Epitaxial growth and phase evolution of ferroelectric La-doped HfO₂ films

Hafnium-oxide-based materials are considered a promising candidate for next-generation nonvolatile memory devices owing to their good CMOS compatibility and robust ferroelectricity at the nanoscale. In this work, we synthesize highly (111)-oriented La-doped HfO₂ (HLO) ferroelectric thin films via pulsed laser deposition. Furthermore, the effect of La dopant concentration, thickness, and growth temperature on the ferroelectricity of HLO films is investigated in detail. A maximum remnant polarization of ∼9 μC/cm² is achieved for only the 5-nm-thick 3 mol. % HLO films without a wake-up process. The 180° inversion of the domain, the butterfly-shaped capacitance–voltage curve, and typical ferroelectric displacement current curve further demonstrate the robust ferroelectricity at the nanoscale. Moreover, the phase evolves from the monoclinic to the orthorhombic and subsequently to the cubic phase with increasing La concentration, which is due to the combined action of oxygen vacancy, epitaxial strain, and chemical pressure. Additionally, in the interface configuration of HLO/La_0.7Sr_0.3MnO₃ (LSMO), the MnO₂^0.7− layer is substituted by the HLO layer on the MnO₂-terminated surface of LSMO, which can be attributed to the fact that the HLO layer with higher electronegativity replaces the MnO₂^0.7− layer with the same electronegativity in the HLO film. Therefore, this study provides a reliable pathway for directly obtaining a lightly doped HLO ferroelectric thin film, which can help to broaden the understanding of the ferroelectric physical mechanisms with element doping.