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.

No description available.

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.

Structural studies with CaCu3Ti4O12 (CCTO) are made since the 1970s, however investigations about their electrical properties only started recently. At 2000, it was reported a high permittivity of ~ 12000 (at 1 KHz) in ceramics of this material which remained constant between the room temperature to ~ 200 °C, and whose physical explanations be still controversial in the scientific society. High dielectric constants allow smaller capacitive components, enabling the size reduction of the electronic devices. In this way, CCTO has attracted the interest of many researchers as technological as scientific point of view. One of the main problem that limit its immediate application as dielectric in ceramic capacitors is its high dielectric loss (~ 0,15) near at room temperature. On the other hand, this material has been prepared by several researchers mainly by the solid state reaction method, in the temperature range of 1000 °C to 1050 °C, with thermal treatment up to 48 h. As result, some secondary phases have be found as in the calcined powders as in the sintered ceramics. Thus, other synthesis methods have been proposed and tested in the last years. In this work, we have studied the CCTO synthesis by a route based on Pechini s method and its sintering using a new method, in which a CO2 laser is used as the main heating source. Besides, the dielectric properties of CCTO ceramics were investigated in order to verify the influence of this sintering process on the ceramic properties as well as onto the understanding of the involved physical mechanisms. The laser sintered ceramics presented high relative density (95 ± 1%), with homogeneous microstructure and dielectric constant at about 2000 with low dielectric loss (0,06) at 1 kHz, when sintered at 1,3 W/mm2. The dielectric loss value obtained in this work is among the lowest ever recorded. Based on our results was also proposed a mechanism to aid in the understanding of the giant dielectric constant in CCTO. Finally, we believe that laser sintering can be an important tool for the optimization of the dielectric properties of CCTO ceramics and consequently future applications in the capacitors and electronic devices industry, whose worldwide consumption is increasing. / Estudos estruturais com o CaCu3Ti4O12 (CCTO) são feitos desde os anos 1970, contudo investigações acerca de suas propriedades elétricas somente se iniciaram recentemente. Em 2000, foi reportado uma alta permissividade de ~ 12000 (a 1 kHz) em cerâmicas deste material, que permanecia constante da temperatura ambiente a ~ 200 °C, cujas explicações físicas ainda são bem controversas na comunidade científica. Constantes dielétricas altas permitem menores componentes capacitivos, oferecendo assim a oportunidade de diminuir o tamanho de dispositivos eletrônicos. Desta forma, o CCTO tem atraído muito o interesse de pesquisadores, tanto do ponto de vista tecnológico quanto científico. Um dos principais problemas que limitam sua imediata aplicação como dielétrico em capacitores cerâmicos é a sua alta perda dielétrica (~ 0,15) próximo à temperatura ambiente. Por outro lado, este material tem sido preparado por diversos pesquisadores principalmente pelo método da reação de estado sólido, no intervalo de temperatura de 1000 °C a 1100 °C, com tratamentos térmicos de até 48 h. Como resultado, algumas fases secundárias têm sido encontradas tanto no pó calcinado quanto na cerâmica sinterizada. Dessa forma, outros métodos de síntese vêm sendo procurados e testados nos últimos anos. Neste trabalho, estudamos a síntese do CCTO por uma rota baseada no método Pechini e sua sinterização usando um novo método, no qual um laser de CO2 é usado como principal fonte de aquecimento. Além disso, estudamos as propriedades dielétricas das cerâmicas de CCTO, a fim de verificar a influência deste novo processo de sinterização em suas propriedades bem como no entendimento dos mecanismos físicos envolvidos. As cerâmicas sinterizadas a laser apresentaram alta densidade relativa (95 ± 1%), com microestrutura homogênea e constante dielétrica em torno de 2000 e baixa perda dielétrica (0,06) a 1 kHz, quando sinterizadas a 1,3 W/mm2. O valor de perda dielétrica obtida neste trabalho está entre os mais baixos já registrados. Baseando-se em nossos resultados também foi proposto um mecanismo para auxiliar no entendimento da constante dielétrica gigante no CCTO. Finalmente, acreditamos que a sinterização a laser pode ser uma importante ferramenta para a otimização das propriedades dielétricas de cerâmicas de CCTO e consequentemente futuras aplicações na indústria de capacitores e dispositivos eletrônicos, cujo consumo mundial é cada vez maior.