A Synaptic Transistor based on Quasi‐2D Molybdenum Oxide

Biological synapses store and process information simultaneously by tuning the connection between two neighboring neurons. Such functionality inspires the task of hardware implementation of neuromorphic computing systems. Ionic/electronic hybrid three‐terminal memristive devices, in which the channel conductance can be modulated according to the history of applied voltage and current, provide a more promising way of emulating synapses by a substantial reduction in complexity and energy consumption. 2D van der Waals materials with single or few layers of crystal unit cells have been a widespread innovation in three‐terminal electronic devices. However, less attention has been paid to 2D transition‐metal oxides, which have good stability and technique compatibility. Here, nanoscale three‐terminal memristive transistors based on quasi‐2D α‐phase molybdenum oxide (α‐MoO₃) to emulate biological synapses are presented. The essential synaptic behaviors, such as excitatory postsynaptic current, depression and potentiation of synaptic weight, and paired‐pulse facilitation, as well as the transition of short‐term plasticity to long‐term potentiation, are demonstrated in the three‐terminal devices. These results provide an insight into the potential application of 2D transition‐metal oxides for synaptic devices with high scaling ability, low energy consumption, and high processing efficiency.     

Economizing Production of Diverse 2D Layered Metal Hydroxides for Efficient Overall Water Splitting

2D layered metal hydroxides (LMH) are promising materials for electrochemical energy conversion and storage. Compared with exfoliation of bulk layered materials, wet chemistry synthesis of 2D LMH materials under mild conditions still remains a big challenge. Here, an “MgO‐mediated strategy” for mass production of various 2D LMH nanosheets is presented by hydrolyzing MgO in metal salt aqueous solutions at room temperature. Benefiting from this economical and scalable strategy, ultrathin LMH nanosheets (M = Ni, Fe, Co, NiFe, and NiCo) and their derivatives (e.g., metal oxides and sulfides) can be synthesized in high yields. More importantly, this strategy opens up opportunities to fabricate hierarchically structured LMH nanosheets, resulting in high‐performance electrocatalysts for the oxygen‐ and hydrogen‐evolution reactions to realize stable overall water splitting with a low cell voltage of 1.55 V at 10 mA cm⁻². This work provides a powerful platform for the synthesis and applications of 2D materials.     

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.     

Coordination Polymer to Atomically Thin,Holey, Metal‐Oxide Nanosheets for Tuning Band Alignment

Holey 2D metal oxides have shown great promise as functional materials for energy storage and catalysts. Despite impressive performance, their processing is challenged by the requirement of templates plus capping agents or high temperatures; these materials also exhibit excessive thicknesses and low yields. The present work reports a metal‐based coordination polymer (MCP) strategy to synthesize polycrystalline, holey, metal oxide (MO) nanosheets with thicknesses as low as two‐unit cells. The process involves rapid exfoliation of bulk‐layered, MCPs (Ce‐, Ti‐, Zr‐based) into atomically thin MCPs at room temperature, followed by transformation into holey 2D MOs upon the removal of organic linkers in aqueous solution. Further, this work represents an extra step for decorating the holey nanosheets using precursors of transition metals to engineer their band alignments, establishing a route to optimize their photocatalysis. The work introduces a simple, high‐yield, room‐temperature, and template‐free approach to synthesize ultrathin holey nanosheets with high‐level functionalities.     

Wide-gap layered oxychalcogenide semiconductors: Materials, electronic structures and optoelectronic properties

Applying the concept of materials design for transparent conductive oxides to layered oxychalcogenides, several p-type and n-type layered oxychalcogenides were proposed as wide-gap semiconductors and their basic optical and electrical properties were examined. The layered oxychalcogenides are composed of ionic oxide layers and covalent chalcogenide layers, which bring wide-gap and conductive properties to these materials, respectively. The electronic structures of the materials were examined by normal/inverse photoemission spectroscopy and energy band calculations. The results of the examinations suggested that these materials possess unique features more than simple wide-gap semiconductors. Namely, the layered oxychalcogenides are considered to be extremely thin quantum wells composed of the oxide and chalcogenide layers or 2D chalcogenide crystals/molecules embedded in an oxide matrix. Observation of step-like absorption edges, large band gap energy and large exciton binding energy demonstrated these features originating from 2D density of states and quantum size effects in these layered materials.     

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.     

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.     

SnO2‐Based Nanomaterials: Synthesis and Application in Lithium‐Ion Batteries

The development of new electrode materials for lithium‐ion batteries (LIBs) has always been a focal area of materials science, as the current technology may not be able to meet the high energy demands for electronic devices with better performance. Among all the metal oxides, tin dioxide (SnO₂) is regarded as a promising candidate to serve as the anode material for LIBs due to its high theoretical capacity. Here, a thorough survey is provided of the synthesis of SnO₂‐based nanomaterials with various structures and chemical compositions, and their application as negative electrodes for LIBs. It covers SnO₂ with different morphologies ranging from 1D nanorods/nanowires/nanotubes, to 2D nanosheets, to 3D hollow nanostructures. Nanocomposites consisting of SnO₂ and different carbonaceous supports, e.g., amorphous carbon, carbon nanotubes, graphene, are also investigated. The use of Sn‐based nanomaterials as the anode material for LIBs will be briefly discussed as well. The aim of this review is to provide an in‐depth and rational understanding such that the electrochemical properties of SnO₂‐based anodes can be effectively enhanced by making proper nanostructures with optimized chemical composition. By focusing on SnO₂, the hope is that such concepts and strategies can be extended to other potential metal oxides, such as titanium dioxide or iron oxides, thus shedding some light on the future development of high‐performance metal‐oxide based negative electrodes for LIBs.     

Ultrathin Two‐Dimensional Multinary Layered Metal Chalcogenide Nanomaterials

Ultrathin two‐dimensional (2D) layered transition metal dichalcogenides (TMDs), such as MoS₂, WS₂, TiS₂, TaS₂, ReS₂, MoSe₂ and WSe₂, have attracted considerable attention over the past six years owing to their unique properties and great potential in a wide range of applications. Aiming to achieve tunable properties and optimal application performances, great effort is devoted to the exploration of 2D multinary layered metal chalcogenide nanomaterials, which include ternary metal chalcogenides with well‐defined crystal structures, alloyed TMDs, heteroatom‐doped TMDs and 2D metal chalcogenide heteronanostructures. These novel 2D multinary layered metal chalcogenide nanomaterials exhibit some unique properties compared to 2D binary TMD counterparts, thus holding great promise in various potential applications including electronics/optoelectronics, catalysis, sensors, biomedicine, and energy storage and conversion with enhanced performances. This article focuses on the state‐of‐art progress on the preparation, characterization and applications of ultrathin 2D multinary layered metal chalcogenide nanomaterials.     

Environmentally‐Friendly Exfoliate and Active Site Self‐Assembly: Thin 2D/2D Heterostructure Amorphous Nickel–Iron Alloy on 2D Materials for Efficient Oxygen Evolution Reaction

A class of 2D layered materials exhibits substantial potential for high‐performance electrocatalysts due to high specific surface area, tunable electronic properties, and open 2D channels for fast ion transport. However, liquid‐phase exfoliation always utilizes organic solvents that are harmful to the environment, and the active sites are limited to edge sites. Here, an environmentally friendly exfoliator in aqueous solution is presented without utilizing any toxic or hazardous substance and active site self‐assembly on the inert base of 2D materials. Benefiting from thin 2D/2D heterostructure and strong interfacial coupling, the resultant highly disordered amorphous NiFe/2D materials (Ti3C2 MXene, graphene and MoS₂) thin nanosheets exhibit extraordinary electrocatalytic performance toward oxygen evolution reaction (OER) in alkaline media. DFT results further verify the experimental results. The study emphasizes a viable idea to probe efficient electrocatalysts by means of the synergistic effect of environmentally friendly exfoliator in aqueous solution and active site self‐assembly on the inert base of 2D materials which forms the unique thin 2D/2D heterostructure in‐suit. This new type of heterostructure opens up a novel avenue for the rational design of highly efficient 2D materials for electrocatalysis.     

Countering the Segregation of Transition‐Metal Ions in LiMn1/3Co1/3Ni1/3O2 Cathode for Ultralong Life and High‐Energy Li‐Ion Batteries

High‐voltage layered lithium transition‐metal oxides are very promising cathodes for high‐energy Li‐ion batteries. However, these materials often suffer from a fast degradation of cycling stability due to structural evolutions. It seriously impedes the large‐scale application of layered lithium transition‐metal oxides. In this work, an ultralong life LiMn_1/3Co_1/3Ni_1/3O₂ microspherical cathode is prepared by constructing an Mn‐rich surface. Its capacity retention ratio at 700 mA g^?1 is as large as 92.9% after 600 cycles. The energy dispersive X‐ray maps of electrodes after numerous cycles demonstrate that the ultralong life of the as‐prepared cathode is attributed to the mitigation of TM‐ions segregation. Additionally, it is discovered that layered lithium transition‐metal oxide cathodes with an Mn‐rich surface can mitigate the segregation of TM ions and the corrosion of active materials. This study provides a new strategy to counter the segregation of TM ions in layered lithium transition‐metal oxides and will help to the design and development of high‐energy cathodes with ultralong life.     

Phosphorene and Phosphorene‐Based Materials – Prospects for Future Applications

Phosphorene, a single‐ or few‐layered semiconductor material obtained from black phosphorus, has recently been introduced as a new member of the family of two‐dimensional (2D) layered materials. Since its discovery, phosphorene has attracted significant attention, and due to its unique properties, is a promising material for many applications including transistors, batteries and photovoltaics (PV). However, based on the current progress in phosphorene production, it is clear that a lot remains to be explored before this material can be used for these applications. After providing a comprehensive overview of recent advancements in phosphorene synthesis, advantages and challenges of the currently available methods for phosphorene production are discussed. An overview of the research progress in the use of phosphorene for a wide range of applications is presented, with a focus on enabling important roles that phosphorene would play in next‐generation PV cells. Roadmaps that have the potential to address some of the challenges in phosphorene research are examined because it is clear that the unprecedented chemical, physical and electronic properties of phosphorene and phosphorene‐based materials are suitable for various applications, including photovoltaics.     

Striated 2D Lattice with Sub‐nm 1D Etch Channels by Controlled Thermally Induced Phase Transformations of PdSe2

2D crystals are typically uniform and periodic in‐plane with stacked sheet‐like structure in the out‐of‐plane direction. Breaking the in‐plane 2D symmetry by creating unique lattice structures offers anisotropic electronic and optical responses that have potential in nanoelectronics. However, creating nanoscale‐modulated anisotropic 2D lattices is challenging and is mostly done using top‐down lithographic methods with ≈10 nm resolution. A phase transformation mechanism for creating 2D striated lattice systems is revealed, where controlled thermal annealing induces Se loss in few‐layered PdSe₂ and leads to 1D sub‐nm etched channels in Pd₂Se₃ bilayers. These striated 2D crystals cannot be described by a typical unit cells of 1–2 Å for crystals, but rather long range nanoscale periodicity in each three directions. The 1D channels give rise to localized conduction states, which have no bulk layered counterpart or monolayer form. These results show how the known family of 2D crystals can be extended beyond those that exist as bulk layered van der Waals crystals by exploiting phase transformations by elemental depletion in binary systems.     

Atom‐by‐Atom Fabrication of Monolayer Molybdenum Membranes

Fabrication of materials in the monolayer regime to acquire fascinating physical properties has attracted enormous interest during the past decade, and remarkable success has been achieved for layered materials adopting weak interlayer van der Waals forces. However, the fabrication of monolayer metal membranes possessing strong intralayer bonding remains elusive. Here, suspended monolayer Mo membranes are fabricated from monolayer MoSe₂ films via selective electron beam (e‐beam) ionization of Se atoms by scanning transmission electron microscopy (STEM). The nucleation and subsequent growth of the Mo membranes are triggered by the formation and aggregation of Se vacancies as seen by atomic resolution sequential STEM imaging. Various novel structural defects and intriguing self‐healing characteristics are unveiled during the growth. In addition, the monolayer Mo membrane is highly robust under the e‐beam irradiation. It is likely that other metal membranes can be fabricated in a similar manner, and these pure metal‐based 2D materials add to the diversity of 2D materials and introduce profound novel physical properties.     

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.     

From Flatland to Spaceland: Higher Dimensional Patterning with Two‐Dimensional Materials

The creation of three‐dimensional (3D) structures from two‐dimensional (2D) nanomaterial building blocks enables novel chemical, mechanical or physical functionalities that cannot be realized with planar thin films or in bulk materials. Here, we review the use of emerging 2D materials to create complex out‐of‐plane surface topographies and 3D material architectures. We focus on recent approaches that yield periodic textures or patterns, and present four techniques as case studies: (i) wrinkling and crumpling of planar sheets, (ii) encapsulation by crumpled nanosheet shells, (iii) origami folding and kirigami cutting to create programmed curvature, and (iv) 3D printing of 2D material suspensions. Work to date in this field has primarily used graphene and graphene oxide as the 2D building blocks, and we consider how these unconventional approaches may be extended to alternative 2D materials and their heterostructures. Taken together, these emerging patterning and texturing techniques represent an intriguing alternative to conventional materials synthesis and processing methods, and are expected to contribute to the development of new composites, stretchable electronics, energy storage devices, chemical barriers, and biomaterials.     

Progress and Prospects of Graphdiyne‐Based Materials in Biomedical Applications

Graphdiyne is a new member of the family of carbon‐based nanomaterials that possess two types of carbon atoms, sp‐ and sp²‐hybridized carbon atoms. As a novel 2D carbon‐based nanomaterial with unique planar structure, such as uniformly distributed nanopores and large conjugated structure, graphdiyne has shown many fascinating properties in mechanics, electronics, and optics since it was first experimentally synthesized in 2010. Up to now, graphdiyne and its derivatives have been reported to be successfully applied in many areas, such as catalysis, energy, environment, and biomedicine, due to these excellent properties. Herein, the current research progress of graphdiyne‐based materials in biomedical fields is summarized, including biosensing, biological protection, cancer therapy, tissue engineering, etc. The advantages of graphdiyne and its derivatives are presented and compared with other carbon‐based materials. Considering the potential biomedical and clinical applications of graphdiyne‐based materials, the toxicity and biocompatibility are also discussed based on current studies. Finally, future perspectives and possible biomedical applications of graphdiyne‐based materials are also discussed.     

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.     

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.     

The Role of Graphene and Other 2D Materials in Solar Photovoltaics

2D materials have attracted considerable attention due to their exciting optical and electronic properties, and demonstrate immense potential for next‐generation solar cells and other optoelectronic devices. With the scaling trends in photovoltaics moving toward thinner active materials, the atomically thin bodies and high flexibility of 2D materials make them the obvious choice for integration with future‐generation photovoltaic technology. Not only can graphene, with its high transparency and conductivity, be used as the electrodes in solar cells, but also its ambipolar electrical transport enables it to serve as both the anode and the cathode. 2D materials beyond graphene, such as transition‐metal dichalcogenides, are direct‐bandgap semiconductors at the monolayer level, and they can be used as the active layer in ultrathin flexible solar cells. However, since no 2D material has been featured in the roadmap of standard photovoltaic technologies, a proper synergy is still lacking between the recently growing 2D community and the conventional solar community. A comprehensive review on the current state‐of‐the‐art of 2D‐materials‐based solar photovoltaics is presented here so that the recent advances of 2D materials for solar cells can be employed for formulating the future roadmap of various photovoltaic technologies.