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Microscopic origin of the high piezoelectric response of Sm-doped BiFeO3 near the morphotropic phase boundary

Rare-earth element-doped BiFeO3 has an ultrahigh piezoelectric response near the morphotropic phase boundary (MPB), making it a promising substitute for toxic lead-based piezoelectric materials. As a ferroelectric–antiferroelectric MPB, its microscopic mechanism, especially the contribution of each phase to the piezoelectric performance, is still unclear. In this work, the origin of the giant piezoelectric response of Sm-doped BiFeO3 thin films was studied by combining nanoscale in situ electric field experiments and atomic-resolution electron microscopy. Two independent reversible phase transitions were found under an external electric field: a phase transition between the polar and nonpolar phases and a phase transition between the polar and antipolar phases. Calculations indicated that the enhancement of the piezoelectric response at the MPB originated from these two reversible phase transitions, which were realized via the nucleation of the nanoscale new phase and the motion of the phase boundary under the external electric field. The above results provide deeper insight into the mechanism of the electromechanical response near the ferroelectric–antiferroelectric MPB in rare-earth element-doped BiFeO3 thin films.Rare-earth element-doped BiFeO3 has an ultrahigh piezoelectric response near the morphotropic phase boundary (MPB), making it a promising substitute for toxic lead-based piezoelectric materials. As a ferroelectric–antiferroelectric MPB, its microscopic mechanism, especially the contribution of each phase to the piezoelectric performance, is still unclear. In this work, the origin of the giant piezoelectric response of Sm-doped BiFeO3 thin films was studied by combining nanoscale in situ electric field experiments and atomic-resolution electron microscopy. Two independent reversible phase transitions were found under an external electric field: a phase transition between the polar and nonpolar phases and a phase transition between the polar and antipolar phases. Calculations indicated that the enhancement of the piezoelectric response at the MPB originated from these two reversible phase transitions, which were realized via the nucleation of the nanoscale new phase and the motion of the phase boundary unde...