Origin of high piezoelectric response in A-site disordered morphotropic phase boundary composition of lead-free piezoelectric 0.93(Na _0.5Bi_0.5)TiO₃-0.07BaTiO₃

Perovskite piezoelectric compositions near the morphotropic phase boundary (MPB) are known to exhibit high piezoelectric response. In lead-based ABO ₃ compound with B-site disorder, the origin of this enhancement has been associated with the presence of an intermediate monoclinic/orthorhombic state that bridges the adjacent ferroelectric rhombohedral and tetragonal phases. However, the origin of high piezoelectric response in lead-free ABO ₃ compounds with A-site disorder has not been conclusively established. We describe a microscopic model derived from comparative analyses of high resolution transmission electron microscopy and neutron diffraction that explains the origin of high piezoelectric response in lead-free MPB compositions of 0.93(Na_0.5Bi_0.5)TiO₃-0. 07BaTiO₃. Direct observation of nanotwins with monoclinic symmetry confirmed the presence of an intermediate bridging phase that facilitates a pathway for polarization reorientation. Monoclinic distortions of an average rhombohedral phase are attributed to localized displacements of atoms along the non-polar directions. © 2013 American Institute of Physics.