Ferroelectric Orthorhombic Phase Research Articles

Rhombohedral R3 Phase of Mn-Doped Hf0.5Zr0.5O2 Epitaxial Films with Robust Ferroelectricity.

HfO2-based ferroelectric materials are emerging as key components for next-generation nanoscale devices, owing to their exceptional nanoscale properties and compatibility with established silicon-based electronics infrastructure. Despite the considerable attention garnered by the ferroelectric orthorhombic phase, the polar rhombohedral phase has remained relatively unexplored due to the inherent challenges in its stabilization. In this study, the successful synthesis of a distinct ferroelectric rhombohedral phase is reported, i.e., the R3 phase, in Mn-doped Hf0.5Zr0.5O2 (HZM) epitaxial thin films, which stands different from the conventional Pca21 and R3m polar phases. These findings reveal that this R3 phase HZM film exhibits a remnant polarization of up to 47 µC cm- 2 at room temperature, along with an exceptional retention capability projected to exceed a decade and an endurance surpassing 109 cycles. Moreover, it is demonstrated that by modulating the concentration of Mn dopant and the film's thickness, it is possible to selectively control the phase transition between the R3, R3m, and Pca21 polar phases. This research not only sheds new light on the ferroelectricity of the HfO2 system but also paves the way for innovative strategies to manipulate ferroelectric properties for enhanced device performance.

Ferroelectricity in Ultrathin HfO2-Based Films by Nanosecond Laser Annealing.

Nonvolatile memory devices based on ferroelectric HfxZr1-xO2 (HZO) show great promise for back-end integrable storage and for neuromorphic accelerators, but their adoption is held back by the inability to scale down the HZO thickness without violating the strict thermal restrictions of the Si CMOS back end of line. In this work, we overcome this challenge and demonstrate the use of nanosecond pulsed laser annealing (NLA) to locally crystallize areas of an ultrathin (3.6 nm) HZO film into the ferroelectric orthorhombic phase. Meanwhile, the heat induced by the pulsed laser is confined to the layers above the Si, allowing for back-end compatible integration. We use a combination of electrical characterization, nanofocused scanning X-ray diffraction (nano-XRD), and synchrotron X-ray photoelectron spectroscopy (SXPS) to gain a comprehensive view of the change in material and interface properties by systematically varying both laser energy and the number of laser pulses on the same sample. We find that NLA can provide remanent polarization up to 2Pr= 11.6 μC/cm2 in 3.6 nm HZO, albeit with a significant wake-up effect. The improved TiN/HZO interface observed by XPS explains why device endurance goes beyond 107 cycles, whereas an identical film processed by rapid thermal processing (RTP) breaks already after 106 cycles. All in all, NLA provides a promising approach to scale down the ferroelectric oxide thickness for emerging HZO ferroelectric devices, which is key for their integration in scaled process nodes.

The origin of ferroelectricity in HfO2 from orbital hybridization and covalency

Fluorite-structured HfO2 ferroelectrics exhibit remarkable ferroelectricity owing to the robust thickness scalability, rendering them promising for next-generation ferroelectric memories. Unlike the well-understood perovskite structured ferroelectrics, such as Pb(Zr,Ti)O3, the origin of ferroelectricity in HfO2 remains elusive, which impedes the experimental fabrication of pure and stable ferroelectric orthorhombic phase in films. This study seeks to elucidate its origin by analyzing the covalent nature of local chemical bonding and changes in orbital hybridization and by catching the typical feather of the half-unit-cell spacer/polar layer in the orthorhombic phase. Notably, we find that the differences in the hybridization intensity of the 2s orbitals of two types of O atoms (OI and OII) and 5d orbitals of Hf atoms play a crucial role in inducing ferroelectric distortion. Furthermore, we demonstrate that the intrinsic mechanisms of stress in enhancing the ferroelectricity of HfO2 originate from the modulation of orbital hybridization intensity of the Hf–O bonds. These insights provide a vital theoretical foundation for further exploration of ferroelectric phase transitions and property modulation in HfO2 and similar fluorite-structured ferroelectrics.

Insights into the ferroelectric orthorhombic phase formation in doped HfO2 thin films

Insights into the ferroelectric orthorhombic phase formation in doped HfO2 thin films

Ta5+-substitution effects on crystal structure and ferroelectric property in HfO2-based films

To investigate the Ta5+-substitution effects on crystal structure and ferroelectric property in HfO2-based films, Ta x Hf1−x O2+δ films with various film thicknesses and Ta content were prepared. The ferroelectric orthorhombic phase was formed in a wide film thickness range of 20–100 nm while in a narrow composition range of x = 0.10–0.14. These thickness-insensitive and composition-sensitive characteristics of Ta5+-substituted HfO2 film are similar to Y3+ rather than Zr4+. The X-ray photoelectron spectroscopy measurement suggests that the ionic state of Ta is not reduced and Ta x Hf1−x O2+δ film has an excess oxygen state. The excess oxygen may consist of a combination of oxygen vacancies and more interstitial oxygens. These defects facilitate the formation of the ferroelectric phasebut also decrease the breakdown voltage and increase the leakage current in Ta5+-substituted HfO2 films. On the other hand, the generation of excess oxygen indicates the possibility of controlling oxygen vacancies which deteriorate fatigue and retention properties.

Mechanisms for enhanced ferroelectric properties in ultra-thin Hf0.5Zr0.5O2 film under low-temperature, long-term annealing

To gain insight into the ferroelectric mechanisms under reduced thermal budget and thickness scaling, a 4.6 nm ultra-thin ferroelectric Hf0.5Zr0.5O2 capacitor compatible with back-end-of-line (BEOL) processes (all conducted at temperatures ≤350 °C) is investigated in this work. Through O3 pretreatment at the bottom electrode (BE) interface and controlled temperature modulation of the crystalline phase, the capacitor exhibits exceptional ferroelectric (FE) properties following low-temperature (350 °C) and long-term (300 s) rapid thermal annealing (RTA). These properties include high remanent polarization (2Pr ∼ 28.53 μC/cm2), low coercive voltage (Vc ∼ 0.43 V), effective leakage suppression, robust endurance (∼1010 cycles without hard breakdown), and a desirable high dielectric constant. The main mechanisms identified include tetragonal phase nucleation under enhanced tensile stress via the oxidized BE layer (TiO2), crystalline growth controlled through RTA temperature modulation, and phase transition to the ferroelectric orthorhombic phase under electric field cycling. This research provides valuable insights for the development of BEOL-compatible nonvolatile FE memories.

Enhanced polarization and endurance properties of ZrO2-based ferroelectric capacitor using HfO2 interfacial layer

Recently discovered ferroelectricity in fluorite-structure ZrO2 thin film has attracted increasing and intense interest due to its lower crystallization temperature and higher content in nature in comparison to hafnium oxide. Here, the effect of HfO2 interfacial layer on the ferroelectric properties of ZrO2 thin films is investigated systematically by designing four types of interfacial structures. It is revealed that the ferroelectric orthorhombic phase, remanent polarization, and endurance can be improved in ZrO2 thin film by inserting both a top- and bottom-HfO2 interfacial layer. A maximal ferroelectric remanent polarization (2P r) of 53.4 μC cm−2 and an optimal endurance performance of 3 × 107 field cycles under frequency of 100 kHz are achieved in Pt/HfO2/ZrO2/HfO2/Pt capacitors, with ferroelectric stacks being crystallized at 450 °C via post-deposition annealing method. X-ray photoelectron spectroscopy analysis confirms that the HfO2 bottom-layer plays a very important role in the formation of a higher ratio o-phase, thus enhancing the ferroelectricity. These results suggest that designing appropriate interfaces would help achieve excellent ferroelectric properties in ZrO2 films.

Improvement of the Ferroelectric Response of La-Doped Hafnium Zirconium Oxide Employing Tungsten Oxide Interfacial Layer with Back-End-of-Line Compatibility.

In this work, the impact of a tungsten oxide (WO3) seed and capping layer for ferroelectric La-doped (Hf, Zr)O2 (La:HZO) based capacitors, designed with back-end-of-line (BEOL) compatibility, is systematically investigated. The WO3 capping layer supplies oxygen to the La:HZO layer throughout the fabrication process and during device cycling. This facilitates the annihilation of oxygen vacancies (Vo) within the La:HZO layer, thereby stabilizing its ferroelectric orthorhombic phase and resulting in an increase of the remanent polarization (Pr) value in the capacitor. Moreover, the effectiveness of the WO3 capping layer depends on the seed layer of the HZO film, suggesting that proper combination of the seed and capping layers should be employed to maximize the ferroelectric response. Finally, a TiN/TiO2 seed layer/La:HZO/WO3 capping layer/TiN capacitor is successfully fabricated and optimized by a complete set of atomic layer deposition (ALD) processes, achieving a superior 2Pr value and endurance value of more than 109 cycles at an electric field of 2.5 MV/cm. The WO3 capping layer is anticipated to offer a viable solution for doped HZO capacitors with reduced thickness, addressing the challenge of elevated Vo levels that favor the tetragonal phase and result in low 2Pr values.

Dimensional Scaling of Ferroelectric Properties of Hafnia-Zirconia Thin Films: Electrode Interface Effects.

Hafnia-based ferroelectric (FE) thin films are promising candidates for semiconductor memories. However, a fundamental challenge that persists is the lack of understanding regarding dimensional scaling, including thickness scaling and area scaling, of the functional properties and their heterogeneity in these films. In this work, excellent ferroelectricity and switching endurance are demonstrated in 4 nm-thick Hf0.5Zr0.5O2 (HZO) capacitors with molybdenum electrodes in capacitors as small as 65 nm × 45 nm in size. The HZO layer in these capacitors can be crystallized into the ferroelectric orthorhombic phase at the low temperature of 400 °C, making them compatible for back-end-of-line (BEOL) FE memories. With the benefits of thickness scaling, low operation voltage (1.2 V) is achieved with high endurance (>1010 cycles); however, a significant fatigue regime is noted. We observed that the bottom electrode, rather than the top electrode, plays a dominant role in the thickness scaling of HZO ferroelectric behavior. Furthermore, ultrahigh switched polarization (remanent polarization 2Pr ∼ 108 μC cm-2) is observed in some nanoscale devices. This study advances the understanding of dimensional scaling effects in HZO capacitors for high-performance FE memories.

Control of intrinsic ferroelectricity and structural phase in pure HfO2 films via crystalline orientation

The ferroelectricity of hafnia-based thin films has garnered considerable attention in both academic researches and industrial applications. However, the fundamental properties, such as high coercivity, the wake-up effect, and the mechanism of ferroelectricity have not been fully elucidated. Here we report the crystallization orientation control of structural phase and ferroelectricity in pure HfO2 thin films. Both (001)- and (111)-oriented HfO2 thin films exhibit a mixture of ferroelectric orthorhombic and non-ferroelectric monoclinic phases. With decreasing film thickness, the orthorhombic phase ratio increases for both orientations, with a consistently higher proportion for (111)-oriented film. Consequently, the ferroelectricity is significantly enhanced in thinner (111)-oriented film. Remarkably, both (001)- and (111)-oriented pure HfO2 thin films demonstrate an intrinsic ferroelectricity. Moreover, the coercive field of the (001)-oriented film appears to be lower than that of the (111)-oriented film. Additionally, oxygen ions migrate more easily in the (001)-oriented film, which exhibits distinct electronic structure and local atomic ordering compared to the (111)-oriented film. These results provide valuable insights into the ferroelectricity of HfO2 and suggest that crystalline orientation is an effective approach to explore the ferroelectric properties in hafnia-based films.

Influence of Biaxial Strain and Interfacial Layer Growth on Ferroelectric Wake-Up and Phase Transition Fields in ZrO2.

Investigations on fluorite-structured ferroelectric HfO2/ZrO2 thin films are aiming to achieve high-performance films required for memory and computing technologies. These films exhibit excellent scalability and compatibility with the complementary metal-oxide semiconductor process used by semiconductor foundries, but stabilizing ferroelectric properties with a low operation voltage in the as-fabricated state of these films is a critical component for technology advancement. After removing the influence of interfacial layers, a linear correlation is observed between the biaxial strain and the electric field for transforming the nonferroelectric tetragonal to the ferroelectric orthorhombic phase in ZrO2 thin films. This observation is supported by applying the principle of energy conservation in combination with ab initio and molecular dynamics simulations. According to the simulations, a rarely reported Pnm21 orthorhombic phase may be stabilized by tuning biaxial strain in the ZrO2 films. This study demonstrates the significant influence of interfacial layers and biaxial strain on the phase transition fields and shows how strain engineering can be used to improve ferroelectric wake-up in ZrO2.

Nanoscale Investigation of the Effect of Annealing Temperature on the Polarization Switching Dynamics of Hf0.5Zr0.5O2 Thin Films

AbstractRecently, HfO2‐based ferroelectric thin films have attracted widespread interest in developing next‐generation nonvolatile memories. To form a metastable ferroelectric orthorhombic phase in HfO2, a post‐annealing process is typically necessary. However, the microscopic mechanism underlying the effect of annealing temperature on ferroelectric domain nucleation and growth is still obscure, despite its importance in optimizing the operation speed of HfO2‐based devices. In this study, the ferroelectric properties and polarization switching of Hf0.5Zr0.5O2 thin films annealed at different temperatures (550–700 °C) are systematically investigated. Evidently, the crystal structure, remnant polarization, and dielectric constant monotonically change with annealing temperature. However, microscopic piezoresponse force microscopy images as well as macroscopic switching current measurements reveal non‐monotonic changes in the polarization switching speed with annealing temperature. This intriguing behavior is ascribed to the difference in the ferroelectric‐domain nucleation process induced by the amount of oxygen vacancies in the Hf0.5Zr0.5O2 thin films annealed at different temperatures. This work demonstrates that controlling the defect concentration of ferroelectric HfO2 by tuning the post‐annealing process is critical for optimizing device performance, particularly polarization switching speed.

(Invited) Role of Oxidant Gas for Atomic Layer Deposition of HfxZr1−XO2 Thin Films on Ferroelectricity of Metal-Ferroelectric-Metal Capacitors

We fabricated 400°C-annealed TiN/HfxZr1−xO2 (HZO)/TiN metal–ferroelectric–metal (MFM) capacitors using H2O and O2 plasma as oxidant gases of thermal (TH) and plasma-enhanced atomic layer deposition (PE-ALD), respectively, for HZO films. The PE-ALD film formed a more ferroelectric orthorhombic phase compared with the TH-ALD case. Therefore, the MFM capacitor with the PE-ALD film showed higher remanent polarization and dielectric constant. For the PE-ALD case, moreover, an oxygen-rich interfacial layer (O-rich-IL) was formed between the HZO film and TiN-bottom electrode during the ALD process. Thus, the MFM capacitor with the PE-ALD film showed less degradation of switching polarization during field cycling compared with the TH-ALD case, because an O-rich-IL should prevent the interface reaction and formation of additional oxygen vacancies in the PE-ALD film during field cycling. Based on these results, it is important to consider the selection of an ALD oxidant gas for the fabrication of HZO-based MFM capacitors.

Symmetry Engineering of Epitaxial Hf0.5Zr0.5O2 Ultrathin Films.

Robust ferroelectricity in HfO2-based ultrathin films has the potential to revolutionize nonvolatile memory applications in nanoscale electronic devices because of their compatibility with the existing Si technology. However, to fully exploit the potential of ferroelectric HfO2-based thin films, it is crucial to develop strategies for the controlled stabilization of various HfO2-based polymorphs in nanoscale heterostructures. This study demonstrates how substrate-orientation-induced anisotropic strain can engineer the crystal symmetry, structural domain morphology, and growth orientation of ultrathin Hf0.5Zr0.5O2 (HZO) films. Epitaxial ultrathin HZO films were grown on the heterostructures of (001)- and (110)-oriented La2/3Sr1/3MnO3/SrTiO3 (LSMO/STO) substrate. Various structural analyses revealed that the (110)-oriented substrate promotes a higher degree of structural order (crystallinity) with improved stability of the (111)-oriented orthorhombic phase (Pca21) of HZO. Conversely, the (001)-oriented substrate not only induces a distorted orthorhombic structure but also facilitates the partial stabilization of nonpolar phases. Electrical measurements revealed robust ferroelectric properties in epitaxial thin films without any wake-up effect, where the well-ordered crystal symmetry stabilized by STO(110) facilitated better ferroelectric characteristics. This study suggests that tuning the epitaxial growth of ferroelectric HZO through substrate orientation can improve the stability of the metastable ferroelectric orthorhombic phase and thereby offer a better understanding of device applications.

Non-centrosymmetric crystallization in ferroelectric hafnium zirconium oxide via photon-assisted defect modulation

Ferroelectricity in Hf1-xZrxO2 (HZO) thin films has garnered significant attention for advanced memory devices. However, the challenge in understanding nanoscale polymorphism and the absence of non-centrosymmetric crystallization techniques compatible with back-end-of-line processes have restricted its broader application to various types of information storage systems. In this study, we report a novel method to generate the ferroelectric orthorhombic phase (o-phase) in HZO films via photon-assisted non-centrosymmetric crystallization. As-prepared HZO films (8 nm) prepare by atomic layer deposition underwent thermal annealing and subsequent deep ultraviolet (DUV) irradiation. The DUV treatment successfully triggered ferroelectricity in HZO films annealed at 300 °C. Moreover, the same post-treatment applied to HZO films annealed at 400 °C led to a further enhanced polarization up to 29.2 μC cm−2 under high bipolar triangular pulses and outstanding reliability for up to 106 bias stress cycles. Finally, based on in-depth microscopic and structural analyses, we proposed the mechanism on the symmetry-breaking phase transformation to the o-phase HZO with advanced ferroelectricity via oxygen vacancy-driven lattice rearrangement.

Enhanced remnant polarization in ferroelectric Hf0.5Zr0.5O2 thin film capacitors through Mo top electrode by post-metallization annealing treatment

Zr-doped HfO2 (Hf0.5Zr0.5O2) ferroelectric thin films have garnered considerable attention due to their appealing attributes, including a large bandgap (>5 eV), low crystallization temperature, and compatibility with CMOS technology. In this study, we present the achievement of a substantial remnant polarization in ferroelectric Hf0.5Zr0.5O2 thin films, fabricated through atomic layer deposition, with Mo and TiN serving as the top and bottom electrodes, respectively. The Mo/Hf0.5Zr0.5O2/TiN capacitor exhibited commendable ferroelectric behavior and demonstrated high endurance within a thermal budget ranging from 400 to 500 °C. Leveraging the relatively low thermal expansion coefficient of the Mo top electrode facilitated the induction of in-plane tensile strain, fostering an increased formation of the ferroelectric orthorhombic phase within the Hf0.5Zr0.5O2 layer. Elevating the post-metallization annealing temperature to 500 °C yielded a substantial increase in 2Pr (≈54 μC/cm2) with excellent endurance exceeding 106 cycles. The influence of annealing temperature on the morphological and structural properties of Hf0.5Zr0.5O2 thin films was comprehensively analyzed through atomic force microscopy and grazing incidence X-ray diffraction analysis.

Pure ZrO2 Ferroelectric Thin Film for Nonvolatile Memory and Neural Network Computing.

The recent discovery of ferroelectricity in pure ZrO2 has drawn much attention, but the information storage and processing performances of ferroelectric ZrO2-based nonvolatile devices remain open for further exploration. Here, a ZrO2 (∼8 nm)-based ferroelectric capacitor using RuO2 oxide electrodes is fabricated, and the ferroelectric orthorhombic phase evolution under electric field cycling is studied. A ferroelectric remnant polarization (2Pr) of >30 μC/cm2, leakage current density of ∼2.79 × 10-8 A/cm2 at 1 MV/cm, and estimated polarization retention of >10 years are achieved. When the ferroelectric capacitor is connected with a transistor, a memory window of ∼0.8 V and eight distinct states can be obtained in such a ferroelectric field-effect transistor (FeFET). Through the conductance manipulation of the FeFET, a high object image recognition accuracy of ∼93.32% is achieved on the basis of the CIFAR-10 dataset in the convolutional neural network (CNN) simulation, which is close to the result of ∼94.20% obtained by floating-point-based CNN software. These results demonstrate the potential of ferroelectric ZrO2 devices for nonvolatile memory and artificial neural network computing.

Low oxidation conditions in pulsed laser deposition enhance polarization without degradation of endurance and retention in Hf0.5Zr0.5O2 films

Interplay between oxygen vacancies and the stabilization of the ferroelectric orthorhombic phase in doped HfO2, as well as the resulting impact on endurance and retention, is far from being well understood. In Hf0.5Zr0.5O2 (HZO) thin films, it is commonly found that high polarization occurs usually at the the expense of robustness upon cycling due to the polarization–endurance dilemma. It has been reported that HZO thin films grown by pulsed laser deposition under the mixed Ar and O2 atmosphere exhibit a high polarization. Here, we show that this strategy enables functional properties tuning, allowing to obtain HZO films with high polarization at low oxidation conditions without degradation of endurance and retention.

Ferroelectricity in Ce0.2-HfO2 films around 500 nm in thickness

CeO2-HfO2 solid solution thin films (Hf1-xCexO2) were deposited on Pt(111)/TiO2/SiO2/Si(100) substrates using the chemical solution deposition method. This study investigates the influence of CeO2 content and annealing temperature on the structure and ferroelectric properties of Hf1-xCexO2 films. Ferroelectric behavior is demonstrated in polycrystalline Hf0.80Ce0.20O2 films with thicknesses ranging from 163 to 524 nm. And the structure of the films is analyzed using glancing incidence X-ray diffraction. The comprehensive results indicate that Hf0.80Ce0.20O2 films annealed at 850 °C exhibit excellent ferroelectricity. Square hysteresis loops associated with the ferroelectric orthorhombic phase are observed, even in the 524-nm-thick film. The remnant polarization (Pr) and coercive field (Ec) range from 16 to 18 μC/cm2 and 1100–1250 kV/cm, respectively, under a maximum applied electric field of 2 MV/cm for all Hf0.80Ce0.20O2 films. Furthermore, the film presents thickness-insensitive characteristic. The current work paves the new way to design high-performance thick HfO2-based ferroelectric films.

Improvement of ferroelectric phase fraction in HfO2 via La-containing co-doping method

In this work, the effect of co-doping lanthanide and VB group elements on the phase fraction of HfO2 is studied by first-principles calculations. A significant increase in the ferroelectric orthorhombic phase fraction can be achieved by doping La with Ta or Nb, which would enhance the ferroelectricity of HfO2. Furthermore, during the screening process, it is observed that oxygen vacancies coupled with dopants can promote the formation of the ferroelectric phase in HfO2. These studies and results provide valuable methods for improving the ferroelectric properties of HfO2.