We have studied the polarization-electric-field hysteresis, the dielectric permittivity dispersion, the piezoelectric properties, the electric-field-induced strain, and the interrelations between these properties for bismuth ferrite $\left({\text{BiFeO}}_3\right)$ ceramics. The results indicate that the domain-wall movement in ${\text{BiFeO}}_3$ is strongly inhibited by charged defects, most probably acceptor-oxygen-vacancy defect pairs. The domain-wall mobility can be considerably increased by preventing the defects from migrating into their stable configuration; this can be achieved by thermal quenching from above the Curie temperature, which freezes the disordered defect state. Similarly, ${\text{Bi}}_2{\text{O}}_3$ loss during annealing at high temperatures contributes to depinning of the domain walls and an increase in the remanent polarization. The possible defects causing the pinning effect are analyzed and discussed. A weakening of the contacts between the grains in the ceramics and crack propagation were observed during poling with constant field at 100 kV/cm. This is probably caused by an electrically induced strain associated with ferroelastic domain reversal. A relatively large piezoelectric ${\text{d}}_{33}$ constant of 44 pC/N was obtained by “cyclic poling,” in which the electric field was released after each applied cycle with the purpose to relax the mechanical stresses and minimize the problem of cracking.

Electro-mechanical interactions between charged point defects and domain walls play a key role in the functional properties of bulk and thin-film ferroelectrics. While for perovskites the macroscopic implications of the ordering degree of defects on domain-wall pinning have been reported, atomistic details of these mechanisms remain unclear. Here, based on atomic and nanoscale analyses, we propose a pinning mechanism associated with conductive domain walls in BiFeO₃, whose origin lies in the dynamic coupling of the p-type defects gathered in the domain-wall regions with domain-wall displacements under applied electric field. Moreover, we confirm that the degree of defect ordering at the walls, which affect the domain-wall conductivity, can be tuned by the cooling rate used during the annealing, allowing us to determine how this ordering affects the atomic structure of the walls. The results are useful in the design of the domain-wall architecture and dynamics for emerging nanoelectronic and bulk applications.

Lead‐based relaxor ferroelectrics are characterized by outstanding piezoelectric and dielectric properties, making them useful in a wide range of applications. Despite the numerous models proposed to describe the relation between their nanoscale polar structure and the large properties, the multiple contributions to these properties are not yet revealed. Here, by combining atomistic and mesoscopic‐scale structural analyses with macroscopic piezoelectric and dielectric measurements across the (100–x)Pb(Mg_1/3Nb_2/3)O₃–xPbTiO₃ (PMN–xPT) phase diagram, a direct link is established between the multiscale structure and the large nonlinear macroscopic response observed in the monoclinic PMN‐xPT compositions. The approach reveals a previously unrecognized softening effect, which is common to Pb‐based relaxor ferroelectrics and arises from the displacements of low‐angle nanodomain walls, facilitated by the nanoscale polar character and lattice strain disorder. This comprehensive comparative study points to the multiple, distinct mechanisms that are responsible for the large piezoelectric response in relaxor ferroelectrics.

Electromechanical properties such as d₃₃ and strain are significantly enhanced at morphotropic phase boundaries (MPBs) between two or more different crystal structures. Many actuators, sensors and MEMS devices are therefore systems with MPBs, usually between polar phases in lead (Pb)-based ferroelectric ceramics. In the search for Pb-free alternatives, systems with MPBs between polar and non-polar phases have recently been theorized as having great promise. While such an MPB was identified in rare-earth (RE) modified bismuth ferrite (BFO) thin films, synthesis challenges have prevented its realization in ceramics. Overcoming these, we demonstrate a comparable electromechanical response to Pb-based materials at the polar-to-non-polar MPB in Sm modified BFO. This arises from ‘dual’ strain mechanisms: ferroelectric/ferroelastic switching and a previously unreported electric-field induced transition of an anti-polar intermediate phase. We show that intermediate phases play an important role in the macroscopic strain response and may have potential to enhance electromechanical properties at polar-to-non-polar MPBs.