Self-Poling of BiFeO₃ Thick Films

Bismuth ferrite (BiFeO₃) is difficult to pole because of the combination of its high coercive field and high electrical conductivity. This problem is particularly pronounced in thick films. The poling, however, must be performed to achieve a large macroscopic piezoelectric response. This study presents evidence of a prominent and reproducible self-poling effect in few-tens-of-micrometer-thick BiFeO₃ films. Direct and converse piezoelectric measurements confirmed that the as-sintered BiFeO₃ thick films yield <i>d</i>₃₃ values of up to ∼20 pC/N. It was observed that a significant self-poling effect only appears in cases when the films are heated and cooled through the ferroelectric-paraelectric phase transition (Curie temperature <i>T</i>_C ∼ 820 °C). These self-poled films exhibit a microstructure with randomly oriented columnar grains. The presence of a compressive strain gradient across the film thickness cooled from above the <i>T</i>_C was experimentally confirmed and is suggested to be responsible for the self-poling effect. Finally, the macroscopic <i>d</i>₃₃ response of the self-poled BiFeO₃ film was characterized as a function of the driving-field frequency and amplitude

Atomic-Level Response of the Domain Walls in Bismuth Ferrite in a Subcoercive-Field Regime

The atomic-level response of zigzag ferroelectric domain walls (DWs) was investigated with in situ bias scanning transmission electron microscopy (STEM) in a subcoercive-field regime. Atomic-level movement of a single DW was observed. Unexpectedly, the change in the position of the DW, determined from the atomic displacement, did not follow the position of the strain field when the electric field was applied. This can be explained as low mobility defect segregation at the initial DW position, such as ordered clusters of oxygen vacancies. Further, the triangular apex of the zigzag wall is pinned, but it changes its shape and becomes asymmetric under electrical stimuli. This phenomenon is accompanied by strain and bound charge redistribution. We report on unique atomic-scale phenomena at the DW level and show that in situ STEM studies with atomic resolution are very relevant as they complement, and sometimes challenge, the knowledge gained from lower resolution studies

Pressure Control of Nonferroelastic Ferroelectric Domains in ErMnO₃

Mechanical pressure controls the structural, electric, and magnetic order in solid-state systems, allowing tailoring of their physical properties. A well-established example is ferroelastic ferroelectrics, where the coupling between pressure and the primary symmetry-breaking order parameter enables hysteretic switching of the strain state and ferroelectric domain engineering. Here, we study the pressure-driven response in a nonferroelastic ferroelectric, ErMnO3, where the classical stress–strain coupling is absent and the domain formation is governed by creation–annihilation processes of topological defects. By annealing ErMnO3 polycrystals under variable pressures in the MPa regime, we transform nonferroelastic vortex-like domains into stripe-like domains. The width of the stripe-like domains is determined by the applied pressure as we confirm by three-dimensional phase field simulations, showing that pressure leads to oriented layer-like periodic domains. Our work demonstrates the possibility to utilize mechanical pressure for domain engineering in nonferroelastic ferroelectrics, providing a lever to control their dielectric and piezoelectric responses