Emergent ultrasmall multiferroics in paraelectric perovskite oxide by hole polarons.

Ultimately small multiferroics with coupled ferroelectric and ferromagnetic order parameters have drawn considerable attention for their tremendous technological potential. Nevertheless, these ferroic orders inevitably disappear below the critical size of several nanometers in conventional ferroelectrics or multiferroics. Here, based on first-principles calculations, we propose a new strategy to overcome this limitation and create ultrasmall multiferroic elements in otherwise nonferroelectric CaTiO3 by engineering the interplay of oxygen octahedral rotations and hole polarons, though both of them are generally believed to be detrimental to ferroelectricity. It is found that the hole doped in CaTiO3 spontaneously forms a localized polaronic state. The lattice distortions associated with a hole polaron interacting with the intrinsic oxygen octahedral rotations in CaTiO3 effectively break the inversion symmetry and create atomic-scale ferroelectricity beyond the critical size limitation. The hole polaron also causes highly localized magnetism attributed to the associated spin-polarized electric state and thus manifests as a multiferroic polaron. Moreover, the hole polaron exhibits high hopping mobility accompanied by rich switching of polarization and magnetic directions, indicating strong magnetoelectric coupling with a mechanism dissimilar from that of conventional multiferroics. The present work provides a new mechanism to engineer inversion symmetry and opens avenues for designing unusual multifunctional materials.