Monoclinic (Mc) phase and electric field induced phase transformation in BaTiO3

Abstract: For decades it has been a well-known fact that among the few ferroelectric compounds in the perovskite family namely BaTiO3, KNbO3, PbTiO3 Na1/2Bi1/2TiO3 the dielectric and piezoelectric properties of BaTiO3 is considerably higher than the others in polycrystalline form at room temperature. Further, similar to ferroelectric alloys exhibiting morphotropic phase boundary, single crystals of BaTiO3 exhibits anomalously large piezoelectric response when poled away from the direction of spontaneous polarization at room temperature. These anomalous features in BaTiO3 remained unexplained so far from the structural stand point. In this work we have used high resolution synchrotron X-ray powder diffraction, atomic resolution aberration corrected transmission electron microscopy, in conjunction with a novel powder poling technique, to reveal that (i) the equilibrium state of BaTiO3 is characterized by coexistence of a subtle monoclinic (Mc) phase and tetragonal phase, and (ii) strong electric field induces an orthorhombic phase at 300 K. These results suggest that BaTiO3 at room temperature is within an instability regime, and that this instability is therefore the fundamental factor responsible for the anomalous dielectric and piezoelectric properties of BaTiO3 as compared to the other homologous ferroelectric perovskite compounds. The results demonstrate that pure BaTiO3 at room temperature more akin to lead-based ferroelectric alloys close to the morphotropic phase boundary where polarization rotation and field induced ferroelectric-ferroelectric phase transformations play fundamental role in influencing the piezoelectric behavior.