Mapping gradient-driven morphological phase transition at the conductive domain walls of strained multiferroic films

TL;DR

This study combines high-resolution microscopy and theoretical modeling to reveal complex morphologies and conductivity at domain walls in strained BiFeO3 films, advancing understanding of their structural and electronic properties for nano-device applications.

Contribution

It provides direct experimental evidence and theoretical analysis of AFD-FE coupling-induced phenomena at domain walls in BiFeO3, highlighting their unique morphologies and conductive behaviors.

Findings

Unusual morphologies at AFD-FE domain walls including kinks and triangle-like regions.

180° AFD-FE walls are conductive with reduced Fe-O-Fe bond angles.

LGD theory explains morphology changes due to tilt gradient energy.

Abstract

The coupling between antiferrodistortion (AFD) and ferroelectric (FE) polarization, universal for all tilted perovskite multiferroics, is known to strongly correlate with domain wall functionalities in the materials. The intrinsic mechanisms of domain wall phenomena, especially AFD-FE coupling-induced phenomena at the domain walls, have continued to intrigue the scientific and technological communities because of the need to develop the future nano-scale electronic devices. Over the past years, theoretical studies often show controversial results, owing to the fact that they are neither sufficiently nor directly corroborated with experimental evidences. In this work, the AFD-FE coupling at uncharged 180{\deg} and 71{\deg} domain walls in BiFeO3 films are investigated by means of aberration-corrected scanning transmission electron microscopy with high resolution (HR-STEM) and rationalized by phenomenological Landau-Ginsburg-Devonshire (LGD) theory. We reveal a peculiar morphology at the AFD-FE walls, including kinks, meandering, triangle-like regions with opposite oxygen displacements and curvature near the interface. The LGD theory confirms that the tilt gradient energy induces these unusual morphology and the features would change delicately with different kinds of domain walls. Moreover, the 180{\deg} AFD-FE walls are proved to be conductive with an unexpected reduction of Fe-O-Fe bond angle, which is distinct from theoretical predictions. By exploring AFD-FE coupling at domain walls and its induced functionalities, we provide exciting evidences into the links between structural distortions and its electronic properties, which benefit a lot for fundamental understanding for domain wall functionalities as well as functional manipulations for novel nano-devices.