Free-standing ferroelectric multilayers: Crossover from thin-film to bulk behavior

TL;DR

This paper introduces free-standing ferroelectric-elastic multilayers as a bridge between thin-film and bulk ferroelectric behaviors, revealing unique phase states and potential advantages for device applications.

Contribution

It develops a nonlinear thermodynamic model to analyze phase states of multilayers, showing how they interpolate between thin-film and bulk properties and can stabilize new ferroelectric phases.

Findings

Polarization states match thin films and bulk in limiting cases.

Misfit strain-temperature phase diagrams differ at intermediate volume fractions.

New ferroelectric phases can be stabilized in multilayers.

Abstract

Ferroelectric films usually have phase states and physical properties very different from those of bulk ferroelectrics. Here we propose free-standing ferroelectric-elastic multilayers as a bridge between these two material systems. Using a nonlinear thermodynamic theory, we determine phase states of such multilayers as a function of temperature, misfit strain, and volume fraction fi of ferroelectric material. The numerical calculations performed for two classical ferroelectrics - PbTiO3 and BaTiO3 - demonstrate that polarization states of multilayers in the limiting cases fi -> 0 and fi -> 1 coincide with those of thin films and bulk crystals. At intermediate volume fractions, however, the misfit strain-temperature phase diagrams of multilayers differ greatly from those of epitaxial films. Remarkably, a ferroelectric phase not existing in thin films and bulk crystals can be stabilized in BaTiO3 multilayers. Owing to additional tunable parameter and reduced clamping, ferroelectric multilayers may be superior for a wide range of device applications.