Fabrication and applications of van der Waals heterostructures

Van der Waals heterostructures(vdWHs) are showing considerable potential in both fundamental exploration and practical applications. Built upon the synthetic successes of(two-dimensional) 2D materials, several synthetic strategies of vdWHs have been developed,allowing the convenient fabrication of diverse vdWHs with decent controllability, quality, and scalability. This review first summarizes the current state of the art in synthetic strategies of vdWHs, including physical combination, deposition, solvothermal synthesis, and synchronous evolution. Then three major applications and their representative vdWH devices have been reviewed, including electronics(tunneling field effect transistors and 2D contact),optoelectronics(photodetector), and energy conversion(electrocatalysts and metal ion batteries), to unveil the potentials of vdWHs in practical applications and provide the general design principles of functional vdWHs for different applications. Besides, moiré superlattices based on vdWHs are discussed to showcase the importance of vdWHs as a platform for novel condensed matter physics. Finally, the crucial challenges towards ideal vdWHs with high performance are discussed, and the outlook for future development is presented. By the systematical integration of synthetic strategies and applications, we hope this review can further light up the rational designs of vdWHs for emerging applications.

Introducing Spin Polarization into Mixed-Dimensional Van der Waals Heterostructures for High-Efficiency Visible-Light Photocatalysis

The low separation efficiency of the photogenerated carrier and the poor activity of the surface redox reaction are the main barrier to further improvement of photocatalytic materials.To address these issues,introducing spin-polarized electrons in single-component photocatalytic materials emerged as a promising approach.However,the decreased redox ability of photocarriers in these materials becomes a new challenge.Herein,we mitigate this challenge with a carbon nitride sheet(CNs)/graphene nanoribbon(GNR)composite material that has a van der Waals heterostructures(vdWHs)and spin-polarized electron properties.Experimental results and theoretical calculations show that the heterostructure has a strong redox ability,high carrier-separation efficiency,and enhanced surface catalytic reaction.Consequently,the mixed-dimensional CNs/GNR vdWHs exhibit remarkable performance for H_(2)and O_(2)generation as well as CO_(2)production under visible-light irradiation without any cocatalyst.The spin-polarized vdWHs discovered in this study revealed a new type of photocatalytic materials and advanced the development of spintronics and photocatalysis.

InSe-Te van der Waals heterostructures for current rectification and photodetection

As the basis of modern electronics and optoelectronics,high-performance,multi-functional p-n junctions have manifested and occupied an important position.However,the performance of the silicon-based p-n junctions declines gradually as the thickness approaches to few nanometers.The heterojunction constructed by two-dimensional(2D)materials can significantly improve the device performance compared with traditional technologies.Here,we report the In Se-Te type-II van der Waals heterostructures with rectification ratio up to 1.56×10^(7) at drain-source voltage of±2 V.The p-n junction exhibits a photovoltaic and photoelectric effect under different laser wavelengths and densities and has high photoresponsivity and detectivity under low irradiated light power.Moreover,the heterojunction has stable photo/dark current states and good photoelectric switching characteristics.Such high-performance heterostructured device based on 2D materials provides a new way for futural electronic and optoelectronic devices.

Two Step Chemical Vapor Deposition of In2Se3/MoSe2 van der Waals Heterostructures

Two-dimensional transition metal dichalcogenides heterostructures have stimulated wide in- terest not only for the fundamental research, but also for the application of next generation electronic and optoelectronic devices. Herein, we report a successful two-step chemical vapor deposition strategy to construct vertically stacked van der Waals epitaxial In2Se3/MoSe2 heterostructures. Transmission electron microscopy characterization reveals clearly that the In2Se3 has well-aligned lattice orientation with the substrate of monolayer MoSe2. Due to the interaction between the In2Se3 and MoSe2 layers, the heterostructure shows the quench- ing and red-shift of photoluminescence. Moreover, the current rectification behavior and photovoltaic effect can be observed from the heterostructure, which is attributed to the unique band structure alignment of the heterostructure, and is further confirmed by Kevin probe force microscopy measurement. The synthesis approach via van der Waals epitaxy in this work can expand the way to fabricate a variety of two-dimensional heterostructures for potential applications in electronic and optoelectronic devices.

Observation of magnetoresistance in CrI_(3)/graphene van der Waals heterostructures

Two-dimensional ferromagnetic van der Waals(2D vdW)heterostructures have opened new avenues for creating artificial materials with unprecedented electrical and optical functions beyond the reach of isolated 2D atomic layered materials,and for manipulating spin degree of freedom at the limit of few atomic layers,which empower next-generation spintronic and memory devices.However,to date,the electronic properties of 2D ferromagnetic heterostructures still remain elusive.Here,we report an unambiguous magnetoresistance behavior in CrI_(3)/graphene heterostructures,with a maximum magnetoresistance ratio of 2.8%.The magnetoresistance increases with increasing magnetic field,which leads to decreasing carrier densities through Lorentz force,and decreases with the increase of the bias voltage.This work highlights the feasibilities of applying two-dimensional ferromagnetic vdW heterostructures in spintronic and memory devices.

Excitonic devices based on two-dimensional transition metal dichalcogenides van der Waals heterostructures

Excitonic devices are an emerging class of technology that utilizes excitons as carriers for encoding, transmitting, and storing information. Van der Waals heterostructures based on transition metal dichalcogenides often exhibit a type II band alignment, which facilitates the generation of interlayer excitons. As a bonded pair of electrons and holes in the separation layer, interlayer excitons offer the chance to investigate exciton transport due to their intrinsic out-of-plane dipole moment and extended exciton lifetime. Furthermore, interlayer excitons can potentially analyze other encoding strategies for information processing beyond the conventional utilization of spin and charge. The review provided valuable insights and recommendations for researchers studying interlayer excitonic devices within van der Waals heterostructures based on transition metal dichalcogenides. Firstly, we provide an overview of the essential attributes of transition metal dichalcogenide materials, focusing on their fundamental properties, excitonic effects, and the distinctive features exhibited by interlayer excitons in van der Waals heterostructures. Subsequently, this discourse emphasizes the recent advancements in interlayer excitonic devices founded on van der Waals heterostructures, with specific attention is given to the utilization of valley electronics for information processing, employing the valley index. In conclusion, this paper examines the potential and current challenges associated with excitonic devices.

Flower-like CuS/γ-Fe_(2)O_(3) van der Waals heterostructures with highefficient electromagnetic wave absorption

The escalating electromagnetic(EM)pollution issues and the demand to elevate military stealth technology make it imperative to develop cost-effective and high-performance electromagnetic wave(EMW)absorbing materials.In this paper,the flower-like CuS/γ-Fe_(2)O_(3) van der Waals(vdW)heterostructures have been synthesized via a facile two-step solvothermal approach.The flower-like CuS skeleton increases the attenuation path of EMW while reducing the material density.Different contents ofγ-Fe_(2)O_(3) nanoparticles anchor between the flower-like CuS nanosheets to constitute a heterogeneous structure,which enables dielectric and magnetic loss synergistically to optimize impedance matching and remarkably improve the EMW absorption performance.The minimum reflection loss(RLmin)is-49.36 dB with a thickness of only 1.6 mm and the effective absorption bandwidth(EAB)reaches 4.64 GHz(13.36–18 GHz).By adjusting the thickness of the absorber,the EAB can cover 96%of the GHz band.Notably,the superior absorption of-61.53 dB at middle frequency band can be obtained by adjusting the amount of Fe_(2)O_(3) addition.In this study,the adjustment of EM parameters and the optimization of impedance matching have been achieved by constructing a novel vdW heterogeneous structure,which provides fresh ideas and references for the design of high-performance EMW absorbing materials.

Twistronics and moiréexcitonic physics in van der Waals heterostructures

Heterostructures composed of two-dimensional van der Waals(vdW)materials allow highly controllable stacking,where interlayer twist angles introduce a continuous degree of freedom to alter the electronic band structures and excitonic physics.Motivated by the discovery of Mott insulating states and superconductivity in magic-angle bilayer graphene,the emerging research fields of“twistronics”and moiréphysics have aroused great academic interests in the engineering of optoelectronic properties and the exploration of new quantum phenomena,in which moirésuperlattice provides a pathway for the realization of artificial excitonic crystals.Here we systematically summarize the current achievements in twistronics and moiréexcitonic physics,with emphasis on the roles of lattice rotational mismatches and atomic registries.Firstly,we review the effects of the interlayer twist on electronic and photonic physics,particularly on exciton properties such as dipole moment and spin-valley polarization,through interlayer interactions and electronic band structures.We also discuss the exciton dynamics in vdW heterostructures with different twist angles,like formation,transport and relaxation processes,whose mechanisms are complicated and still need further investigations.Subsequently,we review the theoretical analysis and experimental observations of moirésuperlattice and moirémodulated excitons.Various exotic moiréeffects are also shown,including periodic potential,moiréminiband,and varying wave function symmetry,which result in exciton localization,emergent exciton peaks and spatially alternating optical selection rule.We further introduce the expanded properties of moirésystems with external modulation factors such as electric field,doping and strain,showing that moirélattice is a promising platform with high tunability for optoelectronic applications and in-depth study on frontier physics.Lastly,we focus on the rapidly developing field of correlated electron physics based on the moirésystem,which is potentially related to the emerging quantum phenomena.

Two-dimensional capillaries assembled by van der Waals heterostructures

Research on two-dimensional materials in the past decades has brought many insights of low-dimensional science on a wide range of related topics.As a novel two-dimensional structure,the atomic-scale capillaries which can conceptually be seen as the empty space left by removing few layers of two-dimensional materials from their bulk van der Waals crystals offer a unique platform of investigating physical and chemical processes of ions,molecules,and atoms under two-dimensional confinements.Investigation of many important problems,such as capillary condensation and water network structure that are difficult to be explored experimentally in other confinement structures,has now been accessible;two-dimensional migration of ions,water,and gases shows abnormal transport properties beyond conventional theory prediction;influence of quantum effect to molecule permeation is observable even at room temperature.All these discoveries greatly extend our fundamental understandings of nano-science,and stimulate the development of potential applications.We review the fabrication of these two-dimensional capillaries which are created by the assembly of van der Waals heterostructures,and discuss the ultimate steric effects in the smallest possible confinements.Exotic interactions between capillary interior and confined particles are also summarized.When coupled with external stimuli,these channels exhibit tunable mass transport behaviors,which not only gives feedback to the mechanism understanding but in turn guides the channel structure optimization.

Two dimensional GeO_(2)/MoSi_(2)N_(4)van der Waals heterostructures with robust type-Ⅱ band alignment

Constructing two-dimensional(2D)van der Waals heterostructures(vdWHs)can expand the electronic and optoelectronic applications of 2D semiconductors.However,the work on the 2D vdWHs with robust band alignment is still scarce.Here,we employ a global structure search approach to construct the vdWHs with monolayer MoSi_(2)N_(4)and widebandgap GeO_(2).The studies show that the GeO_(2)/MoSi_(2)N_(4)vdWHs have the characteristics of direct structures with the band gap of 0.946 eV and typeII band alignment with GeO_(2)and MoSi_(2)N_(4)layers as the conduction band minimum(CBM)and valence band maximum(VBM),respectively.Also,the direct-to-indirect band gap transition can be achieved by applying biaxial strain.In particular,the 2D GeO_(2)/MoSi_(2)N_(4)vdWHs show a robust type-II band alignment under the effects of biaxial strain,interlayer distance and external electric field.The results provide a route to realize the robust type-II band alignment vdWHs,which is helpful for the implementation of optoelectronic nanodevices with stable characteristics.

Rational design of vitamin C/defective carbon van der Waals heterostructure for enhanced activity,durability and storage stability toward oxygen reduction reaction

Metal-free defective carbon materials with abundant active sites have been widely studied as low-cost and efficient oxygen reduction reaction(ORR)electrocatalysts in metal-air batteries.However,the active sites in defective carbon are easily subjected to serious oxidation or hydroxylation during ORR or storage,leading to rapid degradation of activity.Herein,we design a van der Waals heterostructure comprised of vitamin C(VC)and defective carbon(DC)to not only boost the activity but also enhance the durability and storage stability of the DC-VC electrocatalyst.The formation of VC van der Waals between DC and VC is demonstrated to be an effective strategy to protect the defect active sites from oxidation and hydroxylation degradation,thus significantly enhancing the electrochemical durability and storage anti-aging performance.Moreover,the DC-VC van der Waals can reduce the reaction energy barrier to facilitate the ORR.These findings are also confirmed by operando Fourier transform infrared spectroscopy and density functional theory calculations.It is necessary to mention that the preparation of this DC-VC electrocatalyst can be scaled up,and the ORR performance of the largely produced electrocatalyst is demonstrated to be very consistent.Furthermore,the DC-VC-based aluminum-air batteries display very competitive power density with good performance maintenance.

Valley-polarized quantum anomalous Hall effect in van der Waals heterostructures based on monolayer jacutingaite family materials

We numerically study the general valley polarization and anomalous Hall effect in van der Waals(vdW)heterostructures based on monolayer jacutingaite family materials Pt2AX3(A=Hg,Cd,Zn;X=S,Se,Te).We perform a systematic study on the atomic,electronic,and topological properties of vdW heterostructures composed of monolayer Pt2AX3 and two-dimensional ferromagnetic insulators.We show that four kinds of vdW heterostructures exhibit valley-polarized quantum anomalous Hall phase,i.e.,Pt_(2)HgS_(3)/NiBr_(2),Pt_(2)HgSe_(3)/CoBr_(2),Pt_(2)HgSe_(3)/NiBr_(2),and Pt_(2)ZnS_(3)/CoBr_(2),with a maximum valley splitting of 134.2 meV in Pt_(2)HgSe_(3)/NiBr_(2) and sizable global band gap of 58.8 meV in Pt_(2)HgS_(3)/NiBr_(2).Our findings demonstrate an ideal platform to implement applications on topological valleytronics.

Gate-tunable spin valve effect in Fe_(3)GeTe_(2)-based van der Waals heterostructures

Magnetic tunnel junctions(MTJs),a prominent type of spintronic device based on the spin valve effect,have facilitated the development of numerous spintronic applications.The technical appeal for the next-generation MTJ devices has been proposed in two directions:improving device performance by utilizing advanced two-dimensional(2D)ferromagnetic materials or extending device functionalities by exploring the gate-tunable magnetic properties of ferromagnets.Based on the recent development of 2D magnets with the ease of external stimuli,such as electric field,due to their reduced dimensions,reliable prospects for gate-tunable MTJ devices can be achieved,shedding light on the great potential of next-generation MTJs with multiple functionalities for various application environments.While the electrical gate-tunable MTJ device is highly desirable for practical spintronic devices,it has not yet been demonstrated.Here,we demonstrate the experimental realization of a spin valve device by combining a vertical Fe_(3)GeTe_(2)/h-BN/Fe_(3)GeTe_(2) MTJ with an electrolyte gate.The magnetoresistance ratio(MR ratio)of 36%for the intrinsic MTJ confirms the good performance of the device.By electrolyte gating,the tunneling MR ratio of Fe_(3)GeTe_(2)/h-BN/Fe_(3)GeTe_(2) MTJ can be elevated 2.5 times,from 26%to 65%.Importantly,the magnetic fields at which the magnetoresistance switches for the MTJ can be modulated by electrical gating,providing a promising method to control the magnetization configuration of the MTJ.Our work demonstrates a gate-tunable MTJ device toward the possibility for gate-controlled spintronic devices,paving the way for performing 2D magnetism manipulations and exploring innovative spintronic applications.

Wafer-scale vertical van der Waals heterostructures

Wafer-scale van der Waals heterostructures(vdWHs),benefitting from the rich diversity in materials available and stacking geometry,precise controllability in devices structure and performance,and unprecedented potential in practical application,have attracted considerable attention in the field of twodimensional(2D)materials.This article reviews the state-of-the-art research activities that focus on wafer-scale vdWHs and their(opto)electronic applications.We begin with the preparation strategies of vdWHs with wafer size and illustrate them from four key aspects,that is,mechanical-assembly stack,successive deposition,synchronous evolution,and seeded growth.We discuss the fundamental principle,underlying mechanism,advantages,and disadvantages for each strategy.We will then review the applications of large-area vdWHs based devices in electronic,optoelectronic and flexible devices field,unveiling their promising potential for practical application.Ultimately,we will demonstrate the challenges they face and provide some viable solutions on waferscale heterostructure synthesis and device fabrication.

Interlayer coupling effect in van der Waals heterostructures of transition metal dichalcogenides

Van der Waals(vdW)heterobilayers formed by two-dimensional(2D)transition metal dichalcogenides(TMDCs)created a promising platform for various electronic and optical properties,ab initio band results indicate that the band offset of type-Ⅱband alignment in TMDCs vdW heterobilayer could be tuned by introducing Janus WSSe monolayer,instead of an external electric field.On the basis of symmetry analysis,the allowed interlayer hopping channels of TMDCs vdW heterobilayer were determined,and a four-level k·p model was developed to obtain the interlayer hopping.Results indicate that the interlayer coupling strength could be tuned by interlayer electric polarization featured by various band offsets.Moreover,the difference in the formation mechanism of interlayer valley excitons in different TMDCs vdW heterobilayers with various interlayer hopping strength was also clarified.

Quantum tunneling in two-dimensional van der Waals heterostructures and devices

Quantum tunneling with band-structure engineering has been feasibly developed for many applications in electrical,optoelectrical,and magnetic devices.It relies on layer-by-layer design and fabrication,which is an interdisciplinary research field covering material science and technology.Ever since the discovery of two-dimensional(2 D)layered materials,tunneling devices based on 2D van der Waals(vd W)heterostructures have been extensively studied as potential next-generation devices.2 D materials are thin at the atomic scale and extremely flat without surface dangling bonds.Because of these unique characteristics,2 D vd W heterostructures offer superior tunneling performance that reaches the benchmark of traditional Si technology and possess additional ability to scale down device size.Here,we comprehensively review quantum tunneling in 2 D vd W heterostructures,in addition to their unique mechanisms and applications.Moreover,we analyze the possibilities and challenges currently faced by 2 D tunneling devices and provide a perspective on their exploitation for advanced future applications.The investigation of technology-and performancecontrol of 2 D tunneling devices is at their beginning stages;however,these devices should emerge as competitive candidates for realizing low-power supply,fast-speed capability,and high-frequency operating devices.

Enabling novel device functions with black phosphorus/MoS2 van der Waals heterostructures

Van der Waals heterostructure, which consists of various two- dimensional （2D） layered materials stacked along the direction perpendicular to their 2D plane, has emerged as a promising material system for device applications in recent years .

Bidirectional Light-Driven Ion Transport through Porphyrin Metal–Organic Framework-Based van der Waals Heterostructures via pH-Induced Band Alignment Inversion

Heterogeneous two-dimensional layered membranes reconstructed fromnatural or synthetic van derWaals materials enable novel ion transport mechanisms by coupling with the chemical and optoelectronic properties of the layered constituents.Here,we report a light-driven and pH-dependent bidirectional ion transport phenomenon through porphyrin metal–organic framework(PMOF)and transition metal dichalcogenides-based multilayer van der Waals heterostructures with sub-nanometer ionic channels.

Performance optimization of thermionic refrigerators based on van der Waals heterostructures

In this paper, an irreversible thermionic refrigerator model based on van der Waals heterostructure with various irreversibilities is established by utilizing combination of non-equilibrium thermodynamics and finite time thermodynamics. The basic performance characteristics of the refrigerator are obtained. The effects of key factors, such as bias voltages, Schottky barrier heights and heat leakages, on the performance are studied. Results show that cooling rates and coefficients of performances(COPs) can attain the double maximum with proper modulation of barrier heights and bias voltages. Increasing cross-plane thermal resistance as well as decreasing electrode-reservoir thermal resistance and reservoir-reservoir thermal resistance can enhance the performance of the device. The optimal performance region is the interval between the maximum cooling rate point and the maximum COP point. By modulating the bias voltage, the working state of the device can fall into the optimal performance region. The optimal performance of the refrigerator when using single layer graphene and a few layers graphene as electrode material is also compared.

Effects of interlayer coupling on the excitons and electronic structures of WS_(2)/hBN/MoS_(2) van der Waals heterostructures

Inserting hexagonal boron nitride(hBN)as barrier layers into bilayer transition metal dichalcogenides heterointerface has been proved an efficient method to improve two dimensional tunneling optoelectronic device performance.Nevertheless,the physical picture of interlayer coupling effect during incorporation of monolayer(1L-)hBN is not explicit yet.In this article,spectroscopic ellipsometry was used to experimentally obtain the broadband excitonic and critical point properties of WS_(2)/MoS_(2)and WS_(2)/hBN/MoS_(2)van der Waals heterostructures.We find that 1L-hBN can only slightly block the interlayer electron transfer from WS_(2)layer to MoS_(2)layer.Moreover,insertion of 1L-hBN weakens the interlayer coupling effect by releasing quantum confinement and reducing efficient dielectric screening.Consequently,the exciton binding energies in WS_(2)/hBN/MoS_(2)heterostructures blueshift comparing to those in WS_(2)/MoS_(2)heterostructures.In this exciton binding energies tuning process,the reducing dielectric screening effect plays a leading role.In the meantime,the quasi-particle(QP)bandgap remains unchanged before and after 1L-hBN insertion,which is attributed to released quantum confinement and decreased dielectric screening effects canceling each other.Unchanged QP bandgap as along with blueshift exciton binding energies lead to the redshift exciton transition energies in WS_(2)/hBN/MoS_(2)heterostructures.