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.     

Band Engineering for Novel Two‐Dimensional Atomic Layers

The discovery of graphene has sparked much interest in science and lead to the development of an ample variety of novel two‐dimensional (2D) materials. With increasing research interest in the field of 2D materials in recent years, the researchers have shifted their focus from the synthesis to the modification of 2D materials, emphasizing their electronic structures. In this review, the possibilities of altering the band structures are discussed via three different approches: (1) alloying 2D materials, so called ternary 2D materials, such as hexagonal carbonized boron nitrides (h‐BCN) and transition metal dichalcogenides (TMDs) ternary materials; (2) stacking 2D materials vertically, which results in 2D heterostructures named van der Waals (vdW) solids (using hexagonal boron nitrides (h‐BN)/graphene and TMDs stacking as examples), and growing lateral TMDs heterostructrues; (3) controlling the thickness of 2D materials, that is, the number of layers. The electronic properties of some 2D materials are very sensitive to the thickness, such as in TMDs and black phosphorus (BP). The variations of band structures and the resulting physical properties are systematically discussed.     

Field-Induced Superconductivity in MoS2

Semiconducting TMDs are nowadays attracting great interest after the invention of the so-called “Scotch-tape method” established in graphene research. Semiconducting TMDs are front-runners of “post graphene” materials for their finite band gap crucial for device applications. MoS₂ is the most widely used TMD because of its application as a solid lubricant. Scientifically, it shows superconductivity after alkali or alkaline-earth doping with a highest T _c of around 7 K. Recently, we succeeded in inducing superconductivity in the MoS₂ transistor adopting electric double layer (EDL), a nanosized capacitor, as a gate dielectric. The field-induced superconducting transition of MoS₂ was realized with a maximum T _c around 11 K, the highest not only within a reported MoS₂ compound, but also among TMDs. This highest T _c lies in the carrier density region much smaller than a chemically doped compound; a low density region has never been successfully accessed by chemical methods. Combining a HfO₂ (high-k) back gate, quasi-continuous control of carrier density, and thus quantum phase, was demonstrated to unveil the phase diagram; the T _c exhibits strong carrier density dependence with a superconducting dome. Our result implies a common existence of the superconducting dome in 2D band insulators.     

Composition-Controllable Syntheses and Property Modulations from 2D Ferromagnetic Fe5Se8 to Metallic Fe3Se4 Nanosheets

Exploring new-type 2D magnetic materials with high magnetic transition temperature and robust air stability has attracted wide attention for developing innovative spintronic devices. Recently, intercalation of native metal atoms into the van der Waals gaps of 2D layered transition metal dichalcogenides (TMDs) has been developed to form 2D non-layered magnetic TMDs, while only succeeded in limited systems (e.g., Cr₂S₃, Cr₅Te₈). Herein, composition-controllable syntheses of 2D non-layered iron selenide nanosheets (25% Fe-intercalated triclinic Fe₅Se₈ and 50% Fe-intercalated monoclinic Fe₃Se₄) are firstly reported, via a robust chemical vapor deposition strategy. Specifically, the 2D Fe₅Se₈ exhibits intrinsic room-temperature ferromagnetic property, which is explained by the change of electron spin states from layered 1T'-FeSe₂ to non-layered Fe-intercalated Fe₅Se₈ based on density functional theory calculations. In contrast, the ultrathin Fe₃Se₄ presents novel metallic features comparable with that of metallic TMDs. This work hereby sheds light on the composition-controllable synthesis and fundamental property exploration of 2D self-intercalation induced novel TMDs compounds, by propelling their application explorations in nanoelectronics and spintronics-related fields.     

Half‐Metallic Behavior in 2D Transition Metal Dichalcogenides Nanosheets by Dual‐Native‐Defects Engineering

Two‐dimensional transition metal dichalcogenides (TMDs) have been regarded as one of the best nonartificial low‐dimensional building blocks for developing spintronic nanodevices. However, the lack of spin polarization in the vicinity of the Fermi surface and local magnetic moment in pristine TMDs has greatly hampered the exploitation of magnetotransport properties. Herein, a half‐metallic structure of TMDs is successfully developed by a simple chemical defect‐engineering strategy. Dual native defects decorate titanium diselenides with the coexistence of metal‐Ti‐atom incorporation and Se‐anion defects, resulting in a high‐spin‐polarized current and local magnetic moment of 2D Ti‐based TMDs toward half‐metallic room‐temperature ferromagnetism character. Arising from spin‐polarization transport, the as‐obtained T‐TiSe_1.8 nanosheets exhibit a large negative magnetoresistance phenomenon with a value of ?40% (5T, 10 K), representing one of the highest negative magnetoresistance effects among TMDs. It is anticipated that this dual regulation strategy will be a powerful tool for optimizing the intrinsic physical properties of TMD systems.     

Controlling Nanoscale Thermal Expansion of Monolayer Transition Metal Dichalcogenides by Alloy Engineering

2D materials, such as transition metal dichalcogenides (TMDs), graphene, and boron nitride, are seen as promising materials for future high power/high frequency electronics. However, the large difference in the thermal expansion coefficient (TEC) between many of these 2D materials could impose a serious challenge for the design of monolayer‐material‐based nanodevices. To address this challenge, alloy engineering of TMDs is used to tailor their TECs. Here, in situ heating experiments in a scanning transmission electron microscope are combined with electron energy‐loss spectroscopy and first‐principles modeling of monolayer Mo_1?xW_xS₂ with different alloying concentrations to determine the TEC. Significant changes in the TEC are seen as a function of chemical composition in Mo_1?xW_xS₂, with the smallest TEC being reported for a configuration with the highest entropy. This study provides key insights into understanding the nanoscale phenomena that control TEC values of 2D materials.     

High Spin Hall Conductivity in Large-Area Type-II Dirac Semimetal PtTe2

Manipulation of magnetization by electric-current-induced spin–orbit torque (SOT) is of great importance for spintronic applications because of its merits in energy-efficient and high-speed operation. An ideal material for SOT applications should possess high charge-spin conversion efficiency and high electrical conductivity. Recently, transition metal dichalcogenides (TMDs) emerge as intriguing platforms for SOT study because of their controllability in spin–orbit coupling, conductivity, and energy band topology. Although TMDs show great potentials in SOT applications, the present study is restricted to the mechanically exfoliated samples with small sizes and relatively low conductivities. Here, a manufacturable recipe is developed to fabricate large-area thin films of PtTe₂, a type-II Dirac semimetal, to study their capability of generating SOT. Large SOT efficiency together with high conductivity results in a giant spin Hall conductivity of PtTe₂ thin films, which is the largest value among the presently reported TMDs. It is further demonstrated that the SOT from PtTe₂ layer can switch a perpendicularly magnetized CoTb layer efficiently. This work paves the way for employing PtTe₂-like TMDs for wafer-scale spintronic device applications.     

Van der Waals heterostructures based on three-dimensional topological insulators

Three-dimensional (3D) topological insulators (TIs) have generated tremendous research interest over the past decade due to their topologically-protected surface states with linear dispersion and helical spin texture. The topological surface states offer an important platform to realize topological phase transitions, topological magnetoelectric effects and topological superconductivity via 3D TI-based heterostructures. In this review, we summarize the key findings of magneto and quantum transport properties in 3D TIs and their related heterostructures with normal insulators, ferromagnets and superconductors. For intrinsic 3D TIs, the experimental evidences of the topological surface states and their coupling effects are reviewed. Whereas for 3D TI related heterostructures, we focus on some important phenomenological magnetotransport activities and provide explanations for the proximity-induced topological and quantum effects.     

Magnetic Proximity Effect in Graphene/CrBr3 van der Waals Heterostructures

2D van der Waals heterostructures serve as a promising platform to exploit various physical phenomena in a diverse range of novel spintronic device applications. Efficient spin injection is the prerequisite for these devices. The recent discovery of magnetic 2D materials leads to the possibility of fully 2D van der Waals spintronics devices by implementing spin injection through the magnetic proximity effect (MPE). Here, the investigation of MPE in 2D graphene/CrBr₃ van der Waals heterostructures is reported, which is probed by the Zeeman spin Hall effect through non-local measurements. Quantitative estimation of the Zeeman splitting field demonstrates a significant MPE field even in a low magnetic field. Furthermore, the observed anomalous longitudinal resistance changes at the Dirac point R_XX,D with increasing magnetic field near ν = 0 may be attributed to the MPE-induced new ground state phases. This MPE revealed in the graphene/CrBr₃ van der Waals heterostructures therefore provides a solid physics basis and key functionality for next-generation 2D spin logic and memory devices.     

First-Principle Investigation of Structural,Electronic and Magnetic Properties in Mn<Subscript>2</Subscript>RhZ (Z = Si,Ge, and Sn) Heusler Alloys

Mn ₂-based Heusler compounds exhibit different types of anti-site disorder. The electronic structure and magnetism of Heusler alloys Mn₂RhZ (Z = Si, Ge, and Sn) have been studied by first-principle calculations. Mn₂RhSi and Mn₂RhGe are ordinary half-metallic ferrimagnetic metals at equilibrium lattice constants, with a magnetic spin moments obeys to the Slater-Pauling rule and spin polarization of 100 % at the Fermi energy. The tetragonal phase transformation is studied for Mn₂RhSn. The total magnetic moment of Mn₂RhSn in the tetragonal structure is higher compared to the other materials, which results in a large ΔM between the saturation moments of tetragonal and a cubic. The tetragonal Mn₂RhSn predicted to a high spin polarization ratio of 93 %. These properties of these materials are particularly interesting due to their perpendicular magnetic anisotropy (PMA), which was realized in thin films opening the door for application in STT magnetic random access memories (STT-MRAMs)     

Polymorphic Spin,Charge, and Lattice Waves in Vanadium Ditelluride

Lattice distortion, spin interaction, and dimensional crossover in transition metal dichalcogenides (TMDs) have led to intriguing quantum phases such as charge density waves (CDWs) and 2D magnetism. However, the combined effect of many factors in TMDs, such as spin–orbit, electron–phonon, and electron–electron interactions, stabilizes a single quantum phase at a given temperature and pressure, which restricts original device operations with various quantum phases. Here, nontrivial polymorphic quantum states, CDW phases, are reported in vanadium ditelluride (VTe₂) at room temperature, which is unique among various CDW systems; the doping concentration determines the formation of either of the two CDW phases in VTe₂ at ambient conditions. The two CDW polymorphs show different antiferromagnetic spin orderings in which the vanadium atoms create two different stripe-patterned spin waves. First-principles calculations demonstrate that the magnetic ordering is critically coupled with the corresponding CDW in VTe₂, which suggests a rich phase diagram with polymorphic spin, charge, and lattice waves all coexisting in a solid for new conceptual quantum state-switching device applications.     

In situ microscopy techniques for characterizing the mechanical properties and deformation behavior of two-dimensional (2D) materials

Due to the atomic thickness and planar characteristics, two-dimensional (2D) materials such as graphene and transition metal dichalcogenides (TMDs) are considered to be excellent electronic materials, which endow them with great potential for future device applications. The robust and reliable application of their functional devices requires an in-depth understanding of their mechanical properties and deformation behavior, which is also of fundamental importance in nanomechanics. Considering their exceedingly small sizes and thicknesses, this is a very challenge task. In situ microscopy techniques show great superiority in this respect. This review focuses on the progress in in situ microscopy techniques (including atomic force microscopy (AFM), scanning electron microscopy (SEM), and transmission electron microscopy (TEM)) in characterizing the mechanical properties and deformation behavior of 2D materials. The technical characteristics, advantages, disadvantages, and main research fields of various in situ AFM, SEM, and TEM techniques are analyzed in detail, and the corresponding mechanical scenarios from point to plane are realized, including local indentation, planar stretching, friction sliding between atomic layers and atomic movement mechanisms. By virtue of their complementary advantages, in situ integrated microscopy techniques enable the simultaneous study of various mechanical properties, nanomechanical behavior, and inherent atomic mechanisms of 2D materials. Based on the present research, we look forward to further optimized in situ integrated microscopy techniques with high spatiotemporal atomic resolution that can reveal the dynamic structure-performance correlations and corresponding atomic mechanisms between the physical properties, such as mechanical, electrical, optical, thermal, and magnetic properties of 2D materials and their crystal structures, electronic structures, atomic layers, defect densities and other influencing factors under multifield coupling conditions. This will provide beneficial predictions and guidance for the design, construction and application of 2D material-based mechanoelectronic, piezoelectric, photoelectric, thermoelectric, etc. nanoelectronic devices.     

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.     

Reliable Piezoelectricity in Bilayer WSe2 for Piezoelectric Nanogenerators

Recently, piezoelectricity has been observed in 2D atomically thin materials, such as hexagonal‐boron nitride, graphene, and transition metal dichalcogenides (TMDs). Specifically, exfoliated monolayer MoS₂ exhibits a high piezoelectricity that is comparable to that of traditional piezoelectric materials. However, monolayer TMD materials are not regarded as suitable for actual piezoelectric devices due to their insufficient mechanical durability for sustained operation while Bernal‐stacked bilayer TMD materials lose noncentrosymmetry and consequently piezoelectricity. Here, it is shown that WSe₂ bilayers fabricated via turbostratic stacking have reliable piezoelectric properties that cannot be obtained from a mechanically exfoliated WSe₂ bilayer with Bernal stacking. Turbostratic stacking refers to the transfer of each chemical vapor deposition (CVD)‐grown WSe₂ monolayer to allow for an increase in degrees of freedom in the bilayer symmetry, leading to noncentrosymmetry in the bilayers. In contrast, CVD‐grown WSe₂ bilayers exhibit very weak piezoelectricity because of the energetics and crystallographic orientation. The flexible piezoelectric WSe₂ bilayers exhibit a prominent mechanical durability of up to 0.95% of strain as well as reliable energy harvesting performance, which is adequate to drive a small liquid crystal display without external energy sources, in contrast to monolayer WSe₂ for which the device performance becomes degraded above a strain of 0.63%.     

Strongly Surface State Carrier-Dependent Spin–Orbit Torque in Magnetic Topological Insulators

The topological surface states (TSS) in topological insulators (TIs) can exert strong spin–orbit torque (SOT) on adjacent magnetization, offering great potential in implementing energy-efficient magnetic memory devices. However, there are large discrepancies among the reported spin Hall angle values in TIs, and its temperature dependence still remains elusive. Here, the spin Hall angle in a modulation-doped Cr-Bi_xSb_2−xTe₃ (Cr-BST) film is quantitatively determined via both transport and optic approaches, where consistent results are obtained. A large spin Hall angle of ≈90 in the modulation-doped Cr-BST film is demonstrated at 2.5 K, and the spin Hall angle drastically decreases to 0.3–0.5 as the temperature increases. Moreover, by tuning the top TSS carrier concentration, a competition between the top and bottom TSS in contributing to SOT is observed. The above phenomena can account for the large discrepancies among the previously reported spin Hall angle values and reveal the unique role of TSS in generating SOT.     

Ultrahigh‐Sensitive Broadband Photodetectors Based on Dielectric Shielded MoTe2/Graphene/SnS2 p–g–n Junctions

2D atomic sheets of transition metal dichalcogenides (TMDs) have a tremendous potential for next‐generation optoelectronics since they can be stacked layer‐by‐layer to form van der Waals (vdW) heterostructures. This allows not only bypassing difficulties in heteroepitaxy of lattice‐mismatched semiconductors of desired functionalities but also providing a scheme to design new optoelectronics that can surpass the fundamental limitations on their conventional semiconductor counterparts. Herein, a novel 2D h‐BN/p‐MoTe₂/graphene/n‐SnS₂/h‐BN p–g–n junction, fabricated by a layer‐by‐layer dry transfer, demonstrates high‐sensitivity, broadband photodetection at room temperature. The combination of the MoTe₂ and SnS₂ of complementary bandgaps, and the graphene interlayer provides a unique vdW heterostructure with a vertical built‐in electric field for high‐efficiency broadband light absorption, exciton dissociation, and carrier transfer. The graphene interlayer plays a critical role in enhancing sensitivity and broadening the spectral range. An optimized device containing 5?7‐layer graphene has been achieved and shows an extraordinary responsivity exceeding 2600 A W^?1 with fast photoresponse and specific detectivity up to ≈10¹³ Jones in the ultraviolet–visible–near‐infrared spectrum. This result suggests that the vdW p–g–n junctions containing multiple photoactive TMDs can provide a viable approach toward future ultrahigh‐sensitivity and broadband photonic detectors.     

Probing Effective Out‐of‐Plane Piezoelectricity in van der Waals Layered Materials Induced by Flexoelectricity

Many van der Waals layered 2D materials, such as h‐BN, transition metal dichalcogenides (TMDs), and group‐III monochalcogenides, have been predicted to possess piezoelectric and mechanically flexible natures, which greatly motivates potential applications in piezotronic devices and nanogenerators. However, only intrinsic in‐plane piezoelectricity exists in these 2D materials and the piezoelectric effect is confined in odd‐layers of TMDs. The present work is intent on combining the free‐standing design and piezoresponse force microscopy techniques to obtain and directly quantify the effective out‐of‐plane electromechanical coupling induced by strain gradient on atomically thin MoS₂ and InSe flakes. Conspicuous piezoresponse and the measured piezoelectric coefficient with respect to the number of layers or thickness are systematically illustrated for both MoS₂ and InSe flakes. Note that the promising effective piezoelectric coefficient (d^eff₃₃) of about 21.9 pm V^?1 is observed on few‐layered InSe. The out‐of‐plane piezoresponse arises from the net dipole moment along the normal direction of the curvature membrane induced by strain gradient. This work not only provides a feasible and flexible method to acquire and quantify the out‐of‐plane electromechanical coupling on van der Waals layered materials, but also paves the way to understand and tune the flexoelectric effect of 2D systems.     

Graphene‐Assisted Antioxidation of Tungsten Disulfide Monolayers: Substrate and Electric‐Field Effect

Transition metal dichalcogenides (TMDs) have emerged as promising materials to complement graphene for advanced optoelectronics. However, irreversible degradation of chemical vapor deposition‐grown monolayer TMDs via oxidation under ambient conditions limits applications of TMD‐based devices. Here, the growth of oxidation‐resistant tungsten disulfide (WS₂) monolayers on graphene is demonstrated, and the mechanism of oxidation of WS₂ on SiO₂, graphene/SiO₂, and on graphene suspended in air is elucidated. While WS₂ on a SiO₂ substrate begins oxidation within weeks, epitaxially grown WS₂ on suspended graphene does not show any sign of oxidation, attributed to the screening effect of surface electric field caused by the substrate. The control of a local oxidation of WS₂ on a SiO₂ substrate by a local electric field created using an atomic force microscope tip is also demonstrated.     

Strain effects on thermoelectric properties of two-dimensional materials

Two-dimensional (2D) materials, such as graphene, hexagonal boron nitride (hBN), phosphorene, transition metal dichalcogenides (e.g., MoS₂, WS₂, etc.), metal oxides (e.g., MoO₃) have attracted much attention recently due to their extraordinary structural, mechanical and physical properties. In particular, 2D materials have shown great potential for thermal management and thermoelectric energy generation due to their fascinating electrical and thermal transport properties, which can lead to a significantly large figure-of-merit. Also due to their large stretchability, 2D materials are promising for using strain engineering to tune and modulate their electronic and thermal properties, which can further enhance their figure-of-merit. In this article, we give a review on the recent advances in the study of strain-engineering on the thermoelectric properties of 2D materials. We first review some important aspects in thermoelectric effects, such as Peltier effect, Seebeck effect, the coefficient of performance and figure-of-merit (ZT) and discuss why 2D materials are ideal candidates for thermal management and thermoelectric applications. We then briefly discuss the strain (stress) generation in 2D materials and their structure integrity under strain (stress). Next, we discuss how strain affects the electronic properties of 2D materials, followed by the discussion on the effects of strain on the thermal properties of 2D materials. Subsequently, we discuss the strain effects on two important thermoelectric properties, Seebeck coefficient and figure-of-merit ZT. Finally, we present our conclusions and future perspective.     

Lateral Monolayer MoSe2–WSe2 p–n Heterojunctions with Giant Built‐In Potentials

2D transition metal dichalcogenides (TMDs) have exhibited strong application potentials in new emerging electronics because of their atomic thin structure and excellent flexibility, which is out of field of tradition silicon technology. Similar to 3D p–n junctions, 2D p–n heterojunctions by laterally connecting TMDs with different majority charge carriers (electrons and holes), provide ideal platform for current rectifiers, light‐emitting diodes, diode lasers and photovoltaic devices. Here, growth and electrical studies of atomic thin high‐quality p–n heterojunctions between molybdenum diselenide (MoSe₂) and tungsten diselenide (WSe₂) by one‐step chemical vapor deposition method are reported. These p–n heterojunctions exhibit high built‐in potential (≈0.7 eV), resulting in large current rectification ratio without any gate control for diodes, and fast response time (≈6 ms) for self‐powered photodetectors. The simple one‐step growth and electrical studies of monolayer lateral heterojunctions open up the possibility to use TMD heterojunctions for functional devices.