Evolution of mesoscopic domain structure and macroscopic properties in lead-free Bi_0.5Na_0.5TiO₃-BaTiO₃ ferroelectric ceramics

Bismuth sodium titanate and related compounds are promising lead-free ferroelectric materials potentially useful in a wide range of piezoelectric applications. The domain structure plays an important role in determining the piezoelectric and ferroelectric properties and thereby the performance of electromechanical transducers. In this work, piezoresponse force microscopy (PFM) is used to gain insights into the mesoscopic-scale domain structure and its evolution under electric field in the (1−x)Bi_0.5Na_0.5TiO₃-xBaTiO₃ (BNT-BT) piezoceramics with compositions varying from x = 0 to x = 0.08. A phase transition from the rhombohedral phase to the tetragonal phase is observed with increasing BT contents. A relationship is established between the relaxor behavior and the domain structures imaged by PFM, i.e., short-range polar regions without visible domains in relaxor ceramics of pure BNT, while long-range ordered polar states with clear domains in ferroelectric ceramics with the addition of BT content. Distinct micro-domains are observed in the ceramics with compositions close to the morphotropic phase boundary (MPB), but the domain size drops to nanometers in the MPB composition with an increasing domain wall density. An electric field can induce the transformation from the relaxor behavior to a ferroelectric state, accompanied by an increase in domain sizes and a rearrangement/reorientation of the polar domains. This study of domain structure and its evolution in BNT-BT provides a better understanding of the relationship between the crystal structure, mesoscopic-scale domains, and macroscopic properties in these important lead-free piezoelectric ceramics.