Charge-order–driven ferroelectrics are an emerging class of functional materials, distinct from conventional ferroelectrics, where electron-dominated switching can occur at high frequency. Despite their promise, only a few systems exhibiting this behavior have been experimentally realized thus far, motivating the need for new materials. Here, we use density-functional theory to study the effect of artificial structuring on mixed-valence solid-solution La1/3Sr2/3FeO3 (LSFO), a system well studied experimentally. Our calculations show that A-site cation (111)-layered LSFO exhibits a ferroelectric charge-ordered phase in which inversion symmetry is broken by changing the registry of the charge order with respect to the superlattice layering. The phase is energetically degenerate with a ground-state centrosymmetric phase, and the computed switching polarization is 39 μC/cm2, a significant value arising from electron transfer between FeO6 octahedra. Our calculations reveal that artificial structuring of LSFO and other mixed valence oxides with robust charge ordering in the solid solution phase can lead to charge-order–induced ferroelectricity.
Theory of charge order and heavy-electron formation in the mixed-valence compound KNi2Se2
