Effect of Precursor Purge Time on Plasma-Enhanced Atomic Layer Deposition-Prepared Ferroelectric Hf0.5Zr0.5O₂ Phase and Performance

Hafnium oxide-based thin films, in particular hafnium zirconium oxide (HZO), have potential for applications in nonvolatile memory and energy harvesting. Atomic layer deposition (ALD) is the most widely used method for HZO deposition due to its precise thickness control and ability to provide conformal coverage. Previous studies have shown the effects of different metal precursors, oxidizer precursors, and process temperatures on the ferroelectric properties of HZO. However, no mechanism has been identified to describe the different phase stabilities as the metal precursor purge time varies. This study investigates how varying the metal precursor purge time during plasma-enhanced ALD (PE-ALD) influences the phases and properties of the HZO thin films. Grazing incidence X-ray diffraction, Fourier transform infrared spectroscopy, and scanning transmission electron microscopy are used to study the changes in phase of HZO with variation of the metal precursor purge time during the PE-ALD process. The phases observed are correlated with polarization and relative permittivity responses under an electric field, including wake-up and endurance effects. The resulting phases and properties are linked to changes in composition, as measured using time-of-flight secondary ion mass spectrometry and X-ray photoelectron spectroscopy. It is shown that short metal precursor purge times result in increased carbon and nitrogen impurities and stabilization of the antipolar Pbca phase. Long purge times lead to films comprising predominantly the ferroelectric Pca2₁ phase.