Programmable Ferroelectricity in Hf_0.5Zr_0.5O₂ Enabled by Oxygen Defect Engineering

Ferroelectricity, especially the Si-compatible type recently observed in hafnia-based materials, is technologically useful for modern memory and logic applications, but it is challenging to differentiate intrinsic ferroelectric polarization from the polar phase and oxygen vacancy. Here, we report electrically controllable ferroelectricity in a Hf_0.5Zr_0.5O₂-based heterostructure with Sr-doped LaMnO₃, a mixed ionic–electronic conductor, as an electrode. Electrically reversible extraction and insertion of an oxygen vacancy into Hf_0.5Zr_0.5O₂ are macroscopically characterized and atomically imaged in situ. Utilizing this reversible process, we achieved multilevel polarization states modulated by the electric field. Our study demonstrates the usefulness of the mixed conductor to repair, create, manipulate, and utilize advanced ferroelectric functionality. Furthermore, the programmed ferroelectric heterostructures with Si-compatible doped hafnia are desirable for the development of future ferroelectric electronics.