This work consider with monitoring components of komplex permittivity at frequency section of electro-insulation material in process of wetting by dielectric relaxation spectroscopy.

This master’s thesis applies dielectric relaxation spectroscopy to analyse impact of climatic changes on dielectric properties of composite material samples (TSA 220S varnish combined with 60.030 mica). Experiments aim to analyse effect of mica composite mass ratio (0, 4, 8 and 16 % of mica), relative humidity (0, 33, 55, 65, 75 and 95 %) and temperature (23, 30, 40 and 50 C) on complex permitivity as a function of frequency.

The diploma project deals with the numerical modeling, implementation and measurement of dielectric dipoles excited by a coaxial probe. Attention was turned to shape optimization of dipoles from the viewpoint of ultra wideband parameters in the band group 6. (“Bandgroup 6“). Two antennas exhibiting the best parameters were fabricated. Results of measurements were compared with simulation results. Simulations and measurements were in agreement. For the simulations, we use program CST Microwave Studio.

No description available.

High dielectric constant materials are of technological importance as they lead to the miniaturization of the electronic devices. For instance, in the case of memory devices based on capacitive components, such as static and dynamic random access memories, the dielectric constant will ultimately decide the level of miniaturization. In this context, the observation of anomalously high dielectric constant (>10) in the double perovskite Sr2SbMnO6 (SSM) over wide frequency (100 Hz1 MHz) and (190373 K) temperature range has attracted a great deal of attention. However, unfortunately their dielectric losses were also high which limit their use for possible capacitor and related applications. The dielectric loss however was known to decrease with decreasing crystallite size in electroceramics. Therefore, the present work has been focused on the synthesis of nanocrystalline SSM powders by moltensalt route. The characterization of the ceramics fabricated from these powders for their microstructural and dielectric properties. A cubic phase of SSM powder was obtained by calcining the as synthesized powders at 900°C/10h by using sulphate flux. The crystallite size was ~ 60 nm. The activation energy associated with the particle growth was found to be 95 ± 5 kJmol-1 . The ceramic sintered at 1075°C/16h exhibited high dielectric constant (>10at 1 kHz) with low loss (0.72 at 1 kHz) at room temperature. The results are interpreted in terms of a twolayer model with conducting grains partitioned from each other by poorly conducting grain boundaries. Using this model, we attributed the two electrical responses in impedance and modulus formalisms to the grain and grain boundary effects, respectively, while the detected Debyelike relaxation and large dielectric constant were explained in terms of MaxwellWagner relaxation.

Ceramics and polymer-ceramic composites associated with high dielectric constants are of both scientific and industrial interest as these could be used in devices such as capacitors, resonators and filters. High dielectric constant facilitates smaller capacitive components, thus offering the opportunity to miniaturize the electronic devices. Hence there is a continued interest on high dielectric constant materials over a wide range of temperatures. Recently, CaCu3Ti4O12 (CCTO) ceramic which has centro-symmetric body centered cubic structure has attracted considerable attention due to its large dielectric constant (ε ~104-105) which is nearly independent of frequency (upto 10 MHz) and low thermal coefficient of permittivity (TCK) over 100-600K temperature range. Apart from the high dielectric ceramics, high dielectric polymer-ceramic composites have also become promising materials for capacitor applications. By combining the advantages of high dielectric ceramics and low leakage behaviour of polymers, one can fabricate new hybrid materials with high dielectric constants, and high breakdown field to achieve high volume efficiency and energy storage density for capacitor applications. The CCTO polycrystalline powders were generally prepared by the conventional solid-solid reaction route with CaCO3, TiO2 and CuO as the starting materials. This method of preparation often requires high temperatures and longer durations. To overcome these difficulties, in the present investigations, an attempt has been made to synthesize CCTO by adopting microwave assisted heating technique and wet chemical synthesis routes. Also the CCTO crystallites (size varying from nano to micrometers) incorporated in the Polyvinyliden fluoride (PVDF) and Polyaniline (PANI) matrix and several composites with high dielectric constants were fabricated and investigated. Further, the high dielectric constant glasses in the system (100-x)TeO2-xCaCu3Ti4O12, (x=0.5 to 3) were fabricated by the conventional melt-quenching technique and their structural and dielectric properties were studied. The results obtained pertaining to these aforementioned investigations are classified as follows. Chapter 1 is intended to give basic information pertaining to the dielectrics and various mechanisms associated with high dielectric constants. Brief exposure to the high dielectric constant materials is also given. The structural aspects of CCTO, various synthetic routes adopted for the synthesis and the origin of the dielectric anomaly in CCTO are elaborated. In addition, basic information about the high dielectric polymer-ceramic composites and glasses are provided. In chapter 2 the various experimental techniques that were employed to synthesize and characterize the materials under investigation were discussed. Chapter 3 reports the synthesis and characterization of CaCu3Ti4O12, (CCTO) powders by microwave assisted heating at 2.45 GHz, 1.1kW. The processing and sintering were carried out at different temperatures for varied durations. The optimum calcination temperature using microwave heating was found to be 950oC for 20 minutes to obtain cubic CCTO powders. This is found to be fast and energy efficient as compared to that of the conventional methods. The structure, morphology and dielectric properties of the CCTO ceramic processed by microwave assisted heating were studied via X-ray diffraction, Scanning electron microscopy (SEM) and impedance analyser. These studies revealed that, the microwave sintered (MS) samples were less porous than that of the conventional ones. Relative density of about 95% was achieved for the MS pellets (1000oC/60min) while for the conventional sintered (CS) pellets (1100oC/2h) it was only 91%. The dielectric constants for the microwave sintered (1000oC/60min) ceramics were found to vary from 11000 to 6950 in the 100 Hz to 100 kHz frequency range. The presence of larger grains (6-10μm) in the MS samples contributed to the higher dielectric constants. Chapter 4 deals with the synthesis of complex oxalate precursor, CaCu3(TiO)4(C2O4)8 • 9H2O, by the wet chemical route. The various trials and the different reaction schemes involved for the preparation of complex oxalate precursor were highlighted. The oxalate precipitate thus obtained was characterized by the wet chemical analyses, X-ray diffraction, FTIR absorption and TG/DTA analyses. The complex oxalate precursor, CaCu3(TiO)4(C2O4 )8.9H2O was subjected to thermal oxidative decomposition and the products of thermal decomposition were investigated employing XRD,TGA, DTA and FTIR techniques. Nanocrystallites of CaCu3Ti4O12 with the size varying from 30-200 nm were obtained at a temperature as low as 680oC. The nanocrystallites of CaCu3Ti4O12 were characterized using Electron Spin Resonance (ESR) and optical reflectance techniques. The selected area electron diffraction (SAED) pattern with the zone axis [012] and spot pattern in electron diffraction (ED) indicate their single-crystalline nature. The optical reflectance and ESR spectra indicate that the Cu (II) coordination changes from distorted octahedra to nearly flattened tetrahedra (squashed) to square planar geometry with increasing heat treatment temperature. The powders derived from the oxalate precursor have excellent sinterability resulting in high density ceramics which exhibited giant dielectric constants upto 40,000 (1 kHz) at 25oC, accompanied by low dielectric loss < 0.07. The effect of calcium content on the dielectric properties of CaxCu3Ti4O12 (x=0.90, 0.97, 1.0, 1.1 and 1.15) derived from the oxalate route was described in Chapter 5. The structural, morphological and dielectric properties of the ceramics were studied using X-ray diffraction, Scanning Electron Microscope along with Energy Dispersive X-ray Analysis (EDX), and Impedance analyzer. The X-ray diffraction patterns obtained for the x= 0.97, 1.0 and 1.1 ceramics could be indexed to a body– centered cubic perovskite related structure associated with the space group Im3. The microstructural studies revealed that the grains are surrounded by exfoliated sheets of Cu-rich phase. The microstructure that is evolved for the Ca0.97 ceramic more or less resembles that of the Ca1.0 ceramic, but the density of such exfoliated sheets of cu-rich phase is lesser for the Ca0.97 ceramic and none for Ca1.1 ceramic. The sintered pellet (x=0.97) was ground and thinned to the required thickness (~ 20nm) and analyzed using Transmission Electron Microscopy (TEM). The current-voltage (I-V) characteristics of the ceramics exhibited non-linear behaviour. The dielectric properties of these suggest that the sample corresponding to the composition x=0.97, has a reduced dielectric loss while retaining its high dielectric constant. Chapter 6 illustrates the results concerning the fabrication and characterization of nanocrystal composites of Polyaniline (PANI) and CaCu3Ti4O12 (CCTO). These were prepared using a simple procedure involving in-situ polymerization of aniline in dil. HCl. The PANI and the PANI-CCTO composites were subjected to X-ray diffraction, Fourier Transform Infrared (FTIR), Thermo gravimetric, Scanning Electron Microscopic (SEM) and Transmission electron microscopic analyses. The FTIR spectra recorded for the composites was similar to that of pure PANI unlike in the case of X-ray diffraction wherein the characteristics of both PANI and CCTO were reflected. The TGA in essence indicated the composites to have better thermal stability than that of pure PANI. The composite corresponding to 50%CCTO-50%PANI exhibited higher dielectric constant (4.6x106 @100Hz). The presence of the nano crystallites of CCTO embedded in the nanofibers of PANI matrix was established by TEM. The AC conductivity increased slightly upto 2kHz as the CCTO content increased in the PANI which was attributed to the polarization of the charge carriers. The value of dielectric constant obtained was higher than that of the other PANI based composites reported in the literature. Chapter 7 deals with the fabrication and characterization of diphasic Poly(vinylidene fluoride) (PVDF)-CCTO composite. The CCTO crystallites (size varying from nano to micrometers) incorporated in the Polyvinylidene fluoride (PVDF) and composites with varying CCTO content were fabricated. The structural, morphological and dielectric properties of the composites were studied using X-ray diffraction, Thermal analysis, Scanning Electron Microscope (SEM), Transmission Electron Microscopic (TEM) and Impedance analyzer. The room temperature dielectric constant as high as 95 at 100Hz has been realized for the composite with 0.55 Vol.fraction of CCTO (micro sized crystallites), which has increased to about 190 at 150oC. Whereas, the PVDF/CCTO nanocrystal composite with 0.13Vol.fraction of CCTO has exhibited higher room temperature dielectric constant (90 at 100Hz). The PVDF/CCTO nanocrystal composite was further investigated for the breakdown strength and electric modulus. The breakdown strength plotted against the dielectric constant evidenced an inverse relationship of breakdown voltage with the dielectric constant. The relaxation processes associated with these composites were attributed to the interfacial polarization or Maxwell-Wagner-Sillars (MWS) effect. Various theoretical models were employed to rationalize the dielectric behavior of these composites. The fabrication and characterization details of optically clear colored glasses in the system (100-x)TeO2-xCaCu3Ti4O12, (x=0.5 to 3 mol%) are reported in Chapter 8. The color varies from olive green to brown as the CaCu3Ti4O12 (CCTO) content increased in TeO2 matrix. The X-ray powder diffraction and differential scanning calorimetric analyses that were carried out on the as-quenched samples confirmed their amorphous and glassy nature respectively. The optical transmittance of the glasses exhibited typical band-pass filter characteristics. The dielectric constant and loss in the 100 Hz-1MHz frequency range were monitored as a function of temperature (323K673K). The dielectric constant and the loss increased as the CCTO content increased in TeO2 at all the frequencies and temperatures under study. Further, the dielectric constant and the loss were found to be frequency independent in the 323-473 K temperature range. The value obtained for the loss at 1MHz was 0.0019 which was typical of low loss materials, and exhibited near constant loss (NCL) contribution to the ac conductivity in the 100Hz-1MHz frequency range. The electrical relaxation was rationalized using the electrical modulus formalism. These glasses are found to be more stable (a feature which may be of considerable interest) as substrates for high frequency circuit elements in conventional semiconductor industries. Thesis ends with summary and conclusions, though each chapter is provided with conclusions and complete list of references.

Les nanocomposites polymères diélectriques ayant une constante diélectrique élevée et une faible perte diélectrique ont reçu un grand intérêt pour une utilisation dans le domaine du condensateur électrostatique. De manière générale, les performances diélectriques améliorées des nanocomposites sont déterminées par le type et la nature des polymères et des nanocharges sélectionnés, ainsi que par l'effet de couplage interfacial entre les matrices et les nanocharges. Parmi ces facteurs, les propriétés physiques, les géométries et les structures des composants des nanocharges jouent un rôle essentiel dans la détermination des performances diélectriques des nanocomposites. Selon les conductivités des nanocharges, les nanocomposites polymères diélectriques peuvent être classés en deux types: les nanocomposites polymères diélectriques conducteurs (CDPN) et les nanocomposites polymères diélectriques-diélectriques (DDPN). Cependant, la perte diélectrique élevée accompagnée au voisinage du seuil de percolation pour les CDPN et la charge élevée de nanocharges en céramique entravent le développement de nanocomposites polymères diélectriques à haute performance.Tout d'abord, des nanocomposites ternaires BNNS/CNT/PVDF ont été fabriqués. L'incorporation de BNNS dans les nanocomposites binaires CNT/PVDF a amélioré la dispersion des NTC et optimisé le réseau conducteur. La connexion directe entre les CNT pourrait être entravée en augmentant le contenu de BNNS.Deuxièmement, des hybrides CNT@AC à structure cœur-coquille ont été préparés par méthode CVD. La couche de carbone amorphe entrave non seulement le contact direct des NTC, mais améliore également la dispersibilité des NTC dans la matrice de PVDF. Le seuil de percolation augmente avec la prolongation du temps de dépôt du carbone. Plus important encore, la perte diélectrique a subi une forte diminution après le processus de revêtement. Troisièmement, les hybrides BNNSs@C avec des teneurs en carbone différentes ont été synthétisés par la méthode CVD. La fraction de carbone dans les hybrides BNNSs@C pourrait être ajustée avec précision en contrôlant le temps de dépôt de carbone. Les propriétés diélectriques des nanocomposites BNNSs@C/PVDF pourraient être ajustées avec précision en ajustant la teneur en carbone. Les polarisations interfaciales améliorées des interfaces BNNS/C et C/PVDF ont doté les nanocomposites de performances diélectriques améliorées.Quatrièmement, les hybrides TiO2@C NW structurés en noyau et en coquille ont été synthétisés par une combinaison d'une réaction hydrothermale et du procédé CVD. L'épaisseur de la couche de carbone dans les hybrides TiO2@C NW obtenus pourrait être précisément ajustée en contrôlant le temps de dépôt du carbone. De plus, les propriétés diélectriques des nanocomposites TiO2@C NWs/PVDF pourraient être ajustées avec précision en ajustant l'épaisseur de la coque en carbone. Les polarisations interfaciales améliorées des interfaces TiO2/C et C/PVDF ont doté les nanocomposites d'excellentes performances diélectriques.Enfin, des nanofils structurés de TiO2@C@SiO2 structurés à double coques ont été synthétisés par une combinaison de réactions hydrothermales modifiées, de CVD et de réactions sol-gel. L'introduction de carbone comme enveloppe interne entre le noyau de TiO2 et l'enveloppe externe de SiO2 a induit deux types supplémentaires de polarisation interfaciale. Les nanocomposites de PVDF obtenus avec TiO2@C@SiO2 NWs présentaient simultanément une constante diélectrique améliorée et des caractéristiques de perte diélectrique supprimées. La constante diélectrique et la perte de nanocomposites ont augmenté avec l'augmentation de l'épaisseur de la couche interne de carbone et ont diminué avec l'augmentation de l'épaisseur de la couche externe de SiO2. La relation entre la perte diélectrique et l'épaisseur de l'enveloppe extérieure en SiO2 a été démontrée par les résultats de la simulation finie. / Dielectric polymer nanocomposites with a high dielectric constant and low dielectric loss have received broad interest for use in the field of the electrostatic capacitor and they are usually composed of dielectric polymers as matrix and inorganic or organic nanofillers as the reinforcement. Generally, the improved dielectric performance of nanocomposites is decided by the type and nature of selected polymers and nanofillers as well as interfacial coupling effect between matrices and nanofillers. Among these factors, the physical properties, geometries, component structures of nanofillers play a critical role in deciding the dielectric performance of nanocomposites. According to the conductivities of nanofillers, the dielectric polymer nanocomposites can be classified into two types: conductive-dielectric polymer nanocomposites (CDPNs) and dielectric-dielectric polymer nanocomposites (DDPNs). However, the accompanied high dielectric loss in the vicinity of the percolation threshold for CDPNs and high loading of ceramic nanofillers hinders the development of high performance dielectric polymer nanocomposites.Firstly, ternary BNNSs/CNTs/PVDF nanocomposites were fabricated. The incorporation of BNNSs into the binary CNTs/PVDF nanocomposites improved the dispersion of CNTs and optimized the conductive network, which contributed to the enhanced dielectric constant. The direct connection between CNTs could be hindered by increasing the content of BNNS.Secondly, core-shell structured CNTs@AC hybrids were prepared by CVD method. The amorphous carbon layer not only hindered the direct contact of CNTs but also improved the dispersibility of CNTs in the PVDF matrix. The percolation threshold increased with the prolongation of carbon deposition time. More importantly, the dielectric loss underwent a sharp decrease after the coating process, which was attributed to the decrease in leakage current. The results suggested that the influence of AC interlayer on the final dielectric performance after percolation was much more obvious than that before percolation.Thirdly, BNNSs@C hybrids with different carbon contents were synthesized by the CVD method. The carbon fraction in the BNNSs@C hybrids could be accurately adjusted through controlling the carbon deposition time. The dielectric properties of BNNSs@C/PVDF nanocomposites could be accurately tuned by adjusting the carbon content. The improved interfacial polarizations of BNNSs/C and C/PVDF interfaces endowed the nanocomposites with enhanced dielectric performance.Fourthly, core-shell structured TiO2@C NW hybrids were synthesized by a combination of a hydrothermal reaction and the CVD method. The carbon shell thickness in the obtained TiO2@C NW hybrids could be precisely tuned by controlling the carbon deposition time. The TiO2@C NWs/PVDF nanocomposites exhibited a percolative dielectric behavior. Moreover, the dielectric properties of the TiO2@C NWs/PVDF nanocomposites could be accurately adjusted by tuning the carbon shell thickness. The enhanced interfacial polarizations of the TiO2/C and C/PVDF interfaces endowed the nanocomposites with excellent dielectric performance.Lastly, core@double-shells structured TiO2@C@SiO2 nanowires were synthesized by a combination of modified hydrothermal reaction, CVD, and sol-gel reaction. The introducing of carbon as an inner shell between the TiO2 core and SiO2 outer shell induced two additional types of interfacial polarization. The obtained PVDF nanocomposites with TiO2@C@SiO2 NWs exhibited simultaneously enhanced dielectric constant and suppressed dielectric loss characteristics. The dielectric constant and loss of nanocomposites increased with the increase of carbon inner shell thickness and decreased with the increasing of SiO2 outer shell thickness. The relationship between the dielectric loss and SiO2 outer shell thickness was further demonstrated by the finite simulation results.

High dielectric constant materials are of technological importance as they lead to the miniaturization of the electronic devices. In this context, the observation of anomalously high dielectric constant (>104) in the body-centered cubic perovskite-related (Space group Im3) material Calcium Copper Titanate ((CaCu3Ti4O12)(CCTO)) over wide frequency (100 Hz – 1MHz at RT) and temperature (100 – 600 K at 1 kHz ) ranges has attracted a great deal of attention. However, high dielectric constant in CCTO is not well understood yet, though internal barrier layer capacitor (IBLC) mechanism is widely been accepted. Therefore, the present work has been focused on the preparation and characterization of CCTO ceramic and to have an insight into the origin of high dielectric constant. Influence of calcination temperature, processing conditions, microstructure (and hence grain size), composition, doping etc on the electrical characteristics of CCTO ceramics were investigated. Electrical properties were found to be strongly dependent on these parameters. The dielectric constant in CCTO was observed to be reduced considerably on substituting La+3 on Ca+2 site. The formation temperature of CCTO was lowered substantially (when compared to conventional solid-state reaction route) by adopting molten-salt synthesis. The dielectric loss in CCTO was reduced by incorporating glassy phases at the grain boundary. Potential candidates for the practical applications such as charge storage devices, capacitors etc, with dielectric constant as high as 700 at 300 K was accomplished in a three-phase percolative composite fabricated by incorporating Aluminium particle into CCTO-epoxy composite. Polycrystalline CCTO thin films with dielectric constant as high as ~ 5000 (1 kHz and 400 K) were fabricated on Pt(111)/Ti/SiO2/Si substrates using radio frequency magnetron sputtering. Effect of sintering conditions on the microstructural, ferroelectric and varistor properties of CCTO and LCTO ceramics belonging to the high and low dielectric constant members of ACu3M4O12 family of oxides were investigated in detail and are compared. Ferroelectric-like hysteresis loop (P vs E) and weak pyroelectricity were observed in CCTO and plausible mechanisms for this unusual phenomenon have been proposed.

Dielektrická relaxační spektroskopie je jednou z užitečných metod pro studium molekulární dynamiky materiálů. Díky nedávnému pokroku v přístrojové a měřicí technice je dnes možné získat dielektrické spektrum v širokém frekvenčním intervalu a pro velice rozdílné materiály. Cílem mé práce bylo studium dielektrických relaxačních spekter a vodivosti oxidů titanu, niobu, tantalu, lanthanu a hafnia pro katody pracující na principu studené emise. Cílem výzkumu bylo analyzovat frekvenční a teplotní chování těchto oxidů, včetně jejich vodivosti, v širokém frekvenčním a teplotním rozsahu, a pokusit se stanovit původ relaxačního mechanismu. Vzhledem k tomu, že původně zadaný rozsah oxidů byl dosti široký, soustředila se pozornost pouze na oxidy tantalu a niobu, rovněž s ohledem na jejich aplikace v elektrolytických kondenzátorech. Elektrické, tepelné a mechanické (při zpracování) vlastnosti oxidů tantalu a niobu jsou dnes již dobře prozkoumány. K dispozici je však jen málo poznatků o jejich dielektrických relaxačních mechanismech. Výsledky získané pro Ta2O5 ukazují existence relaxačního maxima, nacházejícího se v experimentálně dostupném teplotním a frekvenčním intervalu 187 K – 385 K a 1 Hz – 10 MHz. Frekvence ztrátového maxima se řídí Arrheniovým zákonem s aktivační energií 0.048 eV. Ve vodivostních spektrech vykazují tenké vrstvy Ta2O5 na nízkých frekvencích ustálenou hodnotu a při vysokých frekvencích monotónní nárůst, který závisí na teplotě. Pozorovanou vodivost lze popsat mocninnou funkcí s exponentem nepatrně větším než jedna (tzv. superlineární závislost). Výsledky získané pro Nb2O5 v podobné teplotní a frekvenční oblasti, 218 K – 373 K, 1 Hz – 1 MHz rovněž ukazují jedno relaxační maximum. Frekvence ztrátového maxima se opět řídí Arrheniovým zákonem s poněkud vyšší aktivační energií 0.055 eV. Niobové kondenzátory vykazují vodivostní mechanismus shodný s kondenzátory tantalovými.

Charge trapping dynamics in Si/SiO2/Hf(1-x)SixO2 and III-V film stack systems are characterized using spectroscopic ellipsometry (SE) and second harmonic generation (SHG). For the first time, discrete absorption features within the bandgap of the SiO2 interfacial layer are identified using SE, and their relation to both intrinsic and process-induced defects is proposed. Sensitivity of the absorption features to process conditions is demonstrated and evidence that these defects contribute to Vfb roll-off is presented. Defects in the Hf(1-x)SixO2 films are probed with fs laser-induced internal multi-photon photo-excitation (IMPE) and time dependent electrostatic field induced second harmonic (TD-EFISH) generation. For the as deposited HfO2 films, a unique TD-EFISH response is identified and explained by resonant two photon ionization of a specific point defect and subsequent tunneling of the photoelectrons to the Si substrate. Charge trapping kinetics for all Hf(1-x)SixO2 films are investigated. Two characteristic trap cross sections are identified and found to be insensitive to dielectric film and process conditions, and associated with a surface “harpooning” mechanism. EFISH from non-centrosymmetric III-V media, including GaAs and In0.53Ga0.47As, is also studied. The anisotropic and time dependent SHG response from different chemically treated In0.53Ga0.47As surfaces is clearly distinguishable and associated with a process-induced change in the surface depletion field. / text