Inverse Size‐Scaling Ferroelectricity in Centrosymmetric Insulating Perovskite Oxide DyScO3

Abstract The breaking of inversion symmetry dictates the emergence of electric polarization, whose topological states in superlattices and bulks have received tremendous attention for their intriguing physics brought for novel device design. However, as for substrate oxides such as LaAlO 3 , KTaO 3 , R ScO 3 ( R = rare earth element), their centrosymmetric trivial attributes make their functionality poorly explored. Here, the discovery of nanoscale thickness gradient‐induced nonpolar‐to‐polar phase transition in band insulator DyScO 3 is reported by using atomic resolution transmission electron microscopy. As the free‐standing specimen reduces to a critical thickness ≈5 nm, its inversion symmetry is spontaneously broken by surface charge transfer, which gives rise to asymmetric Dy atomic displacements and ferrodistortive octahedral order, as substantiated by the first‐principles calculations. Apart from the observation of migratable polar vortex structures, the switchable electric polarization by applied electric field is demonstrated by the piezoresponse force microscopy experiments. Given the decisive role of critical size in generating ferroelectricity, a concept of “inverse size‐scaling ferroelectric” is proposed to define a class of such materials. Distinct from the proper and improper ferroelectrics, the findings offer a new platform to explore novel low‐dimensional ferroelectrics and device applications in the future.