Interface-engineered ferroelectricity of epitaxial Hf_0.5Zr_0.5O₂ thin films

Ferroelectric hafnia-based thin films have attracted intense attention due to their compatibility with complementary metal-oxide-semiconductor technology. However, the ferroelectric orthorhombic phase is thermodynamically metastable. Various efforts have been made to stabilize the ferroelectric orthorhombic phase of hafnia-based films such as controlling the growth kinetics and mechanical confinement. Here, we demonstrate a key interface engineering strategy to stabilize and enhance the ferroelectric orthorhombic phase of the Hf_0.5Zr_0.5O₂ thin film by deliberately controlling the termination of the bottom La_0.67Sr_0.33MnO₃ layer. We find that the Hf_0.5Zr_0.5O₂ films on the MnO₂-terminated La_0.67Sr_0.33MnO₃ have more ferroelectric orthorhombic phase than those on the LaSrO-terminated La_0.67Sr_0.33MnO₃, while with no wake-up effect. Even though the Hf_0.5Zr_0.5O₂ thickness is as thin as 1.5 nm, the clear ferroelectric orthorhombic (111) orientation is observed on the MnO₂ termination. Our transmission electron microscopy characterization and theoretical modelling reveal that reconstruction at the Hf_0.5Zr_0.5O₂/ La_0.67Sr_0.33MnO₃ interface and hole doping of the Hf_0.5Zr_0.5O₂ layer resulting from the MnO₂ interface termination are responsible for the stabilization of the metastable ferroelectric phase of Hf_0.5Zr_0.5O₂. We anticipate that these results will inspire further studies of interface-engineered hafnia-based systems.