Sharp Transformation across Morphotropic Phase Boundary in Sub‐6 nm Wake‐Up‐Free Ferroelectric Films by Atomic Layer Technology

Atomic layer engineering is investigated to tailor the morphotropic phase boundary (MPB) between antiferroelectric, ferroelectric, and paraelectric phases. By increasing the HfO(2) seeding layer with only 2 monolayers, the overlying ZrO(2) layer experiences the dramatic phase transition across the MPB. Conspicuous ferroelectric properties including record‐high remanent polarization (2P(r) ≈ 60 µC cm(−2)), wake‐up‐free operation, and high compatibility with advanced semiconductor technology nodes, are achieved in the sub‐6 nm thin film. The prominent antiferroelectric to ferroelectric phase transformation is ascribed to the in‐plane tensile stress introduced into ZrO(2) by the HfO(2) seeding layer. Based on the high‐resolution and high‐contrast images of surface grains extracted precisely by helium ion microscopy, the evolution of the MPB between tetragonal, orthorhombic, and monoclinic phases with grain size is demonstrated for the first time. The result indicates that a decrease in the average grain size drives the crystallization from the tetragonal to polar orthorhombic phases.