Adaptive strain prompting a pseudo-morphotropic phase boundary in ferroelectric (1-x)Na0.5Bi0.5TiO3-xBaTiO3

The understanding of the atomistic origin of the morphotropic phase boundary (MPB) occurring in composition-temperature phase diagrams of ferroelectric solid solutions is a key topic in material science because materials often exhibit anomalous properties at the MPB. Here we reveal mesoscopic-scale structural correlations for a leading Pb-free ferroelectric system, (1-x)Na0.5Bi0.5TiO3-xBaTiO3 (NBT-xBT), by examining atomic pair distribution functions and Raman scattering data at ambient conditions. We demonstrate that the amplification of the piezoelectric properties of NBT-xBT at the MPB are predominantly driven by an easy switchability resulting from a progressive decoupling between strain and polarization as the Ba content increases from zero to the critical MPB composition. It was observed that as Ba content increases towards MPB, competing local correlations, such as A-site chemical order, antiferrodistortive correlations of correlated BO6 tilts, and antipolar Bi shifts, are reduced, which in turn renders favorable conditions for easy switching of local dipoles under external fields. In addition, the evolving characteristics of the atomic dynamics as a function of composition suggest that the local potential functions of the cations are not completely flat at the MPB. Altogether, our results reveal atomistic mechanisms responsible for the observed elevated MPB properties in the case of NBT-xBT which imply that the so-called MPB of NBT-xBT should not be categorized as originally introduced for Pb-containing solid solutions.