Linear Dichroism and Nondestructive Crystalline Identification of Anisotropic Semimetal Few‐Layer MoTe2

Semimetal 1T′ MoTe₂ crystals have attracted tremendous attention owing to their anisotropic optical properties, Weyl semimetal, phase transition, and so on. However, the complex refractive indices (n‐ik) of the anisotropic semimetal 1T′ MoTe₂ still are not revealed yet, which is important to applications such as polarized wide spectrum detectors, polarized surface plasmonics, and nonlinear optics. Here, the linear dichroism of as‐grown trilayer 1T′ MoTe₂ single crystals is investigated. Trilayer 1T′ MoTe₂ shows obvious anisotropic optical absorption due to the intraband transition of d_z² orbits for Mo atoms and p_x orbits for Te atoms. The anisotropic complex refractive indices of few‐layer 1T′ MoTe₂ are experimentally obtained for the first time by using the Pinier equation analysis. Based on the linear dichroism of 1T′ MoTe₂, angle‐resolved polarized optical microscopy is developed to visualize the grain boundary and identify the crystal orientation of 1T′ MoTe₂ crystals, which is also an excellent tool toward the investigation of the optical absorption properties in the visible range for anisotropic 2D transition metal chalcogenides. This work provides a universal and nondestructive method to identify the crystal orientation of anisotropic 2D materials, which opens up an opportunity to investigate the optical application of anisotropic semimetal 2D materials.     

Recent advances in anisotropic two-dimensional materials and device applications

Two-dimensional(2D)materials,such as transition metal dichalcogenides(TMDs),black phosphorus(BP),MXene and borophene,have aroused extensive attention since the discovery of graphene in 2004.They have wide range of applications in many research fields,such as optoelectronic devices,energy storage,catalysis,owing to their striking physical and chemical properties.Among them,anisotropic 2D material is one kind of 2D materials that possess different properties along different directions caused by the intrinsic anisotropic atoms5 arrangement of the 2D materials,mainly including BP,borophene,low-symmetry TMDs(ReSe2 and ReSa)and group IV monochalcogenides(SnS,SnSe,GeS,and GeSe).Recently,a series of new devices has been fabricated based on these anisotropic 2D materials.In this review,we start from a brief introduction of the classifications,crystal structures,preparation techniques,stability,as well as the strategy to discriminate the anisotropic characteristics of 2D materials.Then,the recent advanced applications including electronic devices,optoelectronic devices,thermoelectric devices and nanomechanical devices based on the anisotropic 2D materials both in experiment and theory have been summarized.Finally,the current challenges and prospects in device designs,integration,mechanical analysis,and micro-/nano-fabrication techniques related to anisotropic 2D materials have been discussed.This review is aimed to give a generalized knowledge of anisotropic 2D materials and their current devices applications,and thus inspiring the exploration and development of other kinds of new anisotropic 2D materials and various novel device applications.     

Black Phosphorus: Optical Characterization,Properties and Applications

The rise of black phosphorus (BP) as a new family member of two‐dimensional (2D) materials brings new concepts and applications to the field, because of the infrared band gap and anisotropic properties of such materials. Among many excellent properties of BP, the optical property attracts special attention in recent years. Optical methods have been widely and successfully used in characterizing BP, not only to obtain the structural information (such as thickness and crystalline orientation), but also to probe the fundamental properties of BP in terms of the behavior of electrons, phonons, excitons etc. In this Review, a comprehensive understanding about the optical characterization of BP such as Raman, absorption, and photoluminescence is presented. Also, the unique optical properties and applications explored in recent years are reviewed.     

Black Arsenic: A Layered Semiconductor with Extreme In‐Plane Anisotropy

2D layered materials have emerged in recent years as a new platform to host novel electronic, optical, or excitonic physics and develop unprecedented nanoelectronic and energy applications. By definition, these materials are strongly anisotropic between the basal plane and cross the plane. The structural and property anisotropies inside their basal plane, however, are much less investigated. Black phosphorus, for example, is a 2D material that has such in‐plane anisotropy. Here, a rare chemical form of arsenic, called black‐arsenic (b‐As), is reported as a cousin of black phosphorus, as an extremely anisotropic layered semiconductor. Systematic characterization of the structural, electronic, thermal, and electrical properties of b‐As single crystals is performed, with particular focus on its anisotropies along two in‐plane principle axes, armchair (AC) and zigzag (ZZ). The analysis shows that b‐As exhibits higher or comparable electronic, thermal, and electric transport anisotropies between the AC and ZZ directions than any other known 2D crystals. Such extreme in‐plane anisotropies can potentially implement novel ideas for scientific research and device applications.     

Controlling Photoluminescence Enhancement and Energy Transfer in WS2:hBN:WS2 Vertical Stacks by Precise Interlayer Distances

2D semiconducting transition metal dichalcogenides (TMDs) are endowed with fascinating optical properties especially in their monolayer limit. Insulating hBN films possessing customizable thickness can act as a separation barrier to dictate the interactions between TMDs. In this work, vertical layered heterostructures (VLHs) of WS₂:hBN:WS₂ are fabricated utilizing chemical vapor deposition (CVD)‐grown materials, and the optical performance is evaluated through photoluminescence (PL) spectroscopy. Apart from the prohibited indirect optical transition due to the insertion of hBN spacers, the variation in the doping level of WS₂ drives energy transfer to arise from the layer with lower quantum efficiency to the other layer with higher quantum efficiency, whereby the total PL yield of the heterosystem is increased and the stack exhibits a higher PL intensity compared to the sum of those in the two WS₂ constituents. Such doping effects originate from the interfaces that WS₂ monolayers reside on and interact with. The electron density in the WS₂ is also controlled and subsequent modulation of PL in the heterostructure is demonstrated by applying back‐gated voltages. Other influential factors include the strain in WS₂ and temperature. Being able to tune the energy transfer in the VLHs may expand the development of photonic applications in 2D systems.     

Chemical Vapor Transport Reactions for Synthesizing Layered Materials and Their 2D Counterparts

2D materials, namely thin layers of layered materials, are attracting much attention because of their unique electronic, optical, thermal, and catalytic properties for wide applications. To advance both the fundamental studies and further practical applications, the scalable and controlled synthesis of large‐sized 2D materials is desired, while there still lacks ideal approaches. Alternatively, the chemical vapor transport reaction is an old but powerful technique, and is recently adopted for synthesizing 2D materials, producing bulk crystals of layered materials or corresponding 2D films. Herein, recent advancements in synthesizing both bulk layered and 2D materials by chemical vapor transport reactions are summarized. Beginning with a brief introduction of the fundamentals of chemical vapor transport reactions, chemical vapor transport–based syntheses of bulk layered and 2D materials, mainly exampled by transition metal dichalcogenides and black phosphorus, are reviewed. Particular attention is paid to important factors that can influence the reactions and the growth mechanisms of black phosphorus. Finally, perspectives about the chemical vapor transport–based synthesis of 2D materials are discussed, intending to redraw attentions on chemical vapor transport reactions.     

Recent advances in emerging 2D nanomaterials for biosensing and bioimaging applications

The great success of graphene throws new light on discovering more two-dimensional (2D) layered nanomaterials that stem from atomically thin 2D sheets. Compared with a single element of graphene, emerging graphene-like 2D materials composed of multiple elements that possess more versatility, greater flexibility and better functionality with a wide range of potential applications. In this review, we provide insights into the rapidly emerging 2D materials and their biosensing and bioimaging applications in recent three years, including 2D transition metal nanomaterials, graphitic nitride materials, black phosphorus, and emerging 2D organic polymers. We first briefly highlight their unique 2D morphology and physicochemical properties and then focus on their recent applications in electrochemical biosensing, optical biosensing and bioimaging. The challenges and some thoughts on future perspectives in this field are also addressed.     

Designer Shape Anisotropy on Transition‐Metal‐Dichalcogenide Nanosheets

MoS₂ and generally speaking, the wide family of transition‐metal dichalcogenides represents a solid nanotechnology platform on which to engineer a wealth of new and outperforming applications involving 2D materials. An even richer flexibility can be gained by extrinsically inducing an in‐plane shape anisotropy of the nanosheets. Here, the synthesis of anisotropic MoS₂ nanosheets is proposed as a prototypical example in this respect starting from a highly conformal chemical vapor deposition on prepatterend substrates and aiming at the more general purpose of tailoring anisotropy of 2D nanosheets by design. This is envisioned to be a suitable configuration for strain engineering as far as strain can be spatially redistributed in morphologically different regions. With a similar approach, both the optical and electronic properties of the 2D transition‐metal dichalcogenides can be tailored over macroscopic sample areas in a self‐organized fashion, thus paving the way for new applications in the field of optical metasurfaces, light harvesting, and catalysis.     

Air-Stable Low-Symmetry Narrow-Bandgap 2D Sulfide Niobium for Polarization Photodetection

Low-symmetry 2D materials with unique anisotropic optical and optoelectronic characteristics have attracted a lot of interest in fundamental research and manufacturing of novel optoelectronic devices. Exploring new and low-symmetry narrow-bandgap 2D materials will be rewarding for the development of nanoelectronics and nano-optoelectronics. Herein, sulfide niobium (NbS₃), a novel transition metal trichalcogenide semiconductor with low-symmetry structure, is introduced into a narrowband 2D material with strong anisotropic physical properties both experimentally and theoretically. The indirect bandgap of NbS₃ with highly anisotropic band structures slowly decreases from 0.42 eV (monolayer) to 0.26 eV (bulk). Moreover, NbS₃ Schottky photodetectors have excellent photoelectric performance, which enables fast photoresponse (11.6 µs), low specific noise current (4.6 × 10⁻²⁵ A² Hz⁻¹), photoelectrical dichroic ratio (1.84) and high-quality reflective polarization imaging (637 nm and 830 nm). A room-temperature specific detectivity exceeding 10⁷ Jones can be obtained at the wavelength of 3 µm. These excellent unique characteristics will make low-symmetry narrow-bandgap 2D materials become highly competitive candidates for future anisotropic optical investigations and mid-infrared optoelectronic 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.     

Emerging 2D metal oxides and their applications

In the past decade, several different classes of two-dimensional (2D) materials beyond graphene such as layered polymorphs of group V elements (phophorene, arsenene), Metalenes (gallenene, stanene etc.), Transition Metal–Dichalcogenides (TMDs), group III monochalcogenides, transition metal carbides as well as nitrides have been thoroughly explored. These atomically thin materials have gathered significant focus due to their unique electronic, optical, and magnetic properties, which are seldom found in their bulk counterparts due to the high surface to volume ratios and quantum confined electronic structure. These properties have led to excitement in the research community due to their potential applications in various fields of optoelectronics, energy harvesting and storage, sensing, electronics, magneto-electronics, and thermo-electronic applications. However, there is another emerging class of layered oxide 2D materials, which has been sporadically explored and lacks a systematic compilation of the made progress, potential benefits and research opportunities that may lie ahead. This specific review provides a thorough and systematic summary of research carried out on layered 2D oxides both from an experimental and theoretical perspective. Due to ultra-thin nature of the 2D metal oxides, a majority of the atoms are accessible to the surfaces, which induces new properties and applications in comparison to traditional bulk oxides. We discuss several different classes of metal oxides in their 2D forms such as MO, MO_x, M_xO_y (where M stands for metals; x and y possible oxidation states) as well as Perovskite type oxides in this review specifically focusing on optoelectronics, sensing and electrochemical storage applications. We further make critical comparisons with bulk metal oxides, and elaborate the specific advantages of 2D metal oxides as compared to their bulk counterparts in respective applications. Finally, we conclude by providing a critical assessment and outlook of technical challenges and research opportunities for future development of layered 2D oxides.     

Wrap‐Around Core–Shell Heterostructures of Layered Crystals

Engineered heterostructures create new functionality by integrating dissimilar materials. Combining different 2D crystals naturally produces two distinct classes of heterostructures, vertical van der Waals (vdW) stacks or 2D sheets bonded laterally by covalent line interfaces. When joining thicker layered crystals, the arising structural and topological conflicts can result in more complex geometries. Phase separation during one‐pot synthesis of layered tin chalcogenides spontaneously creates core–shell structures in which large orthorhombic SnS crystals are enclosed in a wrap‐around shell of trigonal SnS₂, forcing the coexistence of parallel vdW layering along with unconventional, orthogonally layered core–shell interfaces. Measurements of the optoelectronic properties establish anisotropic carrier separation near type II core–shell interfaces and extended long‐wavelength light harvesting via spatially indirect interfacial absorption, making multifunctional layered core–shell structures attractive for energy‐conversion applications.     

Anomalous Behavior of 2D Janus Excitonic Layers under Extreme Pressures

Newly discovered 2D Janus transition metal dichalcogenides layers have gained much attention from a theory perspective owing to their unique atomic structure and exotic materials properties, but little to no experimental data are available on these materials. Here, experimental and theoretical studies establish the vibrational and optical behavior of 2D Janus S–W–Se and S–Mo–Se monolayers under high pressures for the first time. Chemical vapor deposition (CVD)-grown classical transition metal dichalcogenides (TMD) monolayers are first transferred onto van der Waals (vdW) mica substrates and converted to 2D Janus sheets by surface plasma technique, and then integrated into a 500 µm size diamond anvil cell for high-pressure studies. The results show that 2D Janus layers do not undergo phase transition up to 15 GPa, and in this pressure regime, their vibrational modes exhibit a nonmonotonic response to the applied pressures (dω/dP). Interestingly, these 2D Janus monolayers exhibit unique blueshift in photoluminescence (PL) upon compression, which is in contrast to many other traditional semiconductor materials. Overall theoretical simulations offer in-depth insights and reveal that the overall optical response is a result of competition between the ab-plane (blueshift) and c-axis (redshift) compression. The overall findings shed the very first light on how 2D Janus monolayers respond under extreme pressures and expand the fundamental understanding of these materials.     

Strain-Engineered Anisotropic Optical and Electrical Properties in 2D Chiral-Chain Tellurium

Atomically thin materials, leveraging their low-dimensional geometries and superior mechanical properties, are amenable to exquisite strain manipulation with a broad tunability inaccessible to bulk or thin-film materials. Such capability offers unexplored possibilities for probing intriguing physics and materials science in the 2D limit as well as enabling unprecedented device applications. Here, the strain-engineered anisotropic optical and electrical properties in solution-grown, sub-millimeter-size 2D Te are systematically investigated through designing and introducing a controlled buckled geometry in its intriguing chiral-chain lattice. The observed Raman spectra reveal anisotropic lattice vibrations under the corresponding straining conditions. The feasibility of using buckled 2D Te for ultrastretchable strain sensors with a high gauge factor (≈380) is further explored. 2D Te is an emerging material boasting attractive characteristics for electronics, sensors, quantum devices, and optoelectronics. The results suggest the potential of 2D Te as a promising candidate for designing and implementing flexible and stretchable devices with strain-engineered functionalities.     

Metal Thio‐ and Selenophosphates as Multifunctional van der Waals Layered Materials

Since the discovery of Dirac physics in graphene, research in 2D materials has exploded with the aim of finding new materials and harnessing their unique and tunable electronic and optical properties. The follow‐on work on 2D dielectrics and semiconductors has led to the emergence and development of hexagonal boron nitride, black phosphorus, and transition metal disulfides. However, the spectrum of good insulating materials is still very narrow. Likewise, 2D materials exhibiting correlated phenomena such as superconductivity, magnetism, and ferroelectricity have yet to be developed or discovered. These properties will significantly enrich the spectrum of functional 2D materials, particularly in the case of high phase‐transition temperatures. They will also advance a fascinating fundamental frontier of size and proximity effects on correlated ground states. Here, a broad family of layered metal thio(seleno)phosphate materials that are moderate‐ to wide‐bandgap semiconductors with incipient ionic conductivity and a host of ferroic properties are reviewed. It is argued that this material class has the potential to merge the sought‐after properties of complex oxides with electronic functions of 2D and quasi‐2D electronic materials, as well as to create new avenues for both applied and fundamental materials research in structural and magnetic correlations.     

Emerging 2D nanomaterials for biomedical applications

Two-dimensional (2D) nanomaterials are an emerging class of biomaterials with remarkable potential for biomedical applications. The planar topography of these nanomaterials confers unique physical, chemical, electronic and optical properties, making them attractive candidates for therapeutic delivery, biosensing, bioimaging, regenerative medicine, and additive manufacturing strategies. The high surface-to-volume ratio of 2D nanomaterials promotes enhanced interactions with biomolecules and cells. A range of 2D nanomaterials, including transition metal dichalcogenides (TMDs), layered double hydroxides (LDHs), layered silicates (nanoclays), 2D metal carbides and nitrides (MXenes), metal–organic framework (MOFs), covalent organic frameworks (COFs) and polymer nanosheets have been investigated for their potential in biomedical applications. Here, we will critically evaluate recent advances of 2D nanomaterial strategies in biomedical engineering and discuss emerging approaches and current limitations associated with these nanomaterials. Due to their unique physical, chemical, and biological properties, this new class of nanomaterials has the potential to become a platform technology in regenerative medicine and other biomedical applications.     

二维原子晶体材料中的各向异性研究概述

二维原子晶体材料简称二维材料,因载流子迁移和热量扩散都被限制在二维平面内,展现出了许多奇特的性质而受到了广泛关注。二维材料的带隙可调特性在场效应管、光电器件、热电器件等领域应用广泛。另外二维材料的自旋自由度和谷自由度的可控性使得二维材料在自旋电子学和谷电子学等领域也引发了深入的研究。不同的二维材料由于晶体结构的特殊性质导致了不同的电学特性或者光学特性的各向异性,包括拉曼光谱、光致发光光谱、二阶谐波谱、光吸收谱、热导率、电导率等性质的各向异性。这些各向异性特性在偏振光电器件、偏振热电器件、仿生器件、偏振光探等领域拥有巨大的发展潜力。二维材料的各向异性还能够用于实现器件性能的最优化。文章介绍了各种二维材料的各向异性的最新研究进展。     

Intrinsic Van Der Waals Magnetic Materials from Bulk to the 2D Limit: New Frontiers of Spintronics

2D van der Waals (vdW) magnets, which present intrinsic ferromagnetic/antiferromagnetic ground states at finite temperatures down to atomic‐layer thicknesses, open a new horizon in materials science and enable the potential development of new spin‐related applications. The layered structure of vdW magnets facilitates their atomic‐layer cleavability and magnetic anisotropy, which counteracts spin fluctuations, thereby providing an ideal platform for theoretically and experimentally exploring magnetic phase transitions in the 2D limit. With reduced dimensions, the susceptibility of 2D magnets to a large variety of external stimuli also makes them more promising than their bulk counterpart in various device applications. Here, the current status of characterization and tuning of the magnetic properties of 2D vdW magnets, particularly the atomic‐layer thickness, is presented. Various state‐of‐the‐art optical and electrical techniques have been applied to reveal the magnetic states of 2D vdW magnets. Other emerging 2D vdW magnets and future perspectives on the stacking strategy are also given; it is believed that they will excite more intensive research and provide unprecedented opportunities in the field of spintronics.     

Few‐Layer GeAs Field‐Effect Transistors and Infrared Photodetectors

The family of 2D semiconductors (2DSCs) has grown rapidly since the first isolation of graphene. The emergence of each 2DSC material brings considerable excitement for its unique electrical, optical, and mechanical properties, which are often highly distinct from their 3D counterparts. To date, studies of 2DSC are majorly focused on group IV (e.g., graphene, silicene), group V (e.g., phosphorene), or group VIB compounds (transition metal dichalcogenides, TMD), and have inspired considerable effort in searching for novel 2DSCs. Here, the first electrical characterization of group IV–V compounds is presented by investigating few‐layer GeAs field‐effect transistors. With back‐gate device geometry, p‐type behaviors are observed at room temperature. Importantly, the hole carrier mobility is found to approach 100 cm² V^?1 s^?1 with ON–OFF ratio over 10⁵, comparable well with state‐of‐the‐art TMD devices. With the unique crystal structure the few‐layer GeAs show highly anisotropic optical and electronic properties (anisotropic mobility ratio of 4.8). Furthermore, GeAs based transistor shows prominent and rapid photoresponse to 1.6 µm radiation with a photoresponsivity of 6 A W^?1 and a rise and fall time of ≈3 ms. This study of group IV–V 2DSC materials greatly expands the 2D family, and can enable new opportunities in functional electronics and optoelectronics based on 2DSCs.     

二维原子晶体材料中的各向异性研究概述

二维原子晶体材料简称二维材料,因载流子迁移和热量扩散都被限制在二维平面内,展现出了许多奇特的性质而受到了广泛关注.二维材料的带隙可调特性在场效应管、光电器件、热电器件等领域应用广泛.另外二维材料的自旋自由度和谷自由度的可控性使得二维材料在自旋电子学和谷电子学等领域也引发了深入的研究.不同的二维材料由于晶体结构的特殊性质导致了不同的电学特性或者光学特性的各向异性,包括拉曼光谱、光致发光光谱、二阶谐波谱、光吸收谱、热导率、电导率等性质的各向异性.这些各向异性特性在偏振光电器件、偏振热电器件、仿生器件、偏振光探等领域拥有巨大的发展潜力.二维材料的各向异性还能够用于实现器件性能的最优化.文章介绍了各种二维材料的各向异性的最新研究进展.