Metal oxides crystallized in perovskite structure are generally modified in two different ways. According to the general structural formula ABO3, the two ways are A-site modification and B-site modification. The primary significance of perovskite metal oxides rests on their importance in electronic devices. A particular class of perovskites, namely Lead Zirconate or modified Lead Zirconate has received a special attention because of their unique antiferroelectricity and various applications in devices. Among the other modifications, A-site modification of PbZrO3 by La is rare and not much explored. Chapter 1 describes various applications of antiferroelectric thin films along with the synthesis and characterization of pure and La modified PbZrO3, which are relevant to the work presented in this thesis. Sol-gel processing and spin coating technique to deposit solid oxide thin films are well known for their low cost of deposition as well as for their ability to achieve better stoichiometric chemical composition. Common crack formation problem of sol-gel grown films can be prevented by ‘drying control chemical adhesive’ like polyvinylpyrrolidone (PVP). Heat treatment of sol-gel derived thin films is generally determined by TGA and DTA. Crystalline phase of deposited solid thin films is determined by XRD whereas effect of modification can be ascertained by XRD peak assignment and relative crystalline peak shifting. Sol-gel grown film thickness is measured by common cross sectional SEM whereas AFM can detail the surface morphology. Chapter 2 summarizes the deposition and characterization of pure and La modified PbZrO3 thin films. Any nonmetal, which is insulator, is dielectric material and show dielectric dispersion in a frequency domain of low field alternative current. Among the most common feature of dielectric dispersion, Maxwell – Wagner type dispersion is well known. Similar kind of dielectric dispersion, named Maxwell – Wagner like dispersion, can be observed while the equivalent circuit consists of parallel G – C along with a series R. Universal power law of ac conductivity is the deciding factor to distinguish the nature of dispersion. Structural phase transition can be determined by dielectric response and it is widely known as dielectric phase transition. Effect of La modification on dielectric phase transition of PbZrO3 thin films depends on stabilization or destabilization of antiferroelectricity. Maximum dielectric constants of pure and modified PbZrO3 thin films depend on the crystallographic orientations of the growth. Chapter 3 presents dielectric properties of pure and La modified PbZrO3 thin films and these properties are correlated to the stabilization or destabilization of antiferroelectricity, relative integrated intensity of (202)O film orientation and trapped electron charge due to oxygen vacancies. Charge storage property of a capacitor is determined by the polarization of the capacitor on application of electric field whereas field dependent integrated area of polarization on withdrawal of electric field determines the recoverable capacitive energy storage. Among the three kinds of capacitors like linear or paraelectric, ferroelectric and antiferroelectric capacitors, antiferroelectric capacitor is known to be best for their ability to store huge amount of recoverable energy. The recoverable energy in antiferroelectrics can be increased by increasing squareness of the P – E hysteresis loop, applicable electric field, polarization or by the all possible combinations of them. Chapter 4 describes the correlation of relative integrated intensity of (202)O [RI(202)O] with critical applied electric field of P – E saturation to provide enhanced squareness of the hysteresis loops. This chapter also describes the variation of charge and recoverable energy storage properties with respect to RI(202)O. Like magnetocaloric effect, electrocaloric effect is capable to alter the temperature of a system by adiabatic polarization or depolarization. From the Maxwell’s relation of thermodynamics, assuming, (∂p ) = (∂s )electrocaloric effect can be calculated from temperature dependent polarization value of a paraelectric, ferroelectric or an antiferroelectric. Chapter 5 presents the electrocaloric effect of pure and La modified PbZrO3 thin films. Summary of present study and discussion have been delineated in Chapter 6 along with the future work which can give more insight into the understanding of antiferroelectric PbZrO3 thin films with respect to Pb and Zr site modification and with respect to different electrodes. (For formulas pl see the pdf file of the thesis)

Transient negative capacitance effects in epitaxial ferroelectric Pb(Zr₀.₂Ti₀.₈)O₃ capacitors are investigated with a focus on the dynamical switching behavior governed by domain nucleation and growth. Voltage pulses are applied to a series connection of the ferroelectric capacitor and a resistor to directly measure the ferroelectric negative capacitance during switching. A time-dependent Ginzburg-Landau approach is used to investigate the underlying domain dynamics. The transient negative capacitance is shown to originate from reverse domain nucleation and unrestricted domain growth. However, with the onset of domain coalescence, the capacitance becomes positive again. The persistence of the negative capacitance state is therefore limited by the speed of domain wall motion. By changing the applied electric field, capacitor area or external resistance, this domain wall velocity can be varied predictably over several orders of magnitude. Additionally, detailed insights into the intrinsic material properties of the ferroelectric are obtainable through these measurements. A new method for reliable extraction of the average negative capacitance of the ferroelectric is presented. Furthermore, a simple analytical model is developed, which accurately describes the negative capacitance transient time as a function of the material properties and the experimental boundary conditions.

The present research work mainly focuses on the fabrication and characterization of single and multilayer thin films based on Bismuth Vanadate (BVO) and Bismuth Titanate (BTO). The multi-target laser ablation technique was used to fabricate single layer thin films of BVO, BVN and BTO; and multilayers composed of BVO and BTO in different structures. The fabricated thin films exhibited dense microstructure and a sharp interface with the substrate. The lattice strain, surface roughness and grain size could be varied as functions of composition and individual layer thickness in different structure fabricated. The optical properties were studied by spectroscopic ellipsometry and optical transmission spectra. The various models that were used for ellipsometric data analysis gave an excellent fitting to the experimental data. The optical constants were determined through multilayer analyses of the films. The band gap of these films was studied by spectroscopic ellipsometry and optical transmission. The optical studies carried out on BVO-BTO bilayer indicated the presence of an interfacial layer in between the BVO and BTO layer, whose refractive index was different from that of the individual layers and is attributed to different nature of the interfacial layer. The ferroelectric nature of BVO films was confirmed by P-E hysteresis loop studies under different applied fields and at various probing frequencies. The same was corroborated via the C-V measurements of these BVO films which exhibited butterfly shaped C-V characteristics. Fatigue studies in these films indicated that the switchable polarization is essentially constant through 105 cycles, after which it starts increasing probably due to the ionic conduction in BVO thin films. The dielectric response of undoped and Nb doped BVO as well as BVBT ML thin films were studied over a wide range of temperatures. The BVO films exhibited remarkable dielectric dispersion at low frequencies especially in the high temperature regime. Further, the frequency and temperature dependence of the dielectric, impedance, modulus and conductivity spectra of these films were investigated in detail. The ac conductivity was found to obey well the double power law in case of ML, indicating the different contributions to the conductivity, the low frequency conductivity being due to the short range translational hopping and the high frequency conductivity is due to the localized or reorientational hopping motion. DC leakage conduction in BVO, BVN and BVBT ML thin films was studied over a wide range of temperatures and applied electric fields. The experimental data were analyzed in light of different models to investigate the dc conduction mechanism in these films which were broadly classified into electrode limited and bulk limited conduction processes. In the case of BVO thin films the dc leakage current exhibited an ohmic nature at low electric fields followed by an onset of the space charge limited conduction (>1). Further in case of BVN films, three distinct regions were observed in I-V characteristics signifying different types of conduction processes in these films. In case of BVBT ML thin films, bulk limited PF mechanism was found to determine the conduction behavior at moderate electric fields. At higher electric fields, a trap filled region was observed which was followed by SCL conduction at higher fields. Therefore the present observation indicates the presence of more than one bulk limited conduction process in BVBT ML thin films. BVO thin films exhibiting good structure and dense morphology were successfully prepared on p-type Si by chemical solution decomposition technique. The C-V characteristics were evaluated for Au/BVO/Si MFS structure which showed a typical high frequency feature of a conventional MFIS structure.