Sara Callori

Ferroelectric PbTiO3/SrRuO3 Superlattices with Broken Inversion Symmetry

We have fabricated PbTiO3/SrRuO3 superlattices with ultrathin SrRuO3 layers. Because of the superlattice geometry, the samples show a large anisotropy in their electrical resistivity, which can be controlled by changing the thickness of the PbTiO3 layers. Therefore, along the ferroelectric direction, SrRuO3 layers can act as dielectric, rather than metallic, elements. We show that, by reducing the concentration of PbTiO3, an increasingly important effect of polarization asymmetry due to compositional inversion symmetry breaking occurs. The results are significant as they represent a new class of ferroelectric superlattices, with a rich and complex phase diagram. By expanding our set of materials we are able to introduce new behaviors that can only occur when one of the materials is not a perovskite titanate. Here, compositional inversion symmetry breaking in bicolor superlattices, due to the combined variation of A and B site ions within the superlattice, is demonstrated using a combination of experimental measurements and first principles density functional theory.

Engineering Polarization Rotation in a Ferroelectric Superlattice

A key property that drives research in ferroelectric perovskite oxides is their strong piezoelectric response in which an electric field is induced by an applied strain, and vice versa for the converse piezoelectric effect. We have achieved an experimental enhancement of the piezoelectric response and dielectric tunability in artificially layered epitaxial PbTiO(3)/CaTiO(3) superlattices through an engineered rotation of the polarization direction. As the relative layer thicknesses within the superlattice were changed from sample to sample we found evidence for polarization rotation in multiple x-ray diffraction measurements. Associated changes in functional properties were seen in electrical measurements and piezoforce microscopy. The results demonstrate a new approach to inducing polarization rotation under ambient conditions in an artificially layered thin film.

Transition from laminar to three-dimensional growth mode in pulsed laser deposited BiFeO3 film on (001) SrTiO3

Real-time specular x-ray reflectivity of pulsed laser deposited BiFeO3 films exhibits unit-cell oscillations, with diffuse scattering intensity out-of-phase with the specular intensity. The growth mode is thus identified as nucleation and coalescence of unit-cell height islands. The growth rate is insensitive to the deposition rate, suggesting self-limiting growth. Beyond several monolayers the diffuse intensity increases abruptly, signaling a transition from two-dimensional to three-dimensional growth. Ex situ atomic force microscopy shows that mounds merge after a few more deposited layers, leaving arrays of mesas with some holes due to incomplete coalescence.

In situ X-ray diffraction and the evolution of polarization during the growth of ferroelectric superlattices

In epitaxially strained ferroelectric thin films and superlattices, the ferroelectric transition temperature can lie above the growth temperature. Ferroelectric polarization and domains should then evolve during the growth of a sample, and electrostatic boundary conditions may play an important role. In this work, ferroelectric domains, surface termination, average lattice parameter and bilayer thickness are simultaneously monitored using in situ synchrotron X-ray diffraction during the growth of BaTiO3/SrTiO3 superlattices on SrTiO3 substrates by off-axis radio frequency magnetron sputtering. The technique used allows for scan times substantially faster than the growth of a single layer of material. Effects of electric boundary conditions are investigated by growing the same superlattice alternatively on SrTiO3 substrates and 20 nm SrRuO3 thin films on SrTiO3 substrates. These experiments provide important insights into the formation and evolution of ferroelectric domains when the sample is ferroelectric during the growth process.

In-situ x-ray diffraction study of the growth of highly strained epitaxial BaTiO3 thin films

In-situ synchrotron x-ray diffraction was performed during the growth of BaTiO3 thin films on SrTiO3 substrates using both off-axis RF magnetron sputtering and pulsed laser deposition techniques. It was found that the films were ferroelectric during the growth process, and the presence or absence of a bottom SrRuO3 electrode played an important role in the growth of the films. Pulsed laser deposited films on SrRuO3 displayed an anomalously high tetragonality and unit volume, which may be connected to the previously predicted negative pressure phase of BaTiO3.