Abstract
Perovskite piezoelectric compositions near the morphotropic phase boundary (MPB) are known to exhibit high piezoelectric response. In lead-based ABO3 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 ABO3 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(Na0.5Bi0.5)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.
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