Origin of Ferroelectricity in BiFeO₃-Based Solid Solutions

We investigate the origin of ferroelectricity in the BiFeO₃-LaFeO₃ system in rhombohedral R3c and tetragonal P4mm symmetries by ab initio density functional theory calculations and compare their electronic features with paraelectric orthorhombic Pnma symmetry. We show that a coherent accommodation of stereo-active lone pair electrons of Bi is the detrimental factor of ferroelectricity. A Bloch function arising from an indirect Bi_6p-Fe_3d hybridization mediated through O_2p is the primary origin of spontaneous polarization (P_s) in the rhombohedral system. In the orthorhombic system, a similar Bloch function was found, whereas a staggered accommodation of stereo-active lone pair electrons of Bi exclusively results in paraelectricity. A giant P_s reported in the tetragonal system originates from an orbital hybridization of Bi_6p and O_2p, where Fe-3d plays a minor role. The P_s in the rhombohedral system decreases with increasing La content, while that in the tetragonal system displays a discontinuous drop at a certain La content. We discuss the electronic factors affecting the P_s evolutions with La content.