2D Ferroelectric Materials Research Articles

Picometer-Level In Situ Manipulation of Ferroelectric Polarization in Van der Waals layered InSe.

Ferroelectric 2D van der Waals (vdW) layered materials are attracting increasing attention due to their potential applications in next-generation nanoelectronics and in-memory computing with polarization-dependent functionalities. Despite the critical role of polarization in governing ferroelectricity behaviors, its origin and relation with local structures in 2D vdW layered materials have not been fully elucidated so far. Here, intralayer sliding of approximately six degrees within each quadruple-layer of the prototype 2D vdW ferroelectrics InSe is directly observed and manipulated using sub-angstrom resolution imaging and in situ biasing in an aberration-corrected scanning transmission electron microscope. The in situ electric manipulation further indicates that the reversal of intralayer sliding can be achieved by altering the electric field direction. Density functional theory calculations reveal that the reversible picometer-level intralayer sliding is responsible for switchable out-of-plane polarization. The observation and manipulation of intralayer sliding demonstrate the structural origin of ferroelectricity in InSe and establish a dynamic structural variation model for future investigations on more 2D ferroelectric materials.

Enhancement of tunneling electroresistance in metal/two-dimensional ferroelectric tunnel junctions: route for polarization-modulated interface transport

In fabricating ferroelectric tunnel junction (FTJ) devices, it is essential to employ low-resistance metals as electrodes interfacing with two-dimensional (2D) ferroelectric materials. For FTJs with a top contact configuration, two interfaces for charge transport are present, namely the vertical interface between the metal electrode and the 2D ferroelectric material, and the lateral interface between the electrode and the central scattering region. These interfaces significantly influence the tunneling electroresistance (TER) of FTJs. However, there exists a notable deficiency in comprehension concerning the physics of charge transport at the interface. In this work, we explore the interface transport properties in FTJs featuring a top contact configuration between metal and the typicalα-In2Se3monolayer. By employing the non-equilibrium Green's function method, we observe a TER ratio of1.15×105% for the Pd top contact interfacing with anα-In2Se3monolayer. The significant TER effect is attributed to polarization-controlled interface transport, which is further elucidated through an analysis of the transport mechanisms influenced by the out-of-plane polarization ofα-In2Se3at the vertical interface and the in-plane polarization at the lateral interface. This investigation of the fundamental physical mechanisms of polarization-controlled interface transport demonstrates significant potential for enhancing non-volatile memory devices.

Spatially Resolved Light-Induced Ferroelectric Polarization in α-In2Se3/Te Heterojunctions.

Light-induced ferroelectric polarization in 2D layered ferroelectric materials holds promise in photodetectors with multilevel current and reconfigurable capabilities. However, translating this potential into practical applications for high-density optoelectronic information storage remains challenging. In this work, an α-In2Se3/Te heterojunction design that demonstrates spatially resolved, multilevel, nonvolatile photoresponsivity is presented. Using photocurrent mapping, the spatially localized light-induced poling state (LIPS) is visualized in the junction region. This localized ferroelectric polarization induced by illumination enables the heterojunction to exhibit enhanced photoresponsivity. Unlike previous reports that observe multilevel polarization enhancement in electrical resistance, the device shows nonvolatile photoresponsivity enhancement under illumination. After polarization saturation, the photocurrent increases up to 1000 times, from 10-12 to 10-9 A under the irradiation of a 520nm laser with a power of 1.69 nW, compared to the initial state in a self-driven mode. The photodetector exhibits high detectivity of 4.6×1010 Jones, with a rise time of 27 µs and a fall time of 28 µs. Furthermore, the device's localized poling characteristics and multilevel photoresponse enable spatially multiplexed optical information storage. These results advance the understanding of LIPS in 2D ferroelectric materials, paving the way for optoelectronic information storage technologies.

Emerging Multifunctionality in 2D Ferroelectrics: A Theoretical Review of the Interplay With Magnetics, Valleytronics, Mechanics, and Optics

Abstract2D ferroelectric materials present promising applications in information storage, sensor technology, and optoelectronics through their coupling with magnetics/valleytronics, mechanics, and optics, respectively. The integration of 2D ferroelectrics with magnetism enhances data storage density in memory devices by enabling electric‐field‐controlled magnetic states. Ferroelectric‐valley coupling holds promise for high‐speed, low‐energy electronics by leveraging the electrical control of valley polarization. Ferroelectric‐strain coupling results in various polar topologies, with potential applications in high‐density data storage technologies and sensor devices. Moreover, the coupling between ferroelectrics and optics facilitates the development of nonlinear photonics based on ferroelectric materials. This review summarizes the latest theoretical progress in the coupling mechanisms, including the Dzyaloshinskii‐Moriya‐interaction‐induced magnetoelectric coupling, symmetry‐linked ferroelectric‐valley coupling, ferroelectric‐strain‐coupling‐generated polar topologies, and second‐harmonic generation through ferroelectric‐light interactions. The current challenges and future opportunities in harnessing the coupling in 2D ferroelectric materials for multifunctional applications are provided.

Two-Dimensional Ferroelectric Materials: Synthesis, Characterization and Applications

In recent years, the continuous advancements in microelectronics have driven the evolution of electronic devices towards miniaturization and integration. However, at the nanoscale level, surface and size effects become significant, imposing constraints on the use of conventional bulk ferroelectric materials in contemporary industry. As a result, in the field of materials research, two-dimensional (2D) ferroelectric materials with stable spontaneous polarization and minimal size effects have gained significant attention. These novel 2D ferroelectric materials have great potential for future nano-level ferroelectric applications, enabling high levels of device integration. To begin with, this paper divides 2D ferroelectric materials into two categories: intrinsic ferroelectrics and sliding ferroelectrics. It also discusses the features and current state of research on each of these categories. Next, typical 2D ferroelectric material preparation and characterization techniques are outlined. Additionally, 2D ferroelectric memory devices like ferroelectric diodes (FD), ferroelectric field effect transistors (FeFET), ferroelectric semiconductor field-effect transistors (FeSFET), and ferroelectric tunnel junctions (FTJ) are introduced. Finally, this review also presents expectations and potential challenges in the domain of 2D ferroelectric materials.

Molecular Engineering Regulation Achieving Out‐of‐Plane Polarization in Rare‐Earth Hybrid Double Perovskites for Ferroelectrics and Circularly Polarized Luminescence

AbstractOut‐of‐plane polarization is a highly desired property of two‐dimensional (2D) ferroelectrics for application in vertical sandwich‐type photoferroelectric devices, especially in ultrathin ferroelectronic devices. Nevertheless, despite great advances that have been made in recent years, out‐of‐plane polarization remains unrealized in the 2D hybrid double perovskite ferroelectric family. Here, from our previous work 2D hybrid double perovskite HQERN ((S3HQ)4EuRb(NO3)8, S3HQ=S‐3‐hydroxylquinuclidinium), we designed a molecular strategy of F‐substitution on organic component to successfully obtain FQERN ((S3FQ)4EuRb(NO3)8, S3FQ=S‐3‐fluoroquinuclidinium) showing circularly polarized luminescence (CPL) response. Remarkably, compared to the monopolar axis ferroelectric HQERN, FQERN not only shows multiferroicity with the coexistence of multipolar axis ferroelectricity and ferroelasticity but also realizes out‐of‐plane ferroelectric polarization and a dramatic enhancement of Curie temperature of 94 K. This is mainly due to the introduction of F‐substituted organic cations, which leads to a change in orientation and a reduction in crystal lattice void occupancy. Our study demonstrates that F‐substitution is an efficient strategy to realize and optimize ferroelectric functional characteristics, giving more possibility of 2D ferroelectric materials for applications in micro‐nano optoelectronic devices.

Molecular Engineering Regulation Achieving Out-of-Plane Polarization in Rare-Earth Hybrid Double Perovskites for Ferroelectrics and Circularly Polarized Luminescence.

Out-of-plane polarization is a highly desired property of two-dimensional (2D) ferroelectrics for application in vertical sandwich-type photoferroelectric devices, especially in ultrathin ferroelectronic devices. Nevertheless, despite great advances that have been made in recent years, out-of-plane polarization remains unrealized in the 2D hybrid double perovskite ferroelectric family. Here, from our previous work 2D hybrid double perovskite HQERN ((S3HQ)4EuRb(NO3)8, S3HQ=S-3-hydroxylquinuclidinium), we designed a molecular strategy of F-substitution on organic component to successfully obtain FQERN ((S3FQ)4EuRb(NO3)8, S3FQ=S-3-fluoroquinuclidinium) showing circularly polarized luminescence (CPL) response. Remarkably, compared to the monopolar axis ferroelectric HQERN, FQERN not only shows multiferroicity with the coexistence of multipolar axis ferroelectricity and ferroelasticity but also realizes out-of-plane ferroelectric polarization and a dramatic enhancement of Curie temperature of 94 K. This is mainly due to the introduction of F-substituted organic cations, which leads to a change in orientation and a reduction in crystal lattice void occupancy. Our study demonstrates that F-substitution is an efficient strategy to realize and optimize ferroelectric functional characteristics, giving more possibility of 2D ferroelectric materials for applications in micro-nano optoelectronic devices.

Intrinsic Out-Of-Plane and In-Plane Ferroelectricity in 2D AgCrS2 with High Curie Temperature.

2D ferroelectric materials have attracted extensive research interest due to potential applications in nonvolatile memory, nanoelectronics and optoelectronics. However, the available 2D ferroelectric materials are scarce and most of them are limited by the uncontrollable preparation. Herein, a novel 2D ferroelectric material AgCrS2 is reported that are controllably synthesized in large-scale via salt-assist chemical vapor deposition growth. By tuning the growth temperature from 800 to 900°C, the thickness of AgCrS2 nanosheets can be precisely modulated from 2.1 to 40nm. Structural and nonlinear optical characterizations demonstrate that AgCrS2 nanosheet crystallizes in a non-centrosymmetric structure with high crystallinity and remarkable air stability. As a result, AgCrS2 of various thicknesses display robust ferroelectric polarization in both in-plane (IP) and out-of-plane (OOP)directions with strong intercorrelation and high ferroelectric phase transition temperature (682 K). Theoretical calculations suggest that the ferroelectricity in AgCrS2 originates from the displacement of Ag atoms in AgS4 tetrahedrons, which changes the dipole moment alignment. Moreover, ferroelectric switching is demonstrated in both lateral and vertical AgCrS2 devices, which exhibit exotic nonvolatile memory behavior with distinct high and low resistance states. This study expands the scope of 2D ferroelectric materials and facilitates the ferroelectric-based nonvolatile memory applications.

Theoretical study of metal contacts to the monolayer ferroelectric material CuInP2S6 and its device applications

Two-dimensional (2D) ferroelectric materials exhibit significant potential for applications in nonvolatile memory and device miniaturization. In the device design stage, it is essential to consider the compatibility between 2D ferroelectric materials and three-dimensional (3D) metal. However, the interface between them introduces complex interactions that could impact the device's performance. In this work, based on the first-principles method, we simulate several 3D metal–2D ferroelectric material contact systems by utilizing different 3D metals in contact with the 2D ferroelectric monolayer CuInP2S6 (CIPS). By calculating the electronic structures of the systems, we find that the Cd(001)–CIPS configuration is the most stable structure, followed by the Ag(111)–CIPS and Au(111)–CIPS systems. Both the Cd(001)–CIPS and Ag(111)–CIPS systems undergo a transition from Schottky to Ohmic contact. Finally, we theoretically design a ferroelectric tunnel junction (FTJ) based on the Cd(001)–CIPS contact system, achieving a tunneling electroresistance ratio of 2.394×105% and a remarkably low resistance–area product of 0.78 Ω·μm2, which makes the proposed FTJ superior to the conventional 3D FTJ. This work provides some insights for the design of nonvolatile storage devices.

Free-standing two-dimensional ferro-ionic memristor

Two-dimensional (2D) ferroelectric materials have emerged as significant platforms for multi-functional three-dimensional (3D) integrated electronic devices. Among 2D ferroelectric materials, ferro-ionic CuInP2S6 has the potential to achieve the versatile advances in neuromorphic computing systems due to its phase tunability and ferro-ionic characteristics. As CuInP2S6 exhibits a ferroelectric phase with insulating properties at room temperature, the external temperature and electrical field should be required to activate the ferro-ionic conduction. Nevertheless, such external conditions inevitably facilitate stochastic ionic conduction, which completely limits the practical applications of 2D ferro-ionic materials. Herein, free-standing 2D ferroelectric heterostructure is mechanically manipulated for nano-confined conductive filaments growth in free-standing 2D ferro-ionic memristor. The ultra-high mechanical bending is selectively facilitated at the free-standing area to spatially activate the ferro-ionic conduction, which allows the deterministic local positioning of Cu+ ion transport. According to the local flexoelectric engineering, 5.76×102-fold increased maximum current is observed within vertical shear strain 720 nN, which is theoretically supported by the 3D flexoelectric simulation. In conclusion, we envision that our universal free-standing platform can provide the extendable geometric solution for ultra-efficient self-powered system and reliable neuromorphic device.

The evolution of 2D vdW ferroelectric materials: Theoretical prediction, experiment confirmation, applications

Since J. Valasek first discovered ferroelectric materials in 1920, researchers have been exploring continuously in various fields through theory and experiments. With the rapid development of the computing technology, energy efficiency and size requirements of semiconductor devices are becoming increasingly demanding. However, the conventional ferroelectric materials, which have been limited by physical size restrictions, can no longer satisfy the above requirements. Two-dimensional (2D) ferroelectric materials can effectively overcome the size limitation of traditional ferroelectrics due to the weak van der Waals force between layers, which is easy to thin while retaining their own unique properties. Currently, a small number of 2D materials have been proved to be ferroelectric properties by experiments and have shown great application potential in nanoscale electrical and optoelectronic devices, expected to become the leaders of next-generation computing. In this review, the current 2D ferroelectric materials are summarized and discussed in detail from seven aspects: theoretical prediction, fabrication methods, ferroelectric characterization methods, principles of typical 2D ferroelectrics, optimization methods of ferroelectric performance, application, and challenges. Finally, the development of 2D ferroelectric materials looks into the future.

Emerging 2D Ferroelectric Devices for In-Sensor and In-Memory Computing.

The quantity of sensor nodes within current computing systems is rapidly increasing in tandem with the sensing data. The presence of a bottleneck in data transmission between the sensors, computing, and memory units obstructs the system's efficiency and speed. To minimize the latency of data transmission between units, novel in-memory and in-sensor computing architectures are proposed as alternatives to the conventional von Neumann architecture, aiming for data-intensive sensing and computing applications. The integration of 2D materials and 2D ferroelectric materials has been expected to build these novel sensing and computing architectures due to the dangling-bond-free surface, ultra-fast polarization flipping, and ultra-low power consumption of the 2D ferroelectrics. Here, the recent progress of 2D ferroelectric devices for in-sensing and in-memory neuromorphic computing is reviewed. Experimental and theoretical progresses on 2D ferroelectric devices, including passive ferroelectrics-integrated 2D devices and active ferroelectrics-integrated 2D devices, are reviewed followed by the integration of perception, memory, and computing application. Notably, 2D ferroelectric devices have been used to simulate synaptic weights, neuronal model functions, and neural networks for image processing. As an emerging device configuration, 2D ferroelectric devices have the potential to expand into the sensor-memory and computing integration application field, leading to new possibilities for modern electronics.

Synthesis, atomic structure and electronic properties of ferroelectric AgBiP2Se6 ultrathin flakes

Layered transition metal thiophosphate ABP2X6(A = Ag or Cu, B = V, Cr, In or Bi, X = S or Se) as a promising 2D ferroelectric material, has attracted great attention nowadays. In this work, ultrathin AgBiP2Se6 sheets down to 6 nm were synthesized for the first time. Atomic force microscopy, double spherical aberration scanning TEM and Raman spectra were performed to investigate the morphology, atomic structure and vibration modes of the samples. The first-principles calculations utilizing density-functional theory(DFT) were also used to analyze the electronic properties, band structures and projected density of states (PDOS) for both ferroelectric (FE) and paraelectric(PE) states of AgBiP2Se6 monolayer.

Applying the Wake-Up-like Effect to Enhance the Capabilities of Two-Dimensional Ferroelectric Field-Effect Transistors.

For traditional ferroelectric field-effect transistors (FeFETs), enhancing the polarization domain of bulk ferroelectric materials is essential to improve device performance. However, there has been limited investigation into the enhancement of polarization field in two-dimensional (2D) ferroelectric material such as CuInP2S6 (CIPS). In this study, similar to bulk ferroelectric materials, CIPS exhibited enhanced polarization field upon application of external cyclic voltage. Moreover, unlike traditional ferroelectric materials, the polarization enhancement of CIPS is not due to redistribution of the defect but rather originates from a mechanism: the long-distance migration of Cu ions. We termed this mechanism the "wake-up-like effect". After incorporating the wake-up-like effect into the graphene/CIPS/WSe2 FeFET device, we successfully increased the hysteresis window and enhanced the current on/off ratio by 4 orders of magnitude. Moreover, the FeFET yielded remarkable achievements, such as multilevel nonvolatile memory with 21 distinct conductance levels, a high on/off ratio exceeding 106, a long retention time exceeding 103 s, and neuromorphic computing with 93% accuracy at recognizing handwritten digits. Introducing the wake-up-like effect to 2D CIPS may pave the way for innovative approaches to achieve advanced multilevel nonvolatile memory and neuromorphic computing capabilities for next-generation micro-nanoelectronic devices.

Strain-induced ferromagnetism and magneto-electric coupling in two-dimensional ferroelectric ZnIn2S4

Two-dimensional (2D) multiferroic materials are currently in high demand due to their significant potential for applications in the field of high-density data storage devices. However, due to the different requirements for generating ferroelectricity and magnetism, 2D multiferroic materials are rare. In this study, we propose that applying strain can induce magnetism in 2D ferroelectric materials with special electronic structures, thereby creating 2D multiferroics. Taking 2D ZnIn2S4 as an example, it shows robust ferroelectricity with an appropriate switching barrier (79.3 meV), and the out-of-plane ferroelectric polarization is 0.0322 C/m2. Applying biaxial tensile strain can change the energy of the flatband near the Fermi level, ultimately resulting in self-doping phenomena and leading to Stoner-type itinerant ferromagnetism. The reversal of ferroelectric polarization in ZnIn2S4 bilayer and ZnIn2S4–In2Se3 heterostructure can manipulate the magnetic moment of the system, exhibiting significant magnetoelectric coupling phenomena. Our findings provide a pathway for designing 2D ferromagnetic and multiferroic materials.

Ferroelectric Polarization‐Mediated Modulation of Optical Properties in 2D van der Waals Architectures

AbstractThe integration of 2D ferroelectric materials with 2D photoelectric materials presents a promising avenue for addressing issues related to controlled doping and device integration in layered semiconductors. The reversible and non‐volatile residual polarization inherent to ferroelectrics can provide stable n‐ or p‐type doping for 2D semiconductors. Despite advances in doping strategies for 2D materials, existing techniques, and post‐doping characterization methodologies exhibit limitations, including the challenge of achieving high‐resolution graphical depictions of doped structures. Here, a WS2/CuInP2S6 heterostructure is demonstarted whereby the residual polarization of ferroelectric CuInP2S6 regions with anti‐parallel directions supplies screening charges of opposite signs to WS2 monolayers. This notably alters the ratio of neutral excitons and negatively charged trions within the recombination luminescence of the direct‐gap semiconductor, thereby offering a viable approach for controllable, non‐volatile modulation in 2D systems. Beyond proposing a feasible strategy for patterned doping and effective regulation in 2D semiconductors through interface engineering, this work enhances the understanding of the interplay between ferroelectrics and semiconductors.

Ferroelectric Bi2O2Te-Based Plasmonic Biosensor for Ultrasensitive Biomolecular Detection.

Ultrasensitive detection of biomarkers, particularly proteins, and microRNA, is critical for disease early diagnosis. Although surface plasmon resonance biosensors offer label-free, real-time detection, it is challenging to detect biomolecules at low concentrations that only induce a minor mass or refractive index change on the analyte molecules. Here an ultrasensitive plasmonic biosensor strategy is reported by utilizing the ferroelectric properties of Bi2O2Te as a sensitive-layer material. The polarization alteration of ferroelectric Bi2O2Te produces a significant plasmonic biosensing response, enabling the detection of charged biomolecules even at ultralow concentrations. An extraordinary ultralow detection limit of 1fm is achieved for protein molecules and an unprecedented 0.1fm for miRNA molecules, demonstrating exceptional specificity. The finding opens a promising avenue for the integration of 2D ferroelectric materials into plasmonic biosensors, with potential applications spanning a wide range.

Chemical Vapor Deposition Growth of 2D Ferroelectric Materials for Device Applications

Abstract2D ferroelectric materials have garnered extensive attention for promising applications in next‐generation electronic devices, which provides a platform to explore ferroelectricity without the critical thickness constraint of traditional perovskite oxide‐based ferroelectric materials. Recent studies have shown that chemical vapor deposition (CVD) can synthesis the large‐area 2D ferroelectric materials, making the 2D ferroelectric materials to be compatible with scalable semiconductor devices. In this Review, the CVD‐grown 2D ferroelectric materials are summarized in terms of materials, properties to devices application view. First, the synthesis strategy and recent advances of the CVD growth of 2D ferroelectric materials are highlighted in the aspects of diverse groups of 2D materials. Second, the recent experimental progress of 2D ferroelectric devices is introduced, and the potential applications of 2D ferroelectric devices are discussed. The availability of the CVD‐grown 2D ferroelectrics provides an abundant playground for not only deep studying the ferroelectric properties, but also conceiving various device applications. Lastly, the perspectives are provided to address the current challenges in terms of materials design, physics mechanism, device, and multifunctional application.

2D Ferroic Materials for Nonvolatile Memory Applications.

The emerging nonvolatile memory technologies based on ferroic materials are promising for producing high-speed, low-power, and high-density memory in the field ofintegrated circuits. Long-range ferroic orders observed in 2D materials have triggered extensive research interest in 2D magnets, 2D ferroelectrics, 2D multiferroics, and their device applications. Devices based on 2D ferroic materials and heterostructures with an atomically smooth interface and ultrathin thickness have exhibited impressive properties and significant potential for developing advanced nonvolatile memory. In this context, a systematic review of emergent 2D ferroic materials is conducted here, emphasizing their recent research on nonvolatile memory applications, with a view to proposing brighter prospects for 2D magnetic materials, 2D ferroelectric materials, 2D multiferroic materials, and their relevant devices.

TMD material investigation for a low hysteresis vdW NCFET logic transistor

Boltzmann limit is inevitable in conventional MOSFETs, which prevent them to be used for low-power applications. Research in device physics can address this problem by selection of proper materials satisfying our requirements. Recently, 2D transition metal di-chalcogenide (TMD) materials are gaining interest because they help alleviate short-channel effects and DIBL problems. The TMD materials are composed by covalently bonded weak van der Waals (vdW) interaction and can be realized as hetero structures with 2D ferro-electric material CuInP2S6 at the gate stack. This paper demonstrates a vdW negative capacitance field effect transistor (NCFET) structure in TCAD and the design was validated for voltage-current Characteristics. Parametric analysis shows MoS2 with phenomenal on/off ratio, narrow hysteresis than the counterparts. Simulation shows that MoS2 vdW NCFET has a high transconductance of 2.36 µS µm−1. A steep slope of 28.54 mV dec−1 is seen in MoS2 vdW NCFET which promises the performance of logic applications at a reduced supply voltage.