Two-dimensional Ferroelectric Materials Research Articles

Photodetector Based on Elemental Ferroelectric Black Phosphorus-like Bismuth.

Two-dimensional ferroelectric materials have emerged as a promising candidate for the development of next-generation photodetectors owing to their inherent photogalvanic effect (PGE) and strong light-matter interactions. Recently, the first-ever elemental-based ferroelectric material, black-phosphorus-like Bi (BP-Bi), has been successfully synthesized. In this work, we investigate the PGE of the monolayer (ML) BP-Bi by using ab initio quantum transport simulation. We find that the photocurrent of the ML BP-Bi in the ferroelectric direction (armchair) is significantly larger than that in the vertical ferroelectric direction [zigzag (ZZ)]. For example, despite the comparable optical absorption rates of BP-Bi in the armchair (ARM) and ZZ directions, the maximum photocurrent (133 mA/W) in the ARM direction is 2 orders of magnitude greater than that (4.70 mA/W) in the ZZ direction. The asymmetry is attributed to the breaking and existence of the mirror inversion symmetries along the ARM and ZZ directions, respectively. Our work paves the way for the research of the low-dimensional ferroelectric photodetector.

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.

Giant tunneling resistance and robust switching behavior in ferroelectric tunnel junctions of WS2/Ga2O3 heterostructures: The influence of metal–semiconductor contacts

The ferroelectric tunneling junctions (FTJs) are widely recognized as one of the non-volatile memories with significant potential. Ferroelectricity usually fades away as materials are thinned down below a critical value, and this problem is particularly acute in the case of shrinking device sizes, thus attracting attention to two-dimensional ferroelectric materials (2DFEMs). In this work, we designed 2D ferroelectric Ga2O3-based FTJs with out-of-plane polarization, and the influence of metal–semiconductor contact in the electrode region on the system is considered. Here, using density functional theory combined with the non-equilibrium Green's function approach to quantum transport calculations, we demonstrate robust ferroelectric polarization-controlled switching behavior between metallic and semiconducting states in Ga2O3/WS2 ferroelectric heterostructures. The potential barrier of the metal–semiconductor contact in the electrode region is lower than that of the intrinsic material, thereby resulting in an increased probability of electron tunneling. Our results reveal the crucial role of 2DFEMs in the construction of FTJs and highlight the significant impact of electrode contact types on performance. This provides a promising approach for developing high-density ferroelectric memories based on 2D ferroelectric semiconductor heterostructures.

Recent progresses in transmission electron microscopy studies of two-dimensional ferroelectrics

The rich potential of two-dimensional materials endows them with superior properties suitable for a wide range of applications, thereby attracting substantial interest across various fields. The ongoing trend towards device miniaturization aligns with the development of materials at progressively smaller scales, aiming to achieve higher integration density in electronics. In the realm of nano-scaling ferroelectric phenomena, numerous new two-dimensional ferroelectric materials have been predicted theoretically and subsequently validated through experimental confirmation. However, the capabilities of conventional tools, such as electrical measurements, are limited in providing a comprehensive investigation into the intrinsic origins of ferroelectricity and its interactions with structural factors. These factors include stacking, doping, functionalization, and defects. Consequently, the progress of potential applications, such as high-density memory devices, energy conversion systems, sensing technologies, catalysis, and more, is impeded. In this paper, we present a review of recent research that employs advanced transmission electron microscopy (TEM) techniques for the direct visualization and analysis of ferroelectric domains, domain walls, and other crucial features at the atomic level within two-dimensional materials. We discuss the essential interplay between structural characteristics and ferroelectric properties on the nanoscale, which facilitates understanding of the complex relationships governing their behavior. By doing so, we aim to pave the way for future innovative applications in this field.

Non-volatile electrical polarization switching via domain wall release in 3R-MoS2 bilayer

Understanding the nature of sliding ferroelectricity is of fundamental importance for the discovery and application of two-dimensional ferroelectric materials. In this work, we investigate the phenomenon of switchable polarization in a bilayer MoS2 with natural rhombohedral stacking, where the spontaneous polarization is coupled with excitonic effects through asymmetric interlayer coupling. Using optical spectroscopy and imaging techniques, we observe how a released domain wall switches the polarization of a large single domain. Our results highlight the importance of domain walls in the polarization switching of non-twisted rhombohedral transition metal dichalcogenides and open new opportunities for the non-volatile control of their optical response.

Atomic-scale manipulation of polar domain boundaries in monolayer ferroelectric In2Se3

Domain boundaries have been intensively investigated in bulk ferroelectric materials and two-dimensional materials. Many methods such as electrical, mechanical and optical approaches have been utilized to probe and manipulate domain boundaries. So far most research focuses on the initial and final states of domain boundaries before and after manipulation, while the microscopic understanding of the evolution of domain boundaries remains elusive. In this paper, we report controllable manipulation of the domain boundaries in two-dimensional ferroelectric In2Se3 with atomic precision using scanning tunneling microscopy. We show that the movements of the domain boundaries can be driven by the electric field from a scanning tunneling microscope tip and proceed by the collective shifting of atoms at the domain boundaries. Our density functional theory calculations reveal the energy path and evolution of the domain boundary movement. The results provide deep insight into domain boundaries in two-dimensional ferroelectric materials and will inspire inventive applications of these materials.

Ferroelectricity-Driven Self-Powered Weak Temperature and Broadband Light Detection in MoS2/CuInP2S6/WSe2 van der Waals Heterojunction Nanoarchitectonics.

Two-dimensional ferroelectric materials enrich the modulation degrees of freedom in self-powered van der Waals temperature/light detectors by incorporating pyroelectric and bulk photovoltaic effects. However, in addition to the low polarization, the practical applications of these materials are limited due to the significant challenge posed by their ultrathin nature, which affects their polarization stability. In this report, we introduce a design for a dual heterostructure-stabilized van der Waals heterojunction that addresses this challenge by improving the performance and extending the operational lifetime of self-powered van der Waals temperature/light detectors. The design is demonstrated using the MoS2/CuInP2S6 (CIPS)/WSe2 van der Waals heterojunction, which exhibits sensitivity to small temperature changes induced by weak light across the ultraviolet to mid-infrared spectrum. It can generate a noticeable pyroelectric current without the need for an external voltage, and its pyroelectric coefficient exceeds 130 and 978 μC/m2 K for 45 and 70 nm CIPS, respectively. The heterojunction offers high detection accuracy, with a temperature variation sensitivity as small as 0.1 K and an optical power intensity detection range from low to 1 μW/cm2. Additionally, the heterojunction exhibits exceptional detectivity (D*) for different light wavelengths. Remarkably, the self-powered detection performance remains stable for months without obvious degradation in the natural environment. These results offer a promising solution for high-performance, self-sustaining temperature/light detection applications and pave the way for the development of future ferroelectricity-driven photodetection technologies.

Recent advances in memristors based on two-dimensional ferroelectric materials

Recent advances in memristors based on two-dimensional ferroelectric materials

Bulk photovoltaic and photoconductivity effects in two-dimensional ferroelectric CuInP2S6 based heterojunctions

The construction of two-dimensional heterojunctions has significantly expanded the modulation degrees of freedom in two-dimensional materials, which has led to the emergence of numerous advanced microelectronics and optoelectronic devices. Extensive research has been conducted on the photovoltaic and photoconductivity effects to achieve higher photodetection performance in heterojunction-based devices. However, the bulk photovoltaic effect, which has excellent potential for applications in self-powered optoelectronics, microelectronics, and energy conversion devices, has not received enough attention. Herein, we construct a two-dimensional ferroelectric heterojunction using multi-layered CuInP2S6 (CIPS) and MoS2 nanoflakes and investigate its photoconductivity effect for photodetection. Furthermore, we observe and analyze the bulk photovoltaic effect in the heterojunction. The photoelectric effect in the MoS2 layer contributes to the photoconductivity effect of the heterojunction, while the room-temperature polar ordering in CIPS contributes to the bulk photovoltaic effect. The heterojunction exhibits high specific detectivity (D*) of 1.89 × 109 Jones, when the optical power intensity is 4.71 mW/cm2. Moreover, the short-circuit photocurrent density is high, reaching about 1.23 mA/cm2 when the optical power intensity is 0.35 W/cm2. This work highlights the potential application of two-dimensional ferroelectric materials in multifunction devices with self-powered detection and energy conversion capabilities.

In-plane ferroelectric monolayer TlNbX4O and its application in bulk photovoltaic effect

A bulk photovoltaic effect (BPVE) in materials without inversion symmetry attracts increasing interest for high-efficiency solar cells beyond the p–n junction paradigm. Herein, we report the photovoltaic effect in an experimentally feasible TlNbX4O monolayer (TlNbX4O-ML, X = Cl, Br, I) with a large ferroelectric polarization. Using first-principles calculations, we demonstrate that TlNbX4O-MLs are ferroelectric semiconductors with moderate switching barriers and higher spontaneous polarizations. Furthermore, we observe fairly giant shift current with the values of 109.6 μA/V2 for TlNbCl4O, 60 μA/V2 for TlNbBr4O, and 56.1 μA/V2 for TlNbI4O. These results unveil distinct features of the BPVE and the potential application of two-dimensional ferroelectric materials for next-generation photovoltaic devices.

Controllable growth α-In2Se3 flakes by chemical vapor deposition

Boosting large-scale application of two-dimensional ferroelectric materials as memory transistors has stimulated intensive research interest. Layered α-In2Se3 features strikingly ferroelectric properties, which allows unique opportunities for the engineering of functional ferroelectric devices. However, the large-scale and controllable growth of the α-In2Se3 has remained a challenge due to the complexity of indium-selenium growth phase diagram. Here, we report the controllable growth of α-In2Se3 flakes using the developed confined-space modulated chemical vapor deposition (CVD) method. The α-In2Se3 flakes are preferred to be deposited on the inner surfaces of the confined space while the β-In2Se3 flakes are mainly grown on the outer surfaces of the confined space. In addition, the grown α-In2Se3 flake possesses a large size of ∼ 60 μm, uniform thickness of ∼ 2.8 nm and distinct ferroelectric properties. Our findings offer an effective and easily accessible method for controllable growth of two-dimensional layered materials and hold promise for further insight into the fascinating physical properties and potential practical devices applications of van der Waal crystals.

Recent advances in two-dimensional ferroelectric materials

Recent advances in two-dimensional ferroelectric materials

Two-dimensional ferroelectrics from high throughput computational screening

We report a high throughput computational search for two-dimensional ferroelectric materials. The starting point is 252 pyroelectric materials from the computational 2D materials database (C2DB) and from these we identify 63 ferroelectrics. In particular we find 49 materials with in-plane polarization, 8 materials with out-of-plane polarization and 6 materials with coupled in-plane and out-of-plane polarization. Most of the known 2D ferroelectrics are recovered by the screening and the far majority of the predicted ferroelectrics are known as bulk van der Waals bonded compounds, which makes them accessible by direct exfoliation. For roughly 25% of the materials we find a metastable state in the non-polar structure, which may imply a first order transition to the polar phase. Finally, we list the magnetic pyroelectrics extracted from the C2DB and focus on the case of VAgP2Se6, which exhibits a three-state switchable polarization vector that is strongly coupled to the magnetic excitation spectrum.

Designing two-dimensional ferroelectric materials from phosphorus-analogue structures

Designing two-dimensional ferroelectric materials from phosphorus-analogue structures

Prediction of two-dimensional monolayer C2O2Fe with chiral magnetic and ferroelectric orders.

Low-dimensional multiferroics are highly desired for applications and contain exotic physical properties. Here we predict a two-dimensional material, C2O2Fe monolayer, through Fe intercalation in the graphene oxide monolayer. The crystal stable texture, chiral spin order, and ferroelectric polarization of the C2O2Fe monolayer are theoretically studied by considering the electron on-site Coulomb interaction and spin orbit coupling, which also manifests the ferroelectric polarization and reversal barrier at 30% biaxial tensile strain comparable with the other two-dimensional ferroelectric materials, such as GeS and GeSe. Moreover, first-principles calculations show that the polarization flipping is accompanied by spin orientation reversal, when the ferroelectric polarization is upward to the plane, a clockwise chiral antiferromagnetic ground state is obtained, while when the polarization is downward, the monolayer shows the anticlockwise chiral antiferromagnetic structure. In this sense, a strong electrically controlled magnetism exists in the designed C2O2Fe monolayer film.

Enhanced bulk photovoltaic effect in two-dimensional ferroelectric CuInP2S6

The photocurrent generation in photovoltaics relies essentially on the interface of p-n junction or Schottky barrier with the photoelectric efficiency constrained by the Shockley-Queisser limit. The recent progress has shown a promising route to surpass this limit via the bulk photovoltaic effect for crystals without inversion symmetry. Here we report the bulk photovoltaic effect in two-dimensional ferroelectric CuInP2S6 with enhanced photocurrent density by two orders of magnitude higher than conventional bulk ferroelectric perovskite oxides. The bulk photovoltaic effect is inherently associated to the room-temperature polar ordering in two-dimensional CuInP2S6. We also demonstrate a crossover from two-dimensional to three-dimensional bulk photovoltaic effect with the observation of a dramatic decrease in photocurrent density when the thickness of the two-dimensional material exceeds the free path length at around 40 nm. This work spotlights the potential application of ultrathin two-dimensional ferroelectric materials for the third-generation photovoltaic cells.

Pure bulk orbital and spin photocurrent in two-dimensional ferroelectric materials

We elucidate a bias-free light-induced orbital and spin current through nonlinear response theory, which generalizes the well-known bulk photovoltaic effect in centrosymmetric broken materials from charge to the spin and orbital degrees of freedom. We use two-dimensional nonmagnetic ferroelectric materials (such as GeS and its analogs) to illustrate this bulk orbital/spin photovoltaic effect, through first-principles calculations. These materials possess a vertical mirror symmetry and time-reversal symmetry but lack of inversion symmetry. We reveal that in addition to the conventional photocurrent that propagates parallel to the mirror plane (under linearly polarized light), the symmetric forbidden photocurrent perpendicular to the mirror actually contains electrons flow, which carries angular momentum information and move oppositely. This generates a pure orbital moment current with zero electric charge current. Such hidden photo-induced pure orbital current could lead to a pure spin current via spin–orbit coupling interactions. Therefore, a four-terminal device can be designed to detect and measure photo-induced charge, orbital, and spin currents simultaneously. All these currents couple with electric polarization P, hence their amplitude and direction can be manipulated through ferroelectric phase transition. Our work provides a route to generalizing nanoscale devices from their photo-induced electronics to orbitronics and spintronics.

Giant tunnel electroresistance in ferroelectric tunnel junctions with metal contacts to two-dimensional ferroelectric materials

Two-dimensional (2D) ferroelectric materials (FEMs) and their application in ferroelectric tunnel junctions (FTJs) have attracted a great deal of attention during the past several years due to their great potential in nonvolatile memory devices. Particularly, the all-2D FTJs, which have only atomic-layer thickness, have been demonstrated to show very high tunnel electroresistance (TER) ratio. Nevertheless, to better integrate with the present semiconductor technology, it is necessary to consider metal contacts in the construction of FTJs with 2D FEMs. However, due to the unknown interaction between traditional metals and 2D FEMs, it is not clear whether ferroelectricity still persists when the 2D FEMS are in contact with metals and whether the corresponding FTJs exhibit high TER effect as demanded for memory devices. To probe this, we construct FTJs with top contact between Au(010) and ${\mathrm{In}}_{2}{\mathrm{Se}}_{3}$, a 2D FEM with out-of-plane ferroelectric polarization. By density functional calculations combined with a nonequilibrium Green function technique, we find that not only the ferroelectricity still persists in the metal/FEM contact, but also a giant TER ratio as high as ${10}^{4}%$ is achieved. The giant TER arises from the change of the metal/FEM contact from a Schottky type to an Ohmic type accompanying with the ferroelectric polarization reversal. In the meantime, the tunnel barrier height between Au(010) and ${\mathrm{In}}_{2}{\mathrm{Se}}_{3}$ is zero, which means good ability of electron injection from metal to semiconductor and low contact resistance. Our study suggests that, by properly selecting the metal materials, giant TER ratio and high performance can be achieved in FTJs constructed with 2D FEMs and metal contacts.

Voting Data-Driven Regression Learning for Accelerating Discovery of Advanced Functional Materials and Applications to Two-Dimensional Ferroelectric Materials.

Regression machine learning is widely applied to predict various materials. However, insufficient materials data usually leads to poor performance. Here, we develop a new voting data-driven method that could generally improve the performance of the regression learning model for accurately predicting properties of materials. We apply it to investigate a large family (2135) of two-dimensional hexagonal binary compounds focusing on ferroelectric properties and find that the performance of the model for electric polarization is indeed greatly improved, where 38 stable ferroelectrics with out-of-plane polarization including 31 metals and 7 semiconductors are screened out. By unsupervised learning, actionable information such as how the number and orbital radius of valence electrons, ionic polarizability, and electronegativity of constituent atoms affect polarization was extracted. Our voting data-driven method not only reduces the size of materials data for constructing a reliable learning model but also enables one to make precise predictions for targeted functional materials.

Electric field control of molecular magnetic state by two-dimensional ferroelectric heterostructure engineering

Two-dimensional multiferroics have attracted tremendous attention due to their intriguing physics and promising applications. However, it has been a major challenge to discover and design two-dimensional multiferroic materials with large electric polarization and strong magnetoelectric coupling. In this work, we propose a strategy to design a two-dimensional van der Waals heterostructure with strong magnetoelectric coupling by stacking a transition metal phthalocyanine (TMPc) molecule with ferroelectric monolayer In2Se3. By first-principles electronic structure calculations, we predict that the magnetic states of the TMPc molecule can be controlled by electrically switching the polarization direction of In2Se3 using an external electric field. This strong magnetoelectric coupling effect originates from the interfacial charge transfer and orbital splitting, resulting in the different magnetic states of TMPc/In2Se3 heterostructures in two opposite ferroelectric phases. Based on the TMPc/In2Se3 heterostructure, a high-density magnetic memory device is proposed for pure electric writing and magnetic reading. Our predictions may open avenues for finding and designing multiferroic heterostructures by using two-dimensional ferroelectric materials and zero-dimensional magnetic molecules with a strong proximity effect.