Surface nucleation of the paraelectric phase in ferroelectric BaTiO3: Atomic scale mapping

TL;DR

This study uses high-resolution electron microscopy to observe the atomic-scale nucleation of paraelectric regions at the surface of BaTiO3 during its ferroelectric-paraelectric transition, revealing the role of mechanical interactions.

Contribution

It provides the first atomic-scale visualization of surface nucleation of paraelectric phases in BaTiO3 and quantifies the nucleation barrier and mechanical effects involved.

Findings

Paraelectric nuclei of a few unit cells form at the surface during transition

The transition involves surface nucleation and growth of cubic phase towards the bulk

Mechanical interactions dominate the nucleation process

Abstract

In ferroelectricity, atomic-scale dipole moments interact collectively to produce strong electro-mechanical coupling and switchable macroscopic polarization. Hence, the functionality of ferroelectrics emerges at a solid-solid phase transformation that is accompanied by a sudden disappearance of an inversion symmetry. Much effort has been put to understand the ferroelectric transition at the polarization length scale. Nevertheless, the dipole-moment origin of ferroelectricity has remained elusive. Here, we used variable-temperature high-resolution transmission electron microscopy to reveal the dipole-moment dynamics during the ferroelectric-to-paraelectric transition. We show that the transition occurs when paraelectric nuclei of the size of a couple of unit cells emerge near the surface. Upon heating, the cubic phase sidewalk grows towards the bulk. We quantified the nucleation barrier and show dominancy of mechanical interactions, helping us demonstrate similarities to predictions of domain nucleation during electric field switching. Our work motivates dynamic atomic-scale characterizations of solid-solid transitions in other materials.