Polarization versus applied field (P-E) hysteresis loop measurements on Pb(Zr,Ti)O3 (PZT) thin films were performed using a controlled-atmosphere probe station. Measurements were made using two different capacitor configurations, each producing differing results. The capacitor configurations included using either the typical arrangement of two top electrodes (planar) or an arrangement using contacts to the top and the bottom electrodes (sandwich). The films included PZT films deposited using pulsed laser deposition (PLD) and commercially-available rfsputtered PZT thin films. Qualitatively similar results were obtained for both types of films. For both PLD and Ramtron PZT films, translation of ferroelectric hysteresis loops along the polarization axis was observed for sandwich capacitors. The magnitude of this voltage was strongly dependent on the partial pressure of oxygen at room temperature. Translations were not observed for the same films using the planar capacitor configuration. However, for both sandwich and planar configurations, the thin film capacitance was sensitive to changes in pO2.

Thin-film composites of BaTiO3 particles in a polymeric matrix were processed by reacting films of a titanium alkoxide, mixed with a polybutadiene-polystyrene triblock copolymer, in aqueous solutions of 1.0 M Ba(OH)2 at temperatures ranging from 60 to 90 °. After reaction, the composite films displayed distinct surface and subsurface morphologies. The film surface consisted of a continuous layer of BaTiO3 grains, the film grain size decreasing from 180 to 60 nm as the reaction temperature increased from 60 to 90 °. The subsurface growth of BaTiO3 depended on the presence of a percolating network of hydrolyzed titanium alkoxide, which enabled the reaction solution to permeate throughout the thin film. The resulting subsurface film morphology was composed of segregated regions of BaTiO3 particles dispersed throughout the polymeric matrix. The growth of subsurface BaTiO3 particles appeared to be constrained by the polymer matrix, resulting in a subsurface particle size of approximately 5 to 10 nm that was independent of the hydrothermal processing temperature. The reacted films displayed a dielectric constant ranging from 10 to 15 at room temperature and a frequency of 10 kHz.

The influence of Pb/Ti ratio on the particle size of hydrothermally derived lead titanate (PbTiO3) powders was investigated. Phase pure PbTiO3 powder was synthesized by reacting nanocrystalline TiC2 powder in a 1 m KOH solution for 15 h at 200°C with Pb/Ti ratios of 1 and 5. Faceted platelet particles with a low aspect ratio were formed in solutions with Pb/Ti ratios of 1 and 5. The observed particle size of PbTiO3 was 200 nm and larger when Pb/Ti = 1, while 50 - 100 nm sized particles formed when Pb/Ti = 5. In support of TEM observations, the BET specific surface area data increased from 4.4 m2/g to 7.3 m2/g as the Pb/Ti ratio was increased from I to 5. PbTiO3 particle size was controlled by either inhibiting or promoting dissolution-precipitation. Dissolution-precipitation in a high pH solution was inhibited by maintaining an excess of Pb ions in solution and it was promoted when input concentrations of Pb and Ti were equivalent.

Composite BaTiO3/polymer films (<1μm thickness) were processed by the in-situ growth of BaTiO3 particles in a polymer matrix. A solution of a polybutadiene/polystyrene triblock copolymer and titanium diisoproxide bis(ethlyacetoacetate) dissolved in toluene was cast onto a Ag-coated substrate. Subsequent hydrothermal treatment of the films in 1.0 M Ba(OH)2 solutions at 80° C resulted in the nucleation and growth of BaTiO3 within the polymer matrix. The volume fraction/connectivity of BaTiO3 was controlled by varying the relative amounts of titanium precursor and polymer in solution. Growth of BaTiO3 within the polymer was examined by infrared spectroscopy and electron microscopy. The dielectric constant of the composite films increased with BaTiO3 content.

PZT thin films with the composition Pb(Zr0.6Ti0 4)O3 were processed via metallo-organic decomposition (MOD) with {111} and {100} orientations. Ferroelectric measurements showed that the {111} and {100} oriented films had remanent polarizations of 19.5 μC/cm2 and 16 μC/cm2, respectively. Both x-ray pole figure analysis and the Harris texture index were used to quantify the degree of {100}, {110}, and {111} orientation in each film, with reasonable agreement between the two methods. The {100} oriented thin film was determined to be 582 times random for the Harris technique versus 522 times random for pole figure analysis, while the {111} oriented film was 41 times random for the Harris technique and 81 times random for pole figure analysis. The axisymmetric texture of the films allow 2-D pole figure analysis to provide a quantitative characterization of film texture.

From the first recorded investigations by Bosetti in 1745 through G.I. Taylor's[2] work on the “Disintegration of Water Droplets in an Electric Field” in 1964, electrostatic atomization of liquids has been put to use in a variety of applications ranging from crop spraying to the propulsion of space vehicles. Here, we have used electrostatic atomization to form micron size droplets of zirconium acetate which pyrolyze to spherical ZrO2 particles for use in sintering studies. Two ZrO2 powders were fabricated. Both are spherical and of similar size distribution, however, in one, the particles are single crystals, while in the other, the particles are polycrystalline. This work discusses the processing of these different particles, and the relative sintering behavior of powders that are composed of either monocrystalline or polycrystalline particles.