Broadband Dielectric Spectroscopy (BDS) in combination with a nanostructured electrode arrangement – which circumvents the conventional need to evaporate metal electrodes onto soft matter – is used to study the molecular dynamics of several glass forming materials confined in nanometric (> 5 nm) layers. Other complementary experimental tools employed in this work include spectroscopic vis-Ellipsometry (SE), AC-chip calorimetry (ACC), X-ray reflectrometry (XRR), Differential Scanning Calorimetry (DSC) and Atomic Force Microscopy (AFM). The latter is used to characterize the topography of the samples and to determine their thicknesses. Under the conditions of annealing samples (Tg + 50K) in high oil-free vacuum (10E-6 mbars) for at least 12 h and carrying out measurements in inert (dry nitrogen or argon) atmosphere, it is found for all studied thin layers that the structural relaxation, and hence the dynamic glass transition – in its mean relaxation times – remains within a margin ±3 K from the respective bulk behaviour. It is revealed, inter alia, that the one-dimensional confinement of thin films introduces restrictions on other (slower) molecular relaxation processes which manifest, depending on the specific system under investigation, as (i) an interruption of the end-to-end (normal mode) fluctuation of the chains, or (ii) a slowing down of the delta-relaxation when the system is cooled towards glass-formation. Furthermore, (iii) evidence is provided to show that the dimensionality of confinement plays a significant role in determining the resulting dynamics. A molecular understanding of these findings is given, and the discussion presented with respect to the on-going international debate about dynamics in confinement.

Die fortwährende Verkleinerung der Strukturbreiten in der Mikroelektronik erfordert es, herkömmliche SiO2 Dielektrika durch Materialien mit kleinerer Dielektrizitätskonstante zu ersetzen. Dafür sind verschiedene „low-k Materialien“ entwickelt worden. Unter diesen sind die Organosilikatgläser, die aus SiO2 Netzwerken mit eingelagerten Methylgruppen bestehen wegen ihrer ausgezeichneten Eigenschaften besonders interessant als Dielektrika zwischen metallischen Leiterbahnen. In dieser Arbeit sind fünf verschiedene dieser „low-k Materialien“ untersucht worden: ein dichtes und vier poröse Materialien, die alle durch plasmagestützte chemische Gasphasenabscheidung hergestellt wurden. Die strukturellen, chemischen und dielektrischen Eigenschaften der Materialien wurden mit Hilfe der analytischen Durchstrahlungselektronenmikroskopie unter Verwendung eines abbildenden GATAN-Energiespektrometers untersucht. Die Bestimmung der radialen Verteilungsfunktion (RDF) zur Charakterisierung der atomaren Nahordnung ermöglicht uns die Ermittlung mittlerer Bindungslängen und – winkel sowie der mikroskopischen Dichte des Materials. Gegenüber SiO2 wurden in den untersuchten „low-k Materialien“ stark veränderte mittlere Si-O, O-O und Si-Si Bindungslängen gefunden. Dieses wirkt sich natürlich auch auf die mittleren Si-O-Si bzw. O-Si-O Bindungswinkel aus, und wie erwartet war auch die mikroskopische Dichte der „low-k Materialien“ kleiner als die Dichte des SiO2. Elektronen Energieverlustspektroskopie (EELS) und Photoelektronenspektroskopie (XPS) wurden zur Charakterisierung der chemischen Umgebung der Atome in den „low-k Materialien“ herangezogen. Die Energien von Ionisationskanten und die Bindungsenergien der Silizium-2p und Sauerstoff-1s Elektronen waren in den „low-k Materialien“ größer als im SiO2. Die Kohlenstoffatome kamen in den „low-k Materialien“ sowohl sp2 als auch sp3 hybridisiert vor. sp2-Hybridisierung liegt vor, wenn Bindungen wie Si=CH2 und C=C im Netzwerk vorkommen, während sp3 Hybridisierung z.B. dann vorkommt, wenn freie Si-Bindungen durch –CH3 Gruppen abgesättigt werden. Die Anteile an sp2- bzw. sp3-hybridisierten Kohlenstoffatome wurden aus der Feinstruktur der K-Energieverlustkanten des Kohlenstoffs abgeschätzt. Das ergab, daß die meisten Kohlenstoffatome in den „low-k Materialien“ sp2-hybridisiert sind. Die dielektrischen Eigenschaften wurden durch Kramers-Kronig-Transformation einer Energieverlustfunktion ermittelt, die aus dem Niedrigverlust-EELS-Spektrum im Bereich der Plasmonenanregungen gewonnen wurde. Die Bandlücke des SiO2 beträgt ungefähr 9 eV während dichte „low-k Materialien“ aufgrund der Unregelmäßigkeiten in ihrem SiO2-Netzwerk zusätzliche Zustandsdichten innerhalb der Bandlücke aufweisen. Die Erzeugung von Poren im „low-k Material“ vermindert offenbar die Zustandsdichte im Bereich der Bandlücke und erweitert diese im Vergleich zum SiO2. Eine Modellrechnung mit der Dichtefunktionaltheorie für ein Strukturmodell, das den „low-k Materialien“ nahe kommt, ist zum Vergleich mit der experimentell gefundenen kombinierten Zustandsdichte herangezogen worden und zeigt eine gute Übereinstimmung. Die im Standard-Herstellungsprozeß vorkommenden Verfahren des Plasmaätzens und der Plasmaveraschung können die Struktur des „low-k Materials“ z.B. an den Seitenwänden von Ätzgräben verändern. Die gestörten Bereiche wurden mit der energiegefilterten Elektronenmikroskopie untersucht. Dabei wurde gefunden, daß sich die Strukturveränderungen der Seitenwände bis zu einer Tiefe in der Größenordnung von ungefähr 10 Nanometern erstrecken. Diese Bereiche sind verarmt an Kohlenstoff und ähneln folglich mehr einem SiO2-Dielektrikum. Die Kohlenstoffverarmung erstreckt sich in die „low-k Schicht“ in Form eines gaussartigen Profils mit maximaler Kohlenstoffkonzentration in der Mitte der Schicht. Die Sauerstoffkonzentration und die mikroskopische Dichte steigen in der Nähe der Seitenwände.

No description available.

Les développements technologiques en télécommunication et microondes tendent depuis plusieurs années vers la miniaturisation des circuits, une réduction des coûts, des masses et des pertes dans ces dispositifs. Les circuits SIW (Substrate Integrated Waveguide) s’inscrivent tout à fait dans cette mouvance et font à l’heure actuelle l’objet de nombreux sujets de recherche avec des applications directes dans l’industrie. Les circuits SINRD (Substrate Integrated Non Radiative Dielectric) utilisent eux les propriétés du substrat usiné (insertion de trous) pour la propagation du signal et des fonctions de l’électronique peuvent également être développées avec cette technologie. La conception de ces circuits passe généralement par des outils peu performants car non dédiés. Dans ce travail de thèse, une méthode numérique dédiée à ces circuits est développée. Elle est validée par comparaison à d’autres méthodes numériques et des mesures. Elle présente des temps de calcul très faibles. De nouveaux dispositifs pour des applications en télécommunications spatiales bas coûts et faibles pertes peuvent ainsi être développés grâce à elle. / For several years, technological developments in telecommunications and microwave circuit tend to miniaturization, low cost and mass reduction, in these devices. SIW Circuits (Substrate Integrated Waveguide) are developed in this manner and are currently the subject of numerous research topics with direct applications in industry. SINRD circuits (Substrate Integrated Non Radiative Dielectric) use micro machined substrate properties (insertion of holes) for signal propagation and electronic functions can be developed with this technology. The design of these circuits generally use unefficient tools that are not dedicated to these circuits. In this thesis, a numerical method dedicated to these circuits is developed. It is validated by comparison with other numerical methods and measurements. It presents very low computation time. New designs for applications in space communications and low-cost lowloss circuits may be developed through it.

Abstract The purpose of this task is to synthesize a dielectric substrate material through a sintering process, which can be used for non-invasive physiological sensor development. Low loss, high dielectric constant ceramic material is used. Sintering process is employed to ensure stable structure and homogeneous dielectric properties of the substrate. Samples were prepared with TiO2 and in combination with CuO and Al2O3. All samples were measured and validated in 500 MHz to 20 GHz frequency range. Characterization measurements were performed with a Vector Network Analyzer, FieldFox N9918A, and connected to Keysight, open ended coaxial probe and performance probe. Reflection based measurement method was used due to its simplicity, speed and requirement of wideband data. The dielectric measurement results of developed samples show non-frequency dispersive behaviour, high dielectric constant and data was also selected at 2.45 GHz in aligned to the industrial, scientific and medical band. The resulting measurements show the highest dielectric constant of 16.6 at 2.45 GHz with a very low loss behaviour. / Målet är att syntetisera ett material, genom sintringsprocess, som kan användas som ett dielektriskt substrat för utveckling av sensorer. Det dielektriska materialet har keramisk materialstruktur och innehar högt dielektricitetskonstant med låga dielektriska materialförluster. Denna uppgift kräver att dielektriska materialet ska vara stabilt och inneha isotropiska egenskaper efter att genomgått sintringsprocess. Proverna förberedes med TiO2 och även i kombination med TiO2 tillsammans med CuO och Al2O3. Proverna mäts i frekvensområdet 500 MHz till 20 GHz. Mätningarna utförs med Vector Network Analyzer, FieldFox N9918A från Keysight. Resultat som visas och jämförs i arbetet är tagna vid 2.45 GHz eftersom det används och är standardiserat för medicinskt frekvensband. Högsta uppmätta dielektricitetskonstant har värdet av 16,6. Resultaten visar även låga förluster i dielektrikumet.

High dielectric constant materials have tremendous impact on miniaturization of devices that are used in various applications like wireless communication systems, microelectronics, global positioning systems, etc. To store electric charge in a very small space necessarily needs a capacitor with very high dielectric constant. Thus, these materials are very important in fabricating capacitors, or metal oxide semiconductor filed effect transistor (MOSFET). Among the existing commercially available devices, silicon-based microelectronic devices are commonly used based on the moderately stable dielectric constants of silicon with low losses and minimal temperature and frequency dependence. However, now-a-days, the perovskite based transition metal oxides have drawn attention that have the ability to fulfill all the requirements for being a good dielectric material in all the industrial applications. In this thesis we have studied a few selected perovskite based transition metal oxide systems in terms of their dielectric and magnetic behaviour. In Chapter 1, we have have given brief introductions about the some application of dielectric materials and the origin of dielectric and magnetic properties in the materials. We have also discussed about the polarisation in the dielectric materials to understand it’s frequency dependence and also to formalise different relaxation behaviour with the help of physical and mathematical explanation. In Chapter 2, we describe the various methodologies adopted in this thesis. In Chapter 3, we have studied the dielectric behaviour of Nd2NiMnO6, a rare earth based double perovskite ferromagnetic insulator. We successfully synthesised and characterised the compounds, settled the valency issues with the help of temperature dependent XAS of the transition metal atom in contrast to the existing controversy available in literature. We have found that this material shows relaxor kind behaviour with a colossal dielectric constant value. We have studied in details the origin of the colossal dielectric constant and the relaxation behaviour along with the a.c and d.c. transport properties. We have shown the origin of the ferromagnetism (TC ∼ 200 K) with a low temperature antiferromagnetic ordering (TN ∼ 55 K) with the help of detailed studies of temperature dependent d.c., a.c. magnetism and their XMCD. We have also investigated the isothermal variation of magnetodielectric and magnetoresistance behaviour as a function of magnetic field and their origin. In Chapter 4,we study the effect of cation anti-site disorder on the magnetic, dielectric and transport properties of another rare earth based ferromagnetic double perovskite insulator La2NiMnO6 by controlling different extent of anti-site disordered. We have confirmed the valency of the transition metal cations using XAS technique and followed by shown, different types of magnetic interaction between the transition metal cations using d.c magnetic, quantitative XMCD analysis and the origin of large dielectric response, a.c. transport & dielectric relaxation using temperature variation dielectric measurement as an experimental evidence in contrast of our previous speculation published in literature. We further have studied, the coupling between the magnetic and electric spin through isothermal magnetodielectric measurement. In Chapter 5, we have successfully synthesised and characterised a solid solution of YMnxIn1−xO3 series via different mol % of In doping in the multiferroic YMnO3 system. YMnO3 is a well known multiferroic material studied rigorously during past few decades. We have seen, YMnO3 which has a antiferromagnetic ordering temperature of ∼ 75 K suppressed with increasing the dopant concentration In. We have figured out the effect of In doping in the suppression of multiferroic phase and extended it to the dielectric properties. We have found that, the temperature dependence of dielectric constant shows an anomaly at the magnetic ordering temperature and studied magnetodielectric coupling. We have also investigated the temperature variation of dielectric relaxation and a.c. transport behaviour as a function of composition. In Chapter 6, we have identified the phase seperation and proposed a phase diagram as function of Gd doping in the Ho2−xGdxCuTiO6 double perovskite, where two end member, namely Ho2CuTiO6 and Gd2CuTiO6 are found to be in two different crystallographic phase as, hexagonal (P63cm) and orthorhombic (Pnmm), respectively. We have characterised the valency of the transition metal cations using XAS.We have seen very less temperature and frequency dependence of dielectric constant in hexagonal phase in compare to the orthorhombic phase and tried to figuring out from experimental analysis by performing temperature dependence dielectric const measurement. We also have shown the effect of doping in the origin of dielectric relaxation, a.c transport and magnetic behaviour of this system. In Chapter 7, we have synthesised and characterised successfully two different rare earth based layered perovskite La3Cu2VO9 and La4Cu3MoO12 compounds are of centrosymmetric space group. We have figured it of the valency of the different atoms present in the compound using XAS. We also do have observed the good temperature stability of dielectric constant of these materials and explored origin of mechanism in the dielectric relaxation, a.c. transport property by performing the temperature dependance dielectric measurement. The magnetic structure also have shown with the help of d.d. magnetic measurements. In Appendix A, we have seen the very stable dielectric constant constant from very low to above room temperature of the 2D nano PbS. The frequency stability of dielectric constant is also remarkable in compare to bulk PbS values available in literature. We have explored the origin of the conductivity and relaxation mechanism performing dielectric constant measurement. In conclusion, we investigate, in this thesis, dielectric properties of different transition metal oxides system and the mechanism of dielectric relaxation, a.c, d.c transport and their origin of magnetic response.

Submitted by Marilene Donadel (marilene.donadel@unioeste.br) on 2018-04-26T18:38:37Z No. of bitstreams: 1 Karina_Sanderson_2017.pdf: 3684654 bytes, checksum: 61d1f7f0f704e49f62966d42bae3ceae (MD5) / Made available in DSpace on 2018-04-26T18:38:37Z (GMT). No. of bitstreams: 1 Karina_Sanderson_2017.pdf: 3684654 bytes, checksum: 61d1f7f0f704e49f62966d42bae3ceae (MD5) Previous issue date: 2017-12-13 / Power distribution companies constantly contaminate the environment with dielectric fluids due to power transformer failures and leaks. In this way, these fluids should be studied, as they may entail the vulnerability of the fauna and flora. In this sense, the objective of this work was to investigate the deleterious effects of vegetal and mineral dielectric fluids, through biodegradability, acute toxicity, chemical attributes and soil degradation (oils and greases) tests as well as soybean phytotechnical characteristics evaluation. In the tests of the immediate biodegradability, vegetal dielectric fluids of crambe, W3, W6 and W9 and one based on mineral oil (Lubrax) were studied. For the acute toxicity tests with Danio rerio and Artemia salina and the soil toxicity tests using soybean (Glycine max L.), the W3 and Lubrax dielectric fluid were used. The biodegradability analysis was evaluated by the action of microorganisms that transformed the sample into CO2, being measured by titulometry. For the acute toxicity studies, two distinct experiments were performed, where the organisms were exposed to different concentrations of the W3 and Lubrax dielectric fluids and to the FSA of the fluids. The FSA of W3 and Lubrax used in the Danio rerio assay were subjected to gas chromatography analysis. The acute toxicity tests with Danio rerio and Artemia salina were carried out in order to know the approximate range of fluid toxicity, taking into account the lower dilution that caused lethality in 50% of organisms (LC50). The soil chemical attributes analyzed were: pH, P, K, Ca, Mg, CTC and V. The content of oils and greases of the dielectric fluids was quantified by the Soxhlet type extraction method. For the phytothecnical evaluations, emergence, plant height, stem diameter, root length, root dry matter, number of pods and grains, and the mass of one thousand grains were analyzed. Vegetable dielectric fluids are biodegradable over a period of 14 days, while mineral oil is difficult to biodegrade. In the acute toxicity study, W3 had a lower LC50 than Lubrax, causing higher mortality in the organisms. The LC50 for the Danio rerio was 2.46 gL-1 (Lubrax) and 0.318 gL-1 (W3). For Artemia salina the LC50 was 4.63 gL-1 (Lubrax) and 0.641 gL-1 (W3). In relation to the FSA tests, the Lubrax one caused a greater toxic effect on the organisms, while the W3 had no toxic effect on 50% of organisms. The LC50 values for Lubrax were 4.89% for the Danio rerio and 7.67% for Artemia salina. Chromatographic analysis of FSA of the fluids was not conclusive, it only suggests that the toxicity may be related to the solubility of all the substances present in Lubrax and not only to the solubility of n-alkanes. The chemical attributes of the soil did not change significantly, only the carbon presented increasing variation in relation to the concentrations of the fluids. There was a reduction of the TOG during the agricultural years and the soils in the presence of W3 presented greater degradation than those with Lubrax. The increase in the concentration of the dielectric fluids caused a reduction in the phytotechnical characteristics of the soybean. Plants from soil contaminated with W3 showed better development compared to plants that were in soil contaminated with Lubrax. / As concessionárias de energia, constantemente, contaminam o meio ambiente com fluidos dielétricos, devido a falhas e vazamentos de transformadores de potência. Desta forma, estes fluidos devem ser estudados, pois podem pode implicar na vulnerabilidade da fauna e da flora. Neste sentido, este trabalho teve como objetivo investigar os efeitos deletérios do fluido dielétrico vegetal e mineral, através de ensaios de biodegradabilidade, toxicidade aguda, ensaios dos atributos químicos e degradação (óleos e graxas) do solo e das avalições das características fitotécnicas da soja. Nos ensaios da biodegradabilidade imediata foram estudados os fluidos dielétricos vegetais de crambe, W3, W6 e W9 e um à base de óleo mineral (Lubrax). Para os ensaios de toxicidade aguda com Danio rerio e Artemia salina e para os ensaios de toxicidade em solo utilizando a soja (Glycine max L.), foram usados o fluido dielétrico W3 e o Lubrax. A análise da biodegradabilidade foi avaliada pela ação de microrganismos que transformaram a amostra em CO2, sendo medido por titulometria. Para os estudos da toxicidade aguda foram realizados dois experimentos distintos, onde os organismos foram expostos às diferentes concentrações de fluido dielétrico W3 e Lubrax e onde foram expostos à FSA dos fluidos. A FSA do W3 e Lubrax utilizado no ensaio com o Danio rerio foram submetida a análise de cromatografia gasosa. Os ensaios de toxicidade aguda com o Danio rerio e a Artemia salina foram realizados com o intuito de se conhecer a faixa aproximada de toxicidade dos fluidos, levando em consideração a menor diluição que causou letalidade em 50% dos organismos (CL50). As análises dos atributos químicos do solo foram: pH, P, K, Ca, Mg, CTC e V. O teor de óleos e graxas dos fluidos dielétricos foi quantificado pelo método de extração em aparelho tipo Soxhlet. Para as avaliações fitotécnicas da soja analisou-se a emergência, altura de planta, diâmetro do caule, comprimento radicular, matéria seca radicular, número de vagens e de grãos e a massa de mil grãos. Os fluidos dielétricos vegetais são biodegradáveis num período de 14 dias, enquanto o óleo mineral é difícil de ser biodegradado. No estudo da toxicidade aguda o W3 apresentou uma CL50 menor do que o Lubrax, causando maior mortalidade nos organismos. A CL50 para o Danio rerio foi de 2,46 gL-1 (Lubrax) e de 0,318 gL-1 (W3). Para a Artemia salina a CL50 foi de 4,63 gL-1 (Lubrax) e 0,641 gL-1 (W3). Em relação aos ensaios com a FSA, o Lubrax causou maior efeito tóxico aos organismos. O W3 não apresentou efeito tóxico a 50% dos organismos. Os valores da CL50 para o Lubrax foi de 4,89% para o Danio rerio e 7,67% Artemia salina. A análise cromatográfica da FSA dos fluidos não foi conclusiva, apenas sugere que a toxicidade pode estar relacionada com a solubilidade de todas as substâncias presentes no Lubrax e não apenas com a solubilidade dos n-alcanos. Os atributos químicos do solo não sofreram alterações significativas, apenas o carbono apresentou variação crescente em relação às concentrações dos fluidos. Houve redução do TOG durante os anos agrícolas e os solos em presença do W3 apresentaram maior degradação do que os em solos com Lubrax. O aumento da concentração dos fluidos dielétricos ocasionou redução nas características fitotécnicas da soja. As plantas em solo contaminadas com W3 apresentaram melhor desenvolvimento em relação às plantas que estavam no solo contaminado com Lubrax.

This work deals with influence nanoparticles, as fillers of polymer, to electrical properties dielectric composite materials. Addition of just a few weight percent of nonofillers has profound impact on the physical, chemical, mechanical and electrical properties orf polymer. Simultaneously is focused on production and diagnostics by the relaxation spectroscopy and measure internal resistance. Examination material is epoxy resin TSA 220S filled Al2O3 and SiO2 nanoparticles.

This diploma thesis is focused on the analysis of basic problematics of dielectrics and nanocomposites. It describes the fabrication of experimental samples of nanocomposites from sealing epoxy resin and nanoparticles of titanium dioxide with various weight filling. Further, the thesis deals with measuring and evaluation of dielectric properties of the samples. It examines the influence of weight filling, temperature and frequency of the electric field on volume resistivity, relative permitivity and loss factor.

The dissertation deals with the time-domain dielectric relaxation spectroscopy of carboxymethylcellulose. The main attention was paid to the experimental part of research, mainly to the design and subsequent development of an experimental setup for the measurement of discharge currents and for their processing and analysis. The subject of the measurement is carboxymethylcellulose (CMC), which is a simple polysaccharide used in wide range of applications, among else also in biomedical engineering. The study of CMC properties has required the development of a new experimental set-up of original design, which includes the equilibration (short-circuiting) of a sample before the measurement, charging and discharging at defined time intervals, switching between these two modes, recording of measurement, adjustments and processing of measured signals up to Fourier transformation into the frequency domain and, finally, calculation of complex permittivity of the sample. The frequency dependence of complex permittivity or its imaginary part, obtained by Fourier transformation of discharge current in time domain, is then referred to as the dielectric spectrum. In view of the fact that current measurements were done at very low levels of measured signal (below 10-12 A) the whole measurement was no easy matter. The framework of the work also necessitated studies and subsequent resolution of problems associated with shielding, grounding, presence of noise and sensitivity to various ambient influences. The research work focused on a reliable and trustworthy measurement of very low discharge currents and, subsequently, mathematical processing of noise present in them, i.e., operations with the original, experimentally established signal in time domain, leading in principle to a digital filtration of measured dielectric data. A further pursued objective is the explanation of dielectric parameters of tested carboxymethylcellulose sample in the widest possible frequency spectrum. The integral part of the research was the selection and application of the method for the transformation of the adjusted signal to the frequency domain. The experimental works, including data processing, were carried out in the Department of Physics, Brno FEEC BUT. Measurements were done with Keithley 617 Electrometer, HP4284A Frequency Analyzer and Janis CCS-400-204 cryogenic system. The results were completed with results obtained at the V Department of Experimental Physics, Centre for Electronic Correlations and Magnetism, University of Augsburg, Germany.