The Ferroelectricity and Crystallinity of Zirconia, Hafnia and Hafnium Zirconium Oxide (HZO) Ultrathin Films Prepared by Atomic Layer Deposition With and Without Post-Annealing

Large stable ferroelectricity in hafnium zirconium oxide (HZO) solid solution ultrathin films (including pure zirconia (ZrO2) and hafnia (HfO2)) and ZrO2/HfO2 bilayer ultrathin films of thickness ranging from 5–12 nm, prepared by thermal atomic layer deposition or remote plasma atomic layer deposition (RP-ALD) has been demonstrated. Ferroelectric crystallization of the ZrO2 ultrathin film with high-pressure orthorhombic (o) space group Pbc21 could be achieved without post-annealing due to the plasma-induced thermal stresses experienced by the film during the RP-ALD process. In contrast, for the ZrO2/HfO2 bilayer ultrathin film, due to the high crystallization temperature of HfO2, post-annealing was needed to achieve sufficient confinement of the sandwiched HfO2 layer by the ZrO2 top layer and Si bottom substrate to promote the high-pressure ferroelectric o-phase in HfO2. The ferroelectric properties of the HZO ultrathin films prepared by RP-ALD were highly dependent on the Hf-to-Zr ratio — an increasing amount of HfO2 has been found to be detrimental to the ferroelectricity, mainly due to the high crystallization temperature of HfO2. Without post-annealing, the ferroelectricity of the HZO ultrathin films was governed by the relative amounts of the amorphous phase and the ferroelectric o-phase induced by the plasma treatment. While with post-annealing, the ferroelectricity was governed by the relative amounts of the ferroelectric o-phase and the non-ferroelectric monoclinic (m) phase.