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Ferroelectric hafnium-zirconium oxide (HZO) is an excellent candidate for low-power non-volatile memory applications due to its demonstrated ferroelectricity at the nanoscale and compatibility with silicon-based technologies. The interface of HZO in contact with its electrode, typically TiN in a metal–ferroelectric–metal (MFM) capacitor configuration, is of particular interest because factors, such as volume confinement, impurity concentration, interfacial layers, thermal expansion mismatch, and defect trapping, are believed to play a crucial role in the ferroelectric performance of HZO-based devices. Processing variables, such as precursor type, oxygen source, dose duration, and deposition temperature, are known to strongly affect the quality of the oxide–metal interface. However, not many studies have focused on the effect of breaking or maintaining vacuum during MFM deposition. In this study, sequential, no-atmosphere processing (SNAP) is employed to avoid atmospheric exposure, where electrode TiN and ferroelectric HZO are deposited sequentially in the atomic layer deposition chamber without breaking vacuum. The effect of breaking vacuum during the sequential deposition steps is elucidated by fabricating and characterizing MFM capacitors with and without intentional vacuum breaks prior to the deposition of the HZO and top TiN. Using x-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry (ToF-SIMS), we reveal that breaking vacuum after bottom TiN electrode deposition leads to interfacial oxidation and increased carbon contamination, which preferentially stabilizes the non-ferroelectric tetragonal phase and lead to diminished remanent polarization. Avoiding carbon impurities and interfacial TiOx at the HZO and TiN interface using SNAP leads to heightened remanent polarization, reduced leakage current density, and elimination of the wake-up effect. Our work highlights the effect of vacuum breaking on the processing-structure-properties of HZO-based capacitors, revealing that maintaining vacuum can significantly improve ferroelectric properties.
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Origin of Ferroelectric Phase Stabilization via the Clamping Effect in Ferroelectric Hafnium Zirconium Oxide Thin Films
Abstract The presence of the top electrode on hafnium oxide‐based thin films during processing has been shown to drive an increase in the amount of metastable ferroelectric orthorhombic phase and polarization performance. This “Clamping Effect,” also referred to as the Capping or Confinement Effect, is attributed to the mechanical stress and confinement from the top electrode layer. However, other contributions to orthorhombic phase stabilization have been experimentally reported, which may also be affected by the presence of a top electrode. In this study, it is shown that the presence of the top electrode during thermal processing results in larger tensile biaxial stress magnitudes and concomitant increases in ferroelectric phase fraction and polarization response, whereas film chemistry, microstructure, and crystallization temperature are not affected. Through etching experiments and measurement of stress evolution for each processing step, it is shown that the top electrode locally inhibits out‐of‐plane expansion in the HZO during crystallization, which prevents equilibrium monoclinic phase formation and stabilizes the orthorhombic phase. This study provides a mechanistic understanding of the clamping effect and orthorhombic phase formation in ferroelectric hafnium oxide‐based thin films, which informs the future design of these materials to maximize ferroelectric phase purity and corresponding polarization behavior.
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- Award ID(s):
- 1832829
- PAR ID:
- 10443506
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Advanced Electronic Materials
- Volume:
- 8
- Issue:
- 12
- ISSN:
- 2199-160X
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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