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The discovery of ferroelectricity in hafnia based thin films has catalyzed significant research focused on understanding the ferroelectric property origins and means to increase stability of the ferroelectric phase. Prior studies have revealed that biaxial tensile stress via an electrode “capping effect” is a suspected ferroelectric phase stabilization mechanism. This effect is commonly reported to stem from a coefficient of thermal expansion (CTE) incongruency between the hafnia and top electrode. Despite reported correlations between ferroelectric phase fraction and electrode CTE, the thick silicon substrate dominates the mechanics and CTE-related stresses, negating any dominant contribution from an electrode CTE mismatch toward the capping effect. In this work, these discrepancies are reconciled, and the origin of these differences deriving from electrode elastic modulus, not CTE, is demonstrated. Pt/M/TaN/Hf0.5Zr0.5O2/TaN/Si devices, where M is platinum, TaN, iridium, tungsten, and ruthenium, were fabricated. Sin2(ψ)-based X-ray diffraction measurements of biaxial stress in the HZO layer reveal a strong correlation between biaxial stress, remanent polarization, and electrode elastic modulus. Conversely, a low correlation exists between the electrode CTE, HZO biaxial stress, and remanent polarization. A higher elastic modulus enhances the resistance to electrode elastic deformation, which intensifies the capping effect during crystallization, and culminates in the tandem restriction of out-of-plane hafnia volume expansion and preferential orientation of the polar c-axis normal to the plane. These behaviors concomitantly increase the ferroelectric phase stability and polarization magnitude. This work provides electrode material selection guidelines toward the development of high-performing ferroelectric hafnia into microelectronic devices, such as nonvolatile memories.
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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:
- 10477195
- Publisher / Repository:
- Wiley
- 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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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.more » « less
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- Free Publicly Accessible Full Text
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Accepted Manuscript
- Journal Article:
- https://doi.org/10.1002/aelm.202200601
