Simultaneous optimization of remanent polarization (2Pr) and long-term endurance remains a critical challenge for Hf0.5Zr0.5O2 (HZO)-based ferroelectric thin films in next-generation non-volatile memory technologies. Here, we introduce a sequenced mixed-oxidant atomic layer deposition (ALD) process that employs an initial deionized H2O pulse followed by controlled O3 exposure to decouple the inherent trade-off between strong ferroelectricity and reliability. The optimized Mix-10s sample delivers a high 2Pr ≈ 48 μC/cm 2 in ~10 nm-thick films, accompanied by wake-up-free characteristics and outstanding cycling stability, retaining 98.9% of the pristine polarization after 10 9 bipolar switching cycles with minimal fatigue. Structural and electrical characterizations, including grazing-incidence X-ray diffraction, transmission electron microscopy, piezoresponse force microscopy, and switching current analysis, reveal a cooperative defect-engineering mechanism. The initial H2O pulse introduces a moderate oxygen vacancy concentration that lowers the kinetic barrier for stabilizing the ferroelectric orthorhombic phase, whereas the subsequent O3 pulse removes residual carbon and hydrogen impurities and suppresses excessive vacancy accumulation, thereby mitigating domain wall pinning and leakage. This hybrid oxidant ALD approach provides a scalable and CMOS compatible pathway toward high-polarization, fatigue free hafnia-based ferroelectrics for advanced memory and neuromorphic applications.
Lv et al. (Fri,) studied this question.