Investigation of structure-dielectric property relationships in zirconium oxide, tantalum pentoxide, and oxide-polymer laminate films for high energy density capacitor applications

Pulsed power applications involve transformation of electrical energy into high-peak power pulses through capacitors. There is an immediate need for fast-response capacitors with decreased volume, weight, and cost for pulsed power applications and power distribution systems. This research challenge is dominated by energy density. Energy density is directly related to dielectric properties such as dielectric polarization, conductivity and breakdown strength of the capacitor dielectric. This research work correlates processing and microstructure of single and multiple component dielectric films with their dielectric properties. The inorganic materials studied in this dissertation include zirconium oxide (ZrO2) and tantalum pentoxide (Ta 2O5) reactive sputtered films. Film crystallization & structure was studied as a function of sputtering growth variables such as sputtering power, sputtering pressure, source frequency, oxygen pressure, substrate temperature, substrate material, and post-deposition annealing temperature. Polycrystalline phase of ZrO2 and amorphous phase of Ta2O 5 were obtained for most sputtering growth variables.;Although the amorphous films have lower permittivity (32 for amorphous & 51 for polycrystalline at 1 kHz), they also have lower AC and DC conductivities (3.4x10-8 S/m for amorphous & 12.2x10 -8 S/m for polycrystalline at 1 kHz), which result in high breakdown strength than polycrystalline films. Amorphous Ta2O5 films are found to be ideal for high-energy density capacitors with energy density of 14 J/cm3 because of their high permittivity, low leakage current density, and high dielectric breakdown strength. Oxide films were combined with different polymers (polyvinyldene flouride-triflouroethylene, polypropylene and polyethylene terephthalate) to produce two different kinds of laminate composites---oxide on polymer and polymer on oxide. Permittivity and conductivity differences in the polymer and oxide films result in an impedance contrast of generally greater than 100 between the constituents. Low and high field dielectric properties were characterized for both laminate composites. All the dielectric films were characterized by impedance spectroscopy at frequencies ranging from 10 mHz to 1 MHz at different temperatures. Complex impedance and modulus analyses were used to resolve the contributions of individual microstructural features (such as grain, grain boundary & interface) from the overall film and composite electrical properties. Activation energies related to electro-active regions (grain boundary ∼1.1 eV, grain ∼0.5 eV) in the film structure were also determined from the temperature dependent impedances. The overall polarization of composite was higher by at least 25% than the sum of the polarizations from the individual layers for all composites. Plasma processed Ta2O5-Polypropylene laminate composite resulted in breakdown strength of ∼870 MV/m, which approximately 10% higher breakdown strength than its highest breakdown constituent (∼775 MV/m). These improved properties were attributed to bulk polymer modification, interface charge blocking/trapping and impedance contrast within the composite. The effect of impedance contrast on breakdown strength was modeled through permittivity contrast using Monte Carlo method. The breakdown model explored the electrostatic effects of adding a high permittivity barrier within an existing dielectric on the breakdown tree. The model also provided knowledge on various breakdown tree characteristics such as speed and shape. The Monte Carlo simulation results suggest that the experimentally observed impedance contrast of 1000 between the layers of the laminate composite can result in improved breakdown strength.