Ferroelectric (Hf,Zr)O2 thin films have attracted increased interest from the ferroelectrics community and the semiconductor industry due to their ability to exhibit ferroelectricity at nanoscale dimensions. The properties and performance of the ferroelectric (Hf,Zr)O2 films generally depend on various factors such as surface energy (e.g., through grain size or thickness), defects (e.g., through dopants, oxygen vacancies, or impurities), electrodes, interface quality, and preferred crystallographic orientation (also known as crystallographic texture or simply texture) of grains and/or domains. Although some factors affecting properties and performance have been studied extensively, the effects of texture on the material properties are still not understood. Here, the influence of texture of the bottom electrode and Hf0.5Zr0.5O2 (HZO) films on properties and performance is reported. The uniqueness of this work is the use of a consistent deposition process known as Sequential, No-Atmosphere Processing (SNAP) that produces films with different preferred orientations yet minimal other differences. The results shown in this study provide both new insight on the importance of the bottom electrode texture and new fundamental processing-structure–property relationships for the HZO films.more » « less
- NSF-PAR ID:
- Publisher / Repository:
- American Institute of Physics
- Date Published:
- Journal Name:
- Journal of Applied Physics
- Medium: X
- Sponsoring Org:
- National Science Foundation
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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.more » « less
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.
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.
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.
We report the dielectric Properties of HfO 2 -based films in the optical–high frequency range. The demonstrated tunability of the optical dielectric constant of HfO 2 -based compounds is of great relevance for optoelectronic applications, e.g., high-refractive index dielectrics for nanoantenna and optical coatings for electronic displays. Since the optical dielectric constant of HfO 2 is determined by the electronic structure and its crystal environment, we tune the physical properties of HfO 2 films on MgO by adding different dopants. In this work, we aim to determine the influence of doping together with the resulting crystal structure on the optical dielectric constant. Hence, we studied 20 mol. % Y-doped HfO 2 (HYO), Hf 0.5 Zr 0.5 O 2 (HZO), and Hf 0.5 Ce 0.5 O 2 (HCO). Among the dopants, Y 2 O 3 has the lowest, ZrO 2 an intermediate, and CeO 2 the highest real part of the optical dielectric constant. The optical dielectric constant is found to be lowest in the cubic HYO films. An intermediate dielectric constant is found in HZO films that is predominantly in the monoclinic phase, but additionally hosts the cubic phase. The highest dielectric constant is observed in HCO films that are predominantly in the cubic phase with inclusions of the monoclinic phase. The observed trend is in good agreement with the dominant role of the dopant type in setting the optical dielectric constant.more » « less