The Polar/Antipolar Phase Boundary of BiMnO3-BiFeO3-PbTiO3: Interplay among Crystal Structure, Point Defects, and Multiferroism

The ferromagnetic perovskite oxide BiMnO3 is a highly topical material, and the solid solutions it forms with antiferromagnetic/ferroelectric BiFeO3 and with ferroelectric PbTiO3 result in distinctive polar/nonpolar morphotropic phase boundaries (MPBs). The exploitation of such a type of MPBs could be a novel approach to engineer novel multiferroics with phase-change magnetoelectric responses, in addition to ferroelectrics with enhanced electromechanical performance. Here, the interplay among crystal structure, point defects, and multiferroic properties of the BiMnO3-BiFeO3-PbTiO3 ternary system at its line of MPBs between polymorphs of tetragonal P4mm (polar) and orthorhombic Pnma (antipolar) symmetries is reported. A strong dependence of the phase coexistence on thermal history is found: phase percentage significantly changes whether the material is quenched or slowly cooled from high temperature. The origin of this phenomenon is investigated with temperature-dependent structural and physical property characterizations. A major role of the complex defect chemistry, where a Bi/Pb-deficiency allows Mn and Fe ions to have a mixed-valence state, in the delicate balance between polymorphs is proposed, and its influence in the magnetic and electric ferroic orders is defined.