Abstract Hf 0.5 Zr 0.5 O 2 (HZO) thin films are promising candidates for non-volatile memory and other related applications due to their demonstrated ferroelectricity at the nanoscale and compatibility with Si processing. However, one reason that HZO has not been fully scaled into industrial applications is due to its deleterious wake-up and fatigue behavior which leads to an inconsistent remanent polarization during cycling. In this study, we explore an interfacial engineering strategy in which we insert 1 nm Al 2 O 3 interlayers at either the top or bottom HZO/TiN interface of sequentially deposited metal-ferroelectric-metal capacitors. By inserting an interfacial layer while limiting exposure to the ambient environment, we successfully introduce a protective passivating layer of Al 2 O 3 that provides excess oxygen to mitigate vacancy formation at the interface. We report that TiN/HZO/TiN capacitors with a 1 nm Al 2 O 3 at the top interface demonstrate a higher remanent polarization (2P r ∼ 42 μ C cm −2 ) and endurance limit beyond 10 8 cycles at a cycling field amplitude of 3.5 MV cm −1 . We use time-of-flight secondary ion mass spectrometry, energy dispersive spectroscopy, and grazing incidence x-ray diffraction to elucidate the origin of enhanced endurance and leakage properties in capacitors with an inserted 1 nm Al 2 O 3 layer. We demonstrate that the use of Al 2 O 3 as a passivating dielectric, coupled with sequential ALD fabrication, is an effective means of interfacial engineering and enhances the performance of ferroelectric HZO devices.
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Large remnant polarization and great reliability characteristics in W/HZO/W ferroelectric capacitors
In this work, the effect of rapid thermal annealing (RTA) temperature on the ferroelectric polarization in zirconium-doped hafnium oxide (HZO) was studied. To maximize remnant polarization (2P r ), in-plane tensile stress was induced by tungsten electrodes under optimal RTA temperatures. We observed an increase in 2P r with RTA temperature, likely due to an increased proportion of the polar ferroelectric phase in HZO. The HZO capacitors annealed at 400°C did not exhibit any ferroelectric behavior, whereas the HZO capacitors annealed at 800°C became highly leaky and shorted for voltages above 1 V. On the other hand, annealing at 700 °C produced HZO capacitors with a record-high 2P r of ∼ 64 μ C cm −2 at a relatively high frequency of 111 kHz. These ferroelectric capacitors have also demonstrated impressive endurance and retention characteristics, which will greatly benefit neuromorphic computing applications.
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- Award ID(s):
- 2023752
- NSF-PAR ID:
- 10354311
- Date Published:
- Journal Name:
- Frontiers in Materials
- Volume:
- 9
- ISSN:
- 2296-8016
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract Ferroelectric switching is demonstrated in CeO2‐doped Hf0.5Zr0.5O2(HZCO) thin films with application in back‐end‐of‐line compatible embedded memories. At low cerium oxide doping concentrations (2.0–5.6 mol%), the ferroelectric orthorhombic phase is stabilized after annealing at temperatures below 400 °C. HZCO ferroelectrics show reliable switching characteristics beyond 1011cycles in TiN/HZCO/TiN capacitors, several orders of magnitude greater than identically processed Hf0.5Zr0.5O2(HZO) capacitors, without sacrificing polarization and retention. Internal photoemission and photoconductivity experiments show that CeO2‐doping introduces in‐gap states in HZCO that are nearly aligned with TiN Fermi level, facilitating electron injection through these states. The enhanced average bulk conduction, which may lead to more uniform thermal dissipation in the HZCO films, delays irreversible degradation via breakdown that leads to device failure after repeated programming cycles.
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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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Abstract As an emerging nonvolatile memory technology, HfO2‐based ferroelectrics exhibit excellent compatibility with silicon CMOS process flows; however, the reliability of polarization switching in these materials remains a major challenge. During repeated field programming and erase of the polarization state of initially pristine HfO2‐based ferroelectric capacitors, the magnitude of the measured polarization increases, a phenomenon known as “wake‐up”. In this study, the authors attempt to understand what causes the wake‐up effect in Hf0.5Zr0.5O2(HZO) capacitors using nondestructive methods that probe statistically significant sample volumes. Synchrotron X‐ray diffraction reveals a concerted shift in HZO Bragg peak position as a function of polarization switching cycle number in films prepared under conditions such that they exhibit extremely large (≈3000%) wake‐up. In contrast, a control sample with insignificant wake‐up shows no such peak shift. Capacitance – voltage measurements show evolution in the capacitance loop with switching cycle number for the wake‐up sample and no change for the control sample. Piezoresponse force microscopy measurements are utilized to visualize the domain switching with wake‐up. The combination of these observations clearly demonstrates that wake‐up is caused by a field‐driven phase transformation of the tetragonal phase to the metastable ferroelectric orthorhombic phase during polarization switching of HZO capacitors.
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Rapid advancements within photovoltaics realm necessitates swift fabrication of the modules using cheap materials through cost effective manufacturing processes to achieve short cost payback time. Photovoltaics manufacturing includes chemical processing of the materials followed by thermal annealing. Yet, long-term annealing of the materials using high temperature furnaces have remained the prevalent post-processing approach in industry which necessitates alternative methods to achieve high performance modules through rapid and economical processes. Intense pulse light (IPL) has been successfully applied as a promising rapid post-process annealing for various thin film photovoltaics, particularly to process the organic-inorganic perovskite solar cell (PSC) layers. In this paper, several results pertinent to the application of IPL on perovskite and SnO2 electron transport thin films are presented and the role of IPL on rapid thermal annealing (RTA) is explained. We show that swift fabrication of PSCs through IPL can result in efficiencies exceeding 16% when the Perovskite film is annealed with aid of CH2I2 alkyl halide additive in the ambient with 60% relative humidity. In addition, the synergy of IPL-alkyl halide interaction for other perovskite chemistries is introduced. We show that achieving to PSCs exceeding 12% efficiency was possible when the perovskite and SnO2 ETL was annealed sequentially through IPL.more » « less
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.3389/fmats.2022.969188
