Tunable and Persistent Macroscopic Polarization in Nominally Centrosymmetric Defective Oxides

Introducing symmetry breaking in materials enables the emergence of functionalities. This can be microscopically and macroscopically driven by applying external stimuli such as mechanical stress, electric field, temperature, and chemical modification. For instance, non‐zero net dipole moments are formed in a material with the presence of local charged defects or their clusters, which can alter the crystal structure, charge states, and electrostatic potential across the material. Here, a conceptual approach is demonstrated to defects‐mediated symmetry breaking that allows for built‐in polarization in a nominally centrosymmetric defective oxide, GdxCe1‐xO2‐δ (CGO) films by creating a macroscopic charge asymmetry. These results show that switchable and enduring polarization in CGO films is governed by the electric field‐driven redistribution of oxygen vacancies with a critical field strength of ≈0.5 MV cm−1 at room temperature. This leads to notable and persistent pyroelectric effect with a coefficient of ≈180 µC m−2 K−1. These findings highlight the potential to develop high‐performance, sustainable, environmentally friendly polar film materials by manipulating ionic defects from their centrosymmetric ground states. This approach provides new opportunities to expand the range of polar materials in current and future energy and electronic applications.