksi tarkkuutta voitiin parantaa huomattavasti lisäämällä korjauskerroin aikaisemmin julkaistuun neljännesaalto-koaksiaaliresonaattorin permittiivisyyden määrittävään yhtälöön. Eristehäviöiden määrittäminen havaittiin luotettavaksi, kun käytettiin mitattavalla materiaalilla muutetun ja tyhjän resonaattorin ominaisuuksien eroja, sekä general mixing model -yhtälöä. Karakterisointimenetelmän herkkyys tutkittiin ilmankosteudelle altistetuilla, sekä pintakäsittelyllä muutetuilla SiO2, Al2O3 ja ZrO2 -jauheilla. Mittaustulokset osoittivat, että partikkelin pinnalle adsorpoituneen veden vaikutus oli kaikkein korostunein, kun mitattiin partikkelien eristehäviöitä. Tämän lisäksi havaittiin myös selkeä korrelaatio general mixing model -teorian kanssa. Näin ollen muuttuneiden eristeominaisuuksien määritysten lisäksi voitiin määrittää jauheen kosteussisältö riittävällä tarkkuudella. Tulokset korreloivat hyvin perinteisen massaeroihin perustuvan määrittämisen kanssa. Partikkelien pinnoitus steariinihapolla aiheutti ainoastaan pienen muutoksen permittiivisyyteen mutta merkittävän muutoksen eristehäviöihin. Toisin kuin suuremman partikkelikoon SiO2:lla ja Al2O3:lla ZrO2 -partikkelin eristehäviö laski huomattavasti steariinihappopinnoituksen jälkeen, 6,2 × 10-3:sta 3,8 × 10-3:een. Karakterisoitaessa magnesium- ja kalsiumtitanaattikomposiittijauheita käyttämällä CaTiO3 -moolisuhteita 0,0, 0,02, 0,05 ja 0,1 menetelmällä havaittiin olevan hyvä herkkyys ja tarkkuus mitattavan materiaalin muutoksille. CaTiO3 -määrän lisäykset aiheuttivat selkeän nousun partikkelien kokonaispermittiivisyyksissä, joka kasvoi 13,4:sta 14,9:ään, sekä häviötangentissa, joka kasvoi 7,1 × 10-3:sta aina 8,5 × 10-3:een. Tämän lisäksi resonaattorin mitattuihin ominaisuuksiin sekä general mixing model -yhtälöön perustuvan teoreettisen määrityksen havaittin korreloivan hyvin CaTiO3 -moolisuhteisiin. Karakterisointimenetelmän osoitettiin soveltuvan eristeominaisuuksien mittaukseen sekä havaitsemaan jopa erittäin pienet muutokset jauheiden eristeominaisuuksissa. Menetelmää voitaisiin hyödyntää usean tyyppisissä jauhemateriaalien ominaisuuksien määrityksissä, kuten esimerkiksi erilaisten komposiittijauheiden analysoinnissa ja laaduntarkkailussa.