2D Intrinsic Ferromagnetic MnP Single Crystals

2D intrinsic ferromagnetic materials are highly anticipated in spintronic devices due to their coveted 2D limited magnetism. However, 2D non‐layered intrinsic ferromagnets have received sporadic attention, which is largely attributed to the fact that their synthesis is still a great challenge. Significantly, manganese phosphide (MnP) is a promising non‐layered intrinsic ferromagnet with excellent properties. Herein, high‐quality 2D MnP single crystals formed over liquid metal tin (Sn) is demonstrated through a facile chemical vapor deposition technique. The introduction of liquid metal Sn provides a fertile ground for the growth of 2D MnP single crystals. Interestingly, 2D MnP single crystals maintain their intrinsic ferromagnetism and exhibit a Curie temperature above room temperature. The research enriches the diversity of 2D intrinsic ferromagnetic materials, opening up opportunities for further exploration of their unique properties and rich applications.     

3R MoS2 with Broken Inversion Symmetry: A Promising Ultrathin Nonlinear Optical Device

Nonlinear 2D layered crystals provide ideal platforms for applications and fundamental studies in ultrathin nonlinear optical (NLO) devices. However, the NLO frequency conversion efficiency constrained by lattice symmetry is still limited by layer numbers of 2D crystals. In this work, 3R MoS₂ with broken inversion symmetry structure are grown and proved to be excellent NLO 2D crystals from monolayer (0.65 nm) toward bulk‐like (300 nm) dimension. Thickness and wavelength‐dependent second harmonic generation spectra offer the selection rules of appropriate working conditions. A model comprising of bulk nonlinear contribution and interface interaction is proposed to interpret the observed nonlinear behavior. Polarization enhancement with two petals along staggered stacking direction appears in 3R MoS₂ is first observed and the robust polarization of 3R MoS₂ crystal is caused by the retained broken inversion symmetry. The results provide a new arena for realizing ultrathin NLO devices for 2D layered materials.     

Anisotropic optical and electronic properties of two-dimensional layered germanium sulfide

Two-dimensional (2D) layered materials,transition-metal dichalcogenides,and black phosphorus have attracted considerable interest from the viewpoints of fundamental physics and device applications.The establishment of new functionalities in anisotropic layered 2D materials is a challenging but rewarding frontier,owing to the remarkable optical properties of these materials and their prospects for new devices.Herein,we report the anisotropic and thicknessdependent optical properties of a 2D layered monochalcogenide of germanium sulfide (GeS).Three Raman-scattering peaks corresponding to the B3g,A1g,and A2g modes with a strong polarization dependence are demonstrated in the GeS flakes,which validates polarized Raman spectroscopy as an effective method for identifying the crystal orientation of anisotropic layered GeS.Photoluminescence (PL) is observed with a peak at ～1.66 eV that originates from the direct optical transition in GeS at room temperature.The polarization-dependent characteristics of the PL,which are revealed for the first time,along with the demonstration of anisotropic absorption,indicate an obvious anisotropic optical transition near the band edge of GeS,which is supported by density functional theory calculations.The significantly thickness-dependent PL is observed and discussed.This anisotropic layered GeS presents opportunities for the discovery of new physical phenomena and will find applications that exploit its anisotropic properties,such as polarization-sensitive photodetectors.     

Structural Phase Transition Effect on Resistive Switching Behavior of MoS2‐Polyvinylpyrrolidone Nanocomposites Films for Flexible Memory Devices

The 2H phase and 1T phase coexisting in the same molybdenum disulfide (MoS₂) nanosheets can influence the electronic properties of the materials. The 1T phase of MoS₂ is introduced into the 2H‐MoS₂ nanosheets by two‐step hydrothermal synthetic methods. Two types of nonvolatile memory effects, namely write‐once read‐many times memory and rewritable memory effect, are observed in the flexible memory devices with the configuration of Al/1T@2H‐MoS₂‐polyvinylpyrrolidone (PVP)/indium tin oxide (ITO)/polyethylene terephthalate (PET) and Al/2H‐MoS₂‐PVP/ITO/PET, respectively. It is observed that structural phase transition in MoS₂ nanosheets plays an important role on the resistive switching behaviors of the MoS₂‐based device. It is hoped that our results can offer a general route for the preparation of various promising nanocomposites based on 2D nanosheets of layered transition metal dichalcogenides for fabricating the high performance and flexible nonvolatile memory devices through regulating the phase structure in the 2D nanosheets.     

Charge‐Trap Memory Based on Hybrid 0D Quantum Dot–2D WSe2 Structure

Recently, layered ultrathin 2D semiconductors, such as MoS₂ and WSe₂ are widely studied in nonvolatile memories because of their excellent electronic properties. Additionally, discrete 0D metallic nanocrystals and quantum dots (QDs) are considered to be outstanding charge‐trap materials. Here, a charge‐trap memory device based on a hybrid 0D CdSe QD–2D WSe₂ structure is demonstrated. Specifically, ultrathin WSe₂ is employed as the channel of the memory, and the QDs serve as the charge‐trap layer. This device shows a large memory window exceeding 18 V, a high erase/program current ratio (reaching up to 10⁴), four‐level data storage ability, stable retention property, and high endurance of more than 400 cycles. Moreover, comparative experiments are carried out to prove that the charges are trapped by the QDs embedded in the Al₂O₃. The combination of 2D semiconductors with 0D QDs opens up a novelty field of charge‐trap memory devices.     

Catalyst‐Selective Growth of Single‐Orientation Hexagonal Boron Nitride toward High‐Performance Atomically Thin Electric Barriers

The ability to control the crystal orientation of 2D van der Waals (vdW) layered materials grown on large‐scale substrates is crucial for tailoring their electrical properties, as well as for integration of functional 2D devices. In general, multiple orientations, i.e., two or four orientations, appear through the crystal rotational symmetry matching between the material and its substrate. Here, it is reported that hexagonal boron nitride (h‐BN), an ideal electric barrier in the family of 2D materials, has a single orientation on inclined Cu (1 0 1) surfaces, where the Cu planes are tilted from the (1 0 1) facet around specific in‐plane axes. Density functional theory (DFT) calculation indicates that this is a manifestation of only one favored h‐BN orientation with the minimum vdW energy on the inclined Cu (1 0 1) surface. Moreover, thanks to the high interfacial strength with the underlying Cu, the single‐orientation h‐BN is free of thermal wrinkles, and exhibits a spatially homogeneous morphology and tunnel conductance. The findings point to a feasible approach to direct growth of single‐orientation, wrinkle‐free h‐BN thin film for high‐performance 2D electrical devices, and will be of benefit for controllable synthesis of other vdW materials.     

Recent Progress in CVD Growth of 2D Transition Metal Dichalcogenides and Related Heterostructures

In recent years, 2D layered materials have received considerable research interest on account of their substantial material systems and unique physicochemical properties. Among them, 2D layered transition metal dichalcogenides (TMDs), a star family member, have already been explored over the last few years and have exhibited excellent performance in electronics, catalysis, and other related fields. However, to fulfill the requirement for practical application, the batch production of 2D TMDs is essential. Recently, the chemical vapor deposition (CVD) technique was considered as an elegant alternative for successfully growing 2D TMDs and their heterostructures. The latest research advances in the controllable synthesis of 2D TMDs and related heterostructures/superlattices via the CVD approach are illustrated here. The controlled growth behavior, preparation strategies, and breakthroughs on the synthesis of new 2D TMDs and their heterostructures, as well as their unique physical phenomena, are also discussed. Recent progress on the application of CVD‐grown 2D materials is revealed with particular attention to electronics/optoelectronic devices and catalysts. Finally, the challenges and future prospects are considered regarding the current development of 2D TMDs and related heterostructures.     

On the Working Mechanisms of Molecules-Based Van der Waals Dielectrics

Sb₂O₃ molecules offer unprecedented opportunities for the integration of a van der Waals (vdW) dielectric and a 2D vdW semiconductor. However, the working mechanisms underlying molecules-based vdW dielectrics remain unclear. Here, the working mechanisms of Sb₂O₃ and two Sb₂O₃-like molecules (As₂O₃ and Bi₂O₃) as dielectrics are systematically investigated by combining first-principles calculations and gate leakage current theories. It is revealed that molecules-based vdW dielectrics have a considerable advantage over conventional dielectric materials: defects hardly affect their insulating properties. This shows that it is unnecessary to synthesize high-quality crystals in practical applications, which has been a long-standing challenge for conventional dielectric materials. Further analysis reveals that a large thermionic-emission current renders Sb₂O₃ difficult to simultaneously satisfy the requirements of dielectric layers in p-MOS and n-MOS, which hinders its application for complementary metal-oxide-semiconductor (CMOS) devices. Remarkably, it is found that As₂O₃ can serve as a dielectric for both p-MOS and n-MOS. This work not only lays a theoretical foundation for the application of molecules-based vdW dielectrics, but also offers an unprecedentedly competitive dielectric (i.e., As₂O₃) for 2D vdW semiconductors-based CMOS devices, thus having profound implications for future semiconductor industry.     

A stacked memory device on logic 3D technology for ultra-high-density data storage

We have demonstrated, for the first time, a novel three-dimensional (3D) memory chip architecture of stacked-memory-devices-on-logic (SMOL) achieving up to 95% of cell-area efficiency by directly building up memory devices on top of front-end CMOS devices. In order to realize the SMOL, a unique 3D Flash memory device and vertical integration structure have been successfully developed. The SMOL architecture has great potential to achieve tera-bit level memory density by stacking memory devices vertically and maximizing cell-area efficiency. Furthermore, various emerging devices could replace the 3D memory device to develop new 3D chip architectures.     

Gate-Coupling-Enabled Robust Hysteresis for Nonvolatile Memory and Programmable Rectifier in Van der Waals Ferroelectric Heterojunctions

Ferroelectric field-effect transistors (FeFETs) are one of the most interesting ferroelectric devices; however, they, usually suffer from low interface quality. The recently discovered 2D layered ferroelectric materials, combining with the advantages of van der Waals heterostructures (vdWHs), may be promising to fabricate high-quality FeFETs with atomically thin thickness. Here, dual-gated 2D ferroelectric vdWHs are constructed using MoS₂, hexagonal boron nitride (h-BN), and CuInP₂S₆ (CIPS), which act as a high-performance nonvolatile memory and programmable rectifier. It is first noted that the insertion of h-BN and dual-gated coupling device configuration can significantly stabilize and effectively polarize ferroelectric CIPS. Through this design, the device shows a record-high performance with a large memory window, large on/off ratio (10⁷), ultralow programming state current (10⁻¹³ A), and long-time endurance (10⁴ s) as nonvolatile memory. As for programmable rectifier, a wide range of gate-tunable rectification behavior is observed. Moreover, the device exhibits a large rectification ratio (3 × 10⁵) with stable retention under the programming state. This demonstrates the promising potential of ferroelectric vdWHs for new multifunctional ferroelectric devices.     

2D Oxide Nanomaterials to Address the Energy Transition and Catalysis

2D oxide nanomaterials constitute a broad range of materials, with a wide array of current and potential applications, particularly in the fields of energy storage and catalysis for sustainable energy production. Despite the many similarities in structure, composition, and synthetic methods and uses, the current literature on layered oxides is diverse and disconnected. A number of reviews can be found in the literature, but they are mostly focused on one of the particular subclasses of 2D oxides. This review attempts to bridge the knowledge gap between individual layered oxide types by summarizing recent developments in all important 2D oxide systems including supported ultrathin oxide films, layered clays and double hydroxides, layered perovskites, and novel 2D‐zeolite‐based materials. Particular attention is paid to the underlying similarities and differences between the various materials, and the subsequent challenges faced by each research community. The potential of layered oxides toward future applications is critically evaluated, especially in the areas of electrocatalysis and photocatalysis, biomass conversion, and fine chemical synthesis. Attention is also paid to corresponding novel 3D materials that can be obtained via sophisticated engineering of 2D oxides.     

Nonvolatile Memories Based on Graphene and Related 2D Materials

The pervasiveness of information technologies is generating an impressive amount of data, which need to be accessed very quickly. Nonvolatile memories (NVMs) are making inroads into high‐capacity storage to replace hard disk drives, fuelling the expansion of the global storage memory market. As silicon‐based flash memories are approaching their fundamental limit, vertical stacking of multiple memory cell layers, innovative device concepts, and novel materials are being investigated. In this context, emerging 2D materials, such as graphene, transition metal dichalcogenides, and black phosphorous, offer a host of physical and chemical properties, which could both improve existing memory technologies and enable the next generation of low‐cost, flexible, and wearable storage devices. Herein, an overview of graphene and related 2D materials (GRMs) in different types of NVM cells is provided, including resistive random‐access, flash, magnetic and phase‐change memories. The physical and chemical mechanisms underlying the switching of GRM‐based memory devices studied in the last decade are discussed. Although at this stage most of the proof‐of‐concept devices investigated do not compete with state‐of‐the‐art devices, a number of promising technological advancements have emerged. Here, the most relevant material properties and device structures are analyzed, emphasizing opportunities and challenges toward the realization of practical NVM devices.     

Triboelectric Series of 2D Layered Materials

Recently, as applications based on triboelectricity have expanded, understanding the triboelectric charging behavior of various materials has become essential. This study investigates the triboelectric charging behaviors of various 2D layered materials, including MoS₂, MoSe₂, WS₂, WSe₂, graphene, and graphene oxide in a triboelectric series using the concept of a triboelectric nanogenerator, and confirms the position of 2D materials in the triboelectric series. It is also demonstrated that the results are obviously related to the effective work functions. The charging polarity indicates the similar behavior regardless of the synthetic method and film thickness ranging from a few hundred nanometers (for chemically exfoliated and restacked films) to a few nanometers (for chemical vapor deposited films). Further, the triboelectric charging characteristics could be successfully modified via chemical doping. This study provides new insights to utilize 2D materials in triboelectric devices, allowing thin and flexible device fabrication.     

Substrate‐Friendly Growth of Large‐Sized Ni(OH)2 Nanosheets for Flexible Electrochromic Films

Large‐area, 2D, anisotropic, direct growth of nanostructures is considered an effective and straightforward way to readily fulfill transparent, flexible technology requirements. In addition, formation of thin hybrid structures by combining with another 2D material brings about dimensional advantages, such as intimate heterostructure functionalities, large specific area, and optical transparency. Here, we demonstrate 2D planar growth of thin Ni(OH)₂ nanosheets on arbitrary rigid and soft supports, by exploiting the growth strategies of oriented attachment induced by interfacial chemistry and the intrinsic driving force of layered structure constitution. Moreover, large‐scale 2D heterohybrids have successfully been prepared by direct conformal growth of Ni(OH)₂ nanosheets overlying MoO₃ nanobelts. Unlike the exfoliation and transfer of 2D materials technique, this approach minimizes multiple process contamination and physical‐handling structural defects. Accordingly, proof‐of‐concept flexible electrochromism is demonstrated in view of its prerequisite to the access of a large homogeneous material coating. The as‐synthesized 2D layered structure affirms its optical and electrochemical superiority through the display of wide optical modulation, high coloration efficiency, good cyclic stability, and flexibility.     

Thinnest Nonvolatile Memory Based on Monolayer h‐BN

2D materials have attracted much interest over the past decade in nanoelectronics. However, it was believed that the atomically thin layered materials are not able to show memristive effect in vertically stacked structure, until the recent discovery of monolayer transition metal dichalcogenide (TMD) atomristors, overcoming the scaling limit to sub‐nanometer. Herein, the nonvolatile resistance switching (NVRS) phenomenon in monolayer hexagonal boron nitride (h‐BN), a typical 2D insulator, is reported. The h‐BN atomristors are studied using different electrodes and structures, featuring forming‐free switching in both unipolar and bipolar operations, with large on/off ratio (up to 10⁷). Moreover, fast switching speed (<15 ns) is demonstrated via pulse operation. Compared with monolayer TMDs, the one‐atom‐thin h‐BN sheet reduces the vertical scaling to ≈0.33 nm, representing a record thickness for memory materials. Simulation results based on ab‐initio method reveal that substitution of metal ions into h‐BN vacancies during electrical switching is a likely mechanism. The existence of NVRS in monolayer h‐BN indicates fruitful interactions between defects, metal ions and interfaces, and can advance emerging applications on ultrathin flexible memory, printed electronics, neuromorphic computing, and radio frequency switches.     

A High‐On/Off‐Ratio Floating‐Gate Memristor Array on a Flexible Substrate via CVD‐Grown Large‐Area 2D Layer Stacking

Memristors such as phase‐change memory and resistive memory have been proposed to emulate the synaptic activities in neuromorphic systems. However, the low reliability of these types of memories is their biggest challenge for commercialization. Here, a highly reliable memristor array using floating‐gate memory operated by two terminals (source and drain) using van der Waals layered materials is demonstrated. Centimeter‐scale samples (1.5 cm × 1.5 cm) of MoS₂ as a channel and graphene as a trap layer grown by chemical vapor deposition (CVD) are used for array fabrication with Al₂O₃ as the tunneling barrier. With regard to the memory characteristics, 93% of the devices exhibit an on/off ratio of over 10³ with an average ratio of 10⁴. The high on/off ratio and reliable endurance in the devices allow stable 6‐level memory applications. The devices also exhibit excellent memory durability over 8000 cycles with a negligible shift in the threshold voltage and on‐current, which is a significant improvement over other types of memristors. In addition, the devices can be strained up to 1% by fabricating on a flexible substrate. This demonstration opens a practical route for next‐generation electronics with CVD‐grown van der Waals layered materials.     

Self‐Formed Channel Devices Based on Vertically Grown 2D Materials with Large‐Surface‐Area and Their Potential for Chemical Sensor Applications

2D layered materials with sensitive surfaces are promising materials for use in chemical sensing devices, owing to their extremely large surface‐to‐volume ratios. However, most chemical sensors based on 2D materials are used in the form of laterally defined active channels, in which the active area is limited to the actual device dimensions. Therefore, a novel approach for fabricating self‐formed active‐channel devices is proposed based on 2D semiconductor materials with very large surface areas, and their potential gas sensing ability is examined. First, the vertical growth phenomenon of SnS₂ nanocrystals is investigated with large surface area via metal‐assisted growth using prepatterned metal electrodes, and then self‐formed active‐channel devices are suggested without additional pattering through the selective synthesis of SnS₂ nanosheets on prepatterned metal electrodes. The self‐formed active‐channel device exhibits extremely high response values (>2000% at 10 ppm) for NO₂ along with excellent NO₂ selectivity. Moreover, the NO₂ gas response of the gas sensing device with vertically self‐formed SnS₂ nanosheets is more than two orders of magnitude higher than that of a similar exfoliated SnS₂‐based device. These results indicate that the facile device fabrication method would be applicable to various systems in which surface area plays an important role.     

Predicting 2D silicon allotropes on SnS<Subscript>2</Subscript>

A first principles study on the stability and structural and electronic properties of two-dimensional silicon allotropes on a semiconducting layered metal-chalcogenide compound,namely SnS2,is performed.The interactions between the two-dimensional silicon layer,commonly known as silicene,and the layered SnS2 template are investigated by analyzing different configurations of silicene.The calculated thermodynamic phase diagram suggests that the most stable configuration of silicene on SnS2 belongs to a family of structures with Si atoms placed on three different planes;so-called dumbbell silicene.This particular dumbbell silicene structure preserves its atomic configuration on SnS2 even at a temperature of 500 K or as a "flake" layer (i.e.,a silicene cluster terminated by H atoms),thanks to the weak interactions between the silicene and the SnS2 layers.Remarkably,an electric field can be used to tune the band gap of the silicene layer on SnS2,eventually changing its electronic behavior from semiconducting to (semi)metallic.The stability of silicene on SnS2 is very promising for the integration of silicene onto semiconducting or insulating substrates.The tunable electronic behavior of the silicene/SnS2 van der Walls heterostructure is very important not only for its use in future nanoelectronic devices,but also as a successful approach to engineering the bang-gap of layered SnS2,paving the way for the use of this layered compound in energy harvesting applications.     

1D and 2D Field Effect Transistors in Gas Sensing: A Comprehensive Review

Rapid progress in the synthesis and fundamental understanding of 1D and 2D materials have solicited the incorporation of these nanomaterials into sensor architectures, especially field effect transistors (FETs), for the monitoring of gas and vapor in environmental, food quality, and healthcare applications. Yet, several challenges have remained unaddressed toward the fabrication of 1D and 2D FET gas sensors for real-field applications, which are related to properties, synthesis, and integration of 1D and 2D materials into the transistor architecture. This review paper encompasses the whole assortment of 1D—i.e., metal oxide semiconductors (MOXs), silicon nanowires (SiNWs), carbon nanotubes (CNTs)—and 2D—i.e., graphene, transition metal dichalcogenides (TMD), phosphorene—materials used in FET gas sensors, critically dissecting how the material synthesis, surface functionalization, and transistor fabrication impact on electrical versus sensing properties of these devices. Eventually, pros and cons of 1D and 2D FETs for gas and vapor sensing applications are discussed, pointing out weakness and highlighting future directions.     

具有2D-EDAPbI4薄覆盖层的环境稳定的FAPbI3基钙钛矿太阳能电池（英文）

二维(2D)卤化铅钙钛矿材料是钙钛矿太阳能电池(PSC)中最有前途的吸光材料之一,具有优异的稳定性和缺陷钝化作用.然而,这些稳定的二维PSC的转换效率仍远远落后于三维钙钛矿电池.在本文中我们通过原位生长的方法将2D EDAPbI4层成功制备在3D FAPbI3层表面。这种合理设计的2D-3D钙钛矿薄膜分层结构可以明显提高电池的效率.另外,由于EDAPbI4层的高抗湿性和抑制迁移, 2D-3D电池器件显示出明显增强的长期稳定性,在200 h内一直保持初始转换效率,甚至在500 h后仍能保持其初始转化效率的90%.