Conventional Ferroelectrics Research Articles

Hafnia-based neuromorphic devices

The excellent complementary metal-oxide-semiconductor compatibility and rich physicochemical properties of hafnia-based materials, in particular the unique ferroelectricity that surpasses of conventional ferroelectrics, make hafnia-based devices promising candidates for industrial applications. This Perspective examines the fundamental properties of hafnia-based materials relevant to neuromorphic devices, including their dielectric, ferroelectric, antiferroelectric properties, and the associated ultra-high oxygen-ion conductivity. It also reviews neuromorphic devices developed leveraging these properties, such as resistive random-access memories, ferroelectric random-access memories, ferroelectric tunnel junctions, and (anti)ferroelectric field-effect transistors. We also discuss the potential of these devices for mimicking synaptic and neuronal functions and address the challenges and future research directions. Hafnia-based neuromorphic devices promise breakthrough performance improvements through material optimization, such as crystallization engineering and innovative device configuration designs, paving the way for advanced artificial intelligence systems.

Physics of Ferroelectric Wurtzite Al1−xScxN Thin Films

AbstractAl1−xScxN emerges as a revolutionary ferroelectric material within the III‐N family. It combines exceptional switchable polarization (80–165 µC cm−2), highly tunable coercive fields (1.5–6.5 MV cm−¹), and a wide bandgap (4.9–5.6 eV). Unlike conventional ferroelectrics, Al1−xScxN exhibits remarkable compatibility with both CMOS and III‐N technologies. It can be fabricated on plastic substrates at low temperatures, demonstrating excellent flexibility and biocompatibility. Remarkably, Al1−xScxN maintains superior performance in harsh environments due to its outstanding thermal stability (up to 1100 °C). These unique characteristics position Al1−xScxN as a highly promising candidate for a wide range of applications, including high‐performance memory, in‐memory computing, neuromorphic computing, and next‐generation wearable and implantable devices, particularly for operation in complex environments. Despite its potential, Al1−xScxN faces challenges such as high coercive fields, significant leakage currents, and limited polarization reversal cycle life. Addressing these challenges require a deeper understanding of the fundamental physics controlling Al1−xScxN films. This review explores the origins of Al1−xScxN's ferroelectricity and phase stability, delves into the fundamental theory of wurtzite ferroelectricity, investigates mechanisms for controlling spontaneous polarization and coercive fields, examines recent research progress in Al1−xScxN ferroelectric devices, and outlines future development directions for this exciting material.

Junctionless accumulation-mode SOI ferroelectric FinFET for synaptic weights

In this work, a novel silicon-on-insulator (SOI) based junctionless-accumulation-mode (JAM) ferroelectric (FE) fin field effect transistor (FinFET) is proposed along with its fabrication process flow at a 3-nm node for synaptic weights. The proposed JAM FE FinFET device can be easily integrated with the fabrication flow of p-FinFET in SOI process flow. The proposed device can be easily incorporated into standard FinFET SOI technology and thus is very attractive with respect to previously proposed devices. Further, using a well-calibrated 3D TCAD simulation setup, we show that the device effectively replicates the behavior required for neuromorphic computing applications. The outcomes of the proposed study emphasize the significance of using the JAM FE FinFET as a synaptic weight device that exhibits a 76 % higher nonvolatile conductance range in the ON-state over existing junctionless and conventional FE FinFET devices. Our simulations show that the proposed device offers continuous linear conductance variation and symmetric switching characteristics, which are essential for neuromorphic applications.

Ferroelectricity Induced by a Combination of Crystallographic Chirality and Axial Vector.

Ferroelectric materials compatible with magnetism and/or conductive properties provide a platform for exploring unconventional phenomena, such as the magnetoelectric effect, nonreciprocal responses, and nontrivial superconductivity. Though recent studies on multiferroics have offered several approaches, the search for magnetic and/or conducting ferroelectric materials is still a challenging issue under the traditional "d0-ness" rule, refusing active d electrons. Here, we propose the emergence of ferroelectricity through a combination of crystallographic chirality and axial vector, accepting even non-d0 magnetic ions. This proposal is demonstrated in quasi-one-dimensional magnetic systems SrM2V2O8 (M = Ni, Mg, and Co). The ferroelectric phase transition is observed by measurements of neutron powder diffraction and dielectric properties in all compositions. Structural analyses and first-principles calculations indicate that these magnetic compounds are identified as proper-type ferroelectrics whose ferroelectric phase transition is achieved by spiral motions of crystallographic screw chains formed by edge-shared MO6 octahedra, considered as the combination of locally defined chirality and axial vector. Computationally predicted magnitude of spontaneous polarization of SrM2V2O8 reaches ∼100 μC/cm2, comparable to that of conventional ferroelectrics, despite the incorporation of non-d0 magnetic elements. The mechanism proposed in this study offers a unique approach to the exploration of new ferroelectrics beyond the traditional paradigms.

First-principles prediction of ferroelectricity in defective wurtzite α-Ga2S3

Abstract Wurtzite-type ferroelectrics have attracted much attention as next generation ferroelectric materials due to high spontaneous polarizations. However, wurtzite-type ferroelectrics require high electric fields to switch their polarization direction, resulting in small margins with breakdown electric fields. To address this issue, considerable efforts have been made to explore wurtzite ferroelectrics with moderate switching barriers. In this study, our first-principles calculations have predicted the ferroelectricity of defective wurtzite α-Ga2S3. The calculated polarization is 60 μC/cm2, which is comparable to or smaller than those of conventional wurtzite ferroelectrics. The minimum energy pathway associated with the polarization switching reveals a moderate switching barrier of 67 meV/atom. The energy landscape for α-Ga2S3 is quite different from that for its isostructural Al-based counterpart α-Al2S3, which our recent theoretical study has predicted to have quadruple-well ferroelectricity. The difference in chemical bonding between cations and sulfide ions accounts for their different energy landscapes for polarization switching.

Depolarization Field-Induced Photovoltaic Effect in Graphene/α-In2Se3/Graphene Heterostructures.

The ferroelectric photovoltaic effect (FPVE) enables alternate pathways for energy conversion that are not allowed in centrosymmetric materials. Understanding the dominant mechanism of the FPVE at the ultrathin limit is important for defining the ultimate efficiency. In contrast to the wide band gap conventional thin-film ferroelectrics, 2D α-In2Se3 has an ideal band gap of 1.3 eV and enables the fabrication of ultrathin and stable heterostructures, providing the perfect platform to explore FPVE in the nanoscale limit. Here, we study the ferroelectric layer thickness-dependent FPVE in vertical few-layer graphene/α-In2Se3/graphene heterostructures. We find that the short-circuit photocurrent is antiparallel to the ferroelectric polarization and increases exponentially with decreasing thickness. We show that the observed behavior is predicted by the depolarization field model, originating from the unscreened bound charges due to the finite density of states in semimetal few-layer graphene. As a result, the heterostructures show enhancement of the power conversion efficiency, reaching 2.56 × 10-3% under 100 W/cm2 in 18 nm thick α-In2Se3, approximately 275 times more than the 50 nm thick α-In2Se3. These results demonstrate the importance of the depolarization field at the nanoscale and define design principles for the potential of harnessing FPVE at reduced dimension.

Interface engineering for facile switching of bulk-strong polarization in Si-compatible vertical superlattices

Ferroelectric thin films incorporating different compositional layers have emerged as a promising approach for enhancing properties and performance of electronic devices. In recent years, superlattices utilizing various interactions between their constituent layers have been used to reveal unusual properties, such as improper ferroelectricity, charged domain walls, and negative capacitance in conventional ferroelectrics. Herein, we report a symmetry scheme based on the interface engineering in which the inherent cell-doubling symmetry allowed atomic distortions (phonons) in any vertically aligned superlattice activate novel interface couplings among atomic distortions of different symmetries and fundamentally improve the ferroelectric properties. In a materialized case, the ionic size difference between Hf4+ and Ce4+ in the HfO2/CeO2 (HCO) ferroelectric/paraelectric superlattice leads to these couplings. These couplings mitigate the phase boundary between polar and non-polar phases, and facilitate polarization switching with a remarkably low coercive field (Ec\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${E}_{c}$$\\end{document}) while preserving the original magnitude of the bulk HfO2 polarization and its scale-free ferroelectric characteristics. We show that the cell-doubled distortions present in any vertical superlattice have unique implications for designing low-voltage ferroelectric switching while retaining bulk-strong charge storing capacities in Si-compatible memory candidates.

Engineering interfacial polarization switching in van der Waals multilayers.

In conventional ferroelectric materials, polarization is an intrinsic property limited by bulk crystallographic structure and symmetry. Recently, it has been demonstrated that polar order can also be accessed using inherently non-polar van der Waals materials through layer-by-layer assembly into heterostructures, wherein interfacial interactions can generate spontaneous, switchable polarization. Here we show that deliberate interlayer rotations in multilayer van der Waals heterostructures modulate both the spatial ordering and switching dynamics of polar domains. The engendered tunability is unparalleled in conventional bulk ferroelectrics or polar bilayers. By means of operando transmission electron microscopy we show how alterations of the relative rotations of three WSe2 layers produce structural polytypes with distinct arrangements of polar domains with either a global or localized switching response. Furthermore, the presence of uniaxial strain generates structural anisotropy that yields a range of switching behaviours, coercivities and even tunable biased responses. We also provide evidence of mechanical coupling between the two interfaces of the trilayer, a key consideration for the control of switching dynamics in polar multilayer structures more broadly.

Domain Dynamics and Resistive Switching in Ferroelectric Al1–xScxN Thin Film Capacitors

AbstractIn this paper, using a combination of pulse testing measurements and piezoresponse force microscopy (PFM), an investigation of the polarization reversal behavior and the accompanying resistive switching in the Al0.72Sc0.28N thin film capacitors is reported. The obtained results reveal a transition from the nucleation‐limited switching (NLS) in the low field range toward the more uniform switching described by the Kolmogorov–Avrami–Ishibashi (KAI) model in the high field range. It is found that the Al0.72Sc0.28N capacitors exhibit an unusually steep change in the switching time– it decreases by five orders of magnitude with a moderate increase of the applied field. This feature is caused by a significantly higher activation field value (≈126 MV cm−1) in comparison with the conventional perovskite ferroelectrics. PFM visualization of the field‐induced domain dynamics has allowed the evaluation of the nucleation rate and domain wall velocity. Furthermore, capacitors in the polydomain state generated by partial switching of polarization exhibit a significant (up to two orders of magnitude) increase in the steady‐state conductance. This effect is likely caused by the injection of strongly inclined conducting 180° domain walls. Resistance tunability offers additional functionalities to the Al1‐xScxN devices where conductive domain walls are used as active elements.

Giant electrostriction-like response from defective non-ferroelectric epitaxial BaTiO3 integrated on Si (100)

Lead-free, silicon compatible materials showing large electromechanical responses comparable to, or better than conventional relaxor ferroelectrics, are desirable for various nanoelectromechanical devices and applications. Defect-engineered electrostriction has recently been gaining popularity to obtain enhanced electromechanical responses at sub 100 Hz frequencies. Here, we report record values of electrostrictive strain coefficients (M31) at frequencies as large as 5 kHz (1.04×10−14 m2/V2 at 1 kHz, and 3.87×10−15 m2/V2 at 5 kHz) using A-site and oxygen-deficient barium titanate thin-films, epitaxially integrated onto Si. The effect is robust and retained upon cycling upto 6 million times. Our perovskite films are non-ferroelectric, exhibit a different symmetry compared to stoichiometric BaTiO3 and are characterized by twin boundaries and nano polar-like regions. We show that the dielectric relaxation arising from the defect-induced features correlates well with the observed giant electrostriction-like response. These films show large coefficient of thermal expansion (2.36 × 10−5/K), which along with the giant M31 implies a considerable increase in the lattice anharmonicity induced by the defects. Our work provides a crucial step forward towards formulating guidelines to engineer large electromechanical responses even at higher frequencies in lead-free thin films.

Emergent ultrasmall multiferroics in paraelectric perovskite oxide by hole polarons.

Ultimately small multiferroics with coupled ferroelectric and ferromagnetic order parameters have drawn considerable attention for their tremendous technological potential. Nevertheless, these ferroic orders inevitably disappear below the critical size of several nanometers in conventional ferroelectrics or multiferroics. Here, based on first-principles calculations, we propose a new strategy to overcome this limitation and create ultrasmall multiferroic elements in otherwise nonferroelectric CaTiO3 by engineering the interplay of oxygen octahedral rotations and hole polarons, though both of them are generally believed to be detrimental to ferroelectricity. It is found that the hole doped in CaTiO3 spontaneously forms a localized polaronic state. The lattice distortions associated with a hole polaron interacting with the intrinsic oxygen octahedral rotations in CaTiO3 effectively break the inversion symmetry and create atomic-scale ferroelectricity beyond the critical size limitation. The hole polaron also causes highly localized magnetism attributed to the associated spin-polarized electric state and thus manifests as a multiferroic polaron. Moreover, the hole polaron exhibits high hopping mobility accompanied by rich switching of polarization and magnetic directions, indicating strong magnetoelectric coupling with a mechanism dissimilar from that of conventional multiferroics. The present work provides a new mechanism to engineer inversion symmetry and opens avenues for designing unusual multifunctional materials.

Quantized ferroelectricity in multivalent ion conductors with non-polar point groups.

Ferroelectricity with switchable polarizations is generally associated with small ion-displacements and occurs only in 10 specific polar point groups, which is not a necessary requirement for ion conduction where the ions can also be electrically displaced but by much longer distances. Herein, through first-principles calculations, we predict the formation of unconventional ferroelectricity based on previous experimental reports on topotactic reaction with an aliovalent cation between trigonal layers of ion conductors. In such systems, the multivalent cations are surrounded by vacant sites that can simultaneously migrate by a much larger distance compared with conventional displacive ferroelectricity, giving rise to a quantized change in polarization even if the crystal lattices do not belong to the 10 polar groups. The deviation from classical principles can be attributed to the long ion displacements in ferroelectric ion conductors during switching that can lead to the transformation between multiple equivalent symmetrical stable states, which cannot be realized by the relatively small ion displacements in current ferroelectrics. The evenly distributed vacant sites due to Coulomb repulsion do not break the insulativity of the systems, while their inhomogeneous distribution under an electric field or in ferroelectric domain walls will give rise to high electrical conductance, which may be utilized for constructing nanoscale artificial ionic synapses that enable neuromorphic computing.

Topological Vortex Domain Engineering for High Dielectric Energy Storage Performance

AbstractEnhancing the energy storage performance of dielectric material through the adoption of a novel domain strategy is highly desirable. In this study, Bi0.5Na0.5TiO3‐based thin films are fabricated with topological vortex domains (VDs) by controlling the grain size and investigated the correlation between these VDs and the macroscopic polarization response, which is crucial for the energy storage performance. The emergence of VDs, in contrast to conventional ferroelectric domains, promotes polarization reversal in dielectric materials. Additionally, in contrast to the severely reduced saturation polarization typically noted in conventional relaxor ferroelectrics (RFE), the presence of VDs in RFE leads to only a slight reduction in saturation polarization. These two advantages contribute to the superior energy storage performance of the films with VDs. This approach offers a novel and promising direction for developing dielectrics with high‐energy storage capabilities.

Extendable piezo/ferroelectricity in nonstoichiometric 2D transition metal dichalcogenides

Engineering piezo/ferroelectricity in two-dimensional materials holds significant implications for advancing the manufacture of state-of-the-art multifunctional materials. The inborn nonstoichiometric propensity of two-dimensional transition metal dichalcogenides provides a spiffy ready-available solution for breaking inversion centrosymmetry, thereby conducing to circumvent size effect challenges in conventional perovskite oxide ferroelectrics. Here, we show the extendable and ubiquitous piezo/ferroelectricity within nonstoichiometric two-dimensional transition metal dichalcogenides that are predominantly centrosymmetric during standard stoichiometric cases. The emerged piezo/ferroelectric traits are aroused from the sliding of van der Waals layers and displacement of interlayer metal atoms triggered by the Frankel defects of heterogeneous interlayer native metal atom intercalation. We demonstrate two-dimensional chromium selenides nanogenerator and iron tellurides ferroelectric multilevel memristors as two representative applications. This innovative approach to engineering piezo/ferroelectricity in ultrathin transition metal dichalcogenides may provide a potential avenue to consolidate piezo/ferroelectricity with featured two-dimensional materials to fabricate multifunctional materials and distinguished multiferroic.

Unconventional polarization fatigue in van der Waals layered ferroelectric ionic conductor CuInP2S6

Recent progress in two-dimensional ferroelectrics greatly expands the versatility and tunability in van der Waals heterostructure based electronics. However, the switching endurance issue that widely plagues conventional ferroelectrics in practical applications is hitherto unexplored for van der Waals layered ferroelectrics. Herein, we report the observation of unusual polarization fatigue behaviors in van der Waals layered CuInP2S6, which also possesses finite ionic conductivity at room temperature. The strong intertwinement of the short-range polarization switching and long-range ionic movement in conjunction with the van der Waals layered structure gives rise to unique morphological and polarization evolutions under repetitive electric cycles. With the help of concerted chemical, structural, lattice vibrational and dielectric analyses, we unravel the critical role of the synergy of ionic migration and surface oxidation on the anomalous polarization enhancement and the eventual polarization degradation. This work provides a general insight into the polarization fatigue characteristics in ionically-active van der Waals ferroelectrics and delivers potential solutions for the realization of fatigue-free capacitors.

Molecular Ferroelectric Crystals with Superior Pyroelectricity, Plasticity, and Recyclability.

The pyroelectric effect is used in a wide range of applications such as infrared (IR) detection and thermal energy harvesting, which require the pyroelectric materials to simultaneously have a high pyroelectric coefficient and a low dielectric constant for high figures of merit. However, in conventional proper ferroelectrics, the positive correlation between the pyroelectric coefficient and the dielectric constant imposes an insurmountable challenge in upgrading the figures of merit. Here, we explored superior pyroelectricity in [(CH3)4N][FeCl4] (TMA-FC) and [(CH3)4N][FeCl3Br] (TMA-FCB) molecular ferroelectric plastic crystals, which could decouple this positive correlation due to the nature of improper polarization behavior. Therefore, TMA-FC and TMA-FCB derive a high pyroelectric coefficient and a low dielectric constant simultaneously, yielding record-high figures of merit around room temperature. Furthermore, the favorable plasticity enables ferroelectric crystals to attach surfaces with different shapes for device design and integration. More interestingly, the molecular ferroelectrics could be softened and reshaped at elevated temperatures without decay in pyroelectricity, making them recyclable for cost savings and e-waste reduction. Combined with the facile fabrication process, the findings of this work would open avenues for employing molecular ferroelectric plastic crystals in the manufacture of high-performance pyroelectric devices.

Enhanced electrostrains in PMN–xPZN solid solutions driven by a rather small electric field

AbstractPb(Mg1/3Nb2/3)O3 (PMN) relaxors have gained a lot of interest due to their unusual dielectric relaxation and high electrostrictive electrostrain. However, the Tm (temperature associated with maximum permittivity) of PMN is lower than room temperature, which limits their future development of electrostrain and practical applications. In this study, we increased the Tm by incorporating a relaxor ferroelectric (FE) end member Pb(Zn1/3Nb2/3)O3 (PZN) rather than a conventional high Curie temperature FE end member to create (1−x)PMN–xPZN solid solutions with x = 0.2–0.5. Their dielectric, FE, and electrostrain properties were systematically investigated. In x = 0.4 composition, we get a maximum electrostrain of 0.134% and an equivalent piezoelectric coefficient of 936 pm/V under a rather small driving field of 5 kV/cm. Furthermore, the electrostrain of the x = 0.5 is greater than 0.1% between 20 and 80°C, indicating its possible applicability in precision displacement actuators. Our findings not only clarify the electrostrain and electrostrictive properties of (1 − x)PMN–xPZN system but also show an innovative way to improve electrostrain properties by constructing relaxor–relaxor type solid solutions that can be applied to other FE systems.

Recent Advances in Layered Two‐Dimensional Ferroelectrics from Material to Device

AbstractWith the advent of the post Moore era, modern electronics require further device miniaturization of all electronic components, particularly ferroelectric memories, due to the need for massive data storage. This demand stimulates the exploration of robust switchable ferroelectric polarizations at the atomic scale. In this scenario, van der Waals ferroelectrics have recently gained increasing attention because of their stable layered structure at nanometer thickness, offering the opportunity to realize two‐dimensional ferroelectricity that is long‐sought in conventional thin film ferroelectrics. In this review, recent advancements are summarized in layered ferroelectrics with highlights of the fundamentals of intrinsic two‐dimensional ferroelectricity, the emergence of artificial stacking ferroelectricity, and related protype devices with exotic functions. In addition, the unique polarization control in van der Waals ferroelectrics is discussed. Although great challenges remain unsolved, these studies undoubtedly advance the integration of 2D ferroelectrics in electronics.

Recent Progress and Applications of HfO2-Based Ferroelectric Memory

The discovery of ferroelectricity in hafnium oxide (HfO <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> ) based thin films in 2011 renewed the interest in ferroelectrics. These new ferroelectrics possess completely different crystal morphology with conventional perovskite ferroelectrics, and present more robust ferroelectric properties upon aggressive scaling and compatibility with standard integrated circuit fabrication processes. In this article, we give a brief introduction to the conventional ferroelectric memories, then review the basic properties, recent progress, and memory applications of these HfO <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> -based ferroelectrics.

Origin of the Critical Thickness in Improper Ferroelectric Thin Films

Improper ferroelectrics are expected to be more robust than conventional ferroelectrics against depolarizing field effects and to exhibit a much-desired absence of critical thickness. Recent studies, however, revealed the loss of ferroelectric response in epitaxial improper ferroelectric thin films. Here, we investigate improper ferroelectric hexagonal YMnO3 thin films and find that the polarization suppression, and hence functionality, in the thinner films is due to oxygen off-stoichiometry. We demonstrate that oxygen vacancies form on the film surfaces to provide the necessary charge to screen the large internal electric field resulting from the positively charged YMnO3 surface layers. Additionally, we show that by modifying the oxygen concentration of the films, the phase transition temperatures can be substantially tuned. We anticipate that our findings are also valid for other ferroelectric oxide films and emphasize the importance of controlling the oxygen content and cation oxidation states in ferroelectrics for their successful integration in nanoscale applications.