Intrinsic polarization switching mechanisms in BiFeO3

A first-principles-based effective Hamiltonian technique is used to investigate the polarization switching mechanisms in two polymorphic phases of BiFeO3 having no defects. The switching mechanism is homogeneous for any switching field in the rhombohedral phase, while in the supertetragonal phase it changes from the classical nucleation and domain-wall motion to nucleation-limited switching with virtually no propagation, and then to homogeneous switching with increasing electric field. The first two inhomogeneous switching mechanisms of the supertetragonal phase of BiFeO3 are thus intrinsic in nature, and can be well described by the classical and nucleation-limited switching models, respectively. The reason behind their absence in the rhombohedral phase is also indicated. Moreover, the field-induced changes of switching mechanism within the supertetragonal phase are further elucidated from an energetic point of view.