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.     

3D Mesoporous van der Waals Heterostructures for Trifunctional Energy Electrocatalysis

The emergence of van der Waals (vdW) heterostructures of 2D materials has opened new avenues for fundamental scientific research and technological applications. However, the current concepts and strategies of material engineering lack feasibilities to comprehensively regulate the as‐obtained extrinsic physicochemical characters together with intrinsic properties and activities for optimal performances. A 3D mesoporous vdW heterostructure of graphene and nitrogen‐doped MoS₂ via a two‐step sequential chemical vapor deposition method is constructed. Such strategy is demonstrated to offer an all‐round engineering of 2D materials including the morphology, edge, defect, interface, and electronic structure, thereby leading to robustly modified properties and greatly enhanced electrochemical activities. The hydrogen evolution is substantially accelerated on MoS₂, while the oxygen reduction and evolution are significantly improved on graphene. This work provides a powerful overall engineering strategy of 2D materials for electrocatalysis, which is also enlightening for other nanomaterials and energy‐related applications.     

Recent Advances of Porous Graphene: Synthesis,Functionalization, and Electrochemical Applications

Graphene is a 2D sheet of sp² bonded carbon atoms and tends to aggregate together, due to the strong π–π stacking and van der Waals attraction between different layers. Its unique properties such as a high specific surface area and a fast mass transport rate are severely blocked. To address these issues, various kinds of 2D holey graphene and 3D porous graphene are either self‐assembled from graphene layers or fabricated using graphene related materials such as graphene oxide and reduced graphene oxide. Porous graphene not only possesses unique pore structures, but also introduces abundant exposed edges and accelerates mass transfer. The properties and applications of these porous graphenes and their composites/hybrids have been extensively studied in recent years. Herein, recent progress and achievements in synthesis and functionalization of various 2D holey graphene and 3D porous graphene are reviewed. Of special interest, electrochemical applications of porous graphene and its hybrids in the fields of electrochemical sensing, electrocatalysis, and electrochemical energy storage, are highlighted. As the closing remarks, the challenges and opportunities for the future research of porous graphene and its composites are discussed and outlined.     

Graphene‐Based Mixed‐Dimensional van der Waals Heterostructures for Advanced Optoelectronics

Although the library of 2D atomic crystals has greatly expanded over the past years, research into graphene is still one of the focuses for both academia and business communities. Due to its unique electronic structure, graphene offers a powerful platform for exploration of novel 2D physics, and has significantly impacted a wide range of fields including energy, electronics, and photonics. Moreover, the versatility of combining graphene with other functional components provides a powerful strategy to design artificial van der Waals (vdWs) heterostructures. Aside from the stacked 2D–2D vdWs heterostructure, in a broad sense graphene can hybridize with other non‐2D materials through vdWs interactions. Such mixed‐dimensional vdWs (MDWs) structures allow considerable freedom in material selection and help to harness the synergistic advantage of different dimensionalities, which may compensate for graphene's intrinsic shortcomings. A succinct overview of representative advances in graphene‐based MDWs heterostructures is presented, ranging from assembly strategies to applications in optoelectronics. The scientific merit and application advantages of these hybrid structures are particularly emphasized. Moreover, considering possible breakthroughs in new physics and application potential on an industrial scale, the challenges and future prospects in this active research field are highlighted.     

Structure and electronic transport in graphene wrinkles

Wrinkling is a ubiquitous phenomenon in two-dimensional membranes. In particular, in the large-scale growth of graphene on metallic substrates, high densities of wrinkles are commonly observed. Despite their prevalence and potential impact on large-scale graphene electronics, relatively little is known about their structural morphology and electronic properties. Surveying the graphene landscape using atomic force microscopy, we found that wrinkles reach a certain maximum height before folding over. Calculations of the energetics explain the morphological transition and indicate that the tall ripples are collapsed into narrow standing wrinkles by van der Waals forces, analogous to large-diameter nanotubes. Quantum transport calculations show that conductance through these "collapsed wrinkle" structures is limited mainly by a density-of-states bottleneck and by interlayer tunneling across the collapsed bilayer region. Also through systematic measurements across large numbers of devices with wide "folded wrinkles", we find a distinct anisotropy in their electrical resistivity, consistent with our transport simulations. These results highlight the coupling between morphology and electronic properties, which has important practical implications for large-scale high-speed graphene electronics.     

Dirac Semimetal Heterostructures: 3D Cd3As2 on 2D Graphene

Dirac semimetal is an emerging class of quantum matters, ranging from 2D category, such as, graphene and surface states of topological insulator to 3D category, for instance, Cd₃As₂ and Na₃Bi. As 3D Dirac semimetals typically possess Fermi‐arc surface states, the 2D–3D Dirac van der Waals heterostructures should be promising for future electronics. Here, graphene–Cd₃As₂ heterostructures are fabricated through direct layer‐by‐layer stacking. The electronic coupling results in a notable interlayer charge transfer, which enables us to modulate the Fermi level of graphene through Cd₃As₂. A planar graphene p–n–p junction is achieved by selective modification, which demonstrates quantized conductance plateaus. Moreover, compared with the bare graphene device, the graphene–Cd₃As₂ hybrid device presents large nonlocal signals near the Dirac point due to the charge transfer from the spin‐polarized surface states in the adjacent Cd₃As₂. The results enrich the family of van der Waals heterostructure and should inspire more studies on the application of Dirac/Weyl semimetals in spintronics.     

Fatigue Behavior of Polymer Encapsulated Graphene to Mitigate Interfacial Fatigue Damage

In applications such as flexible electronic devices, graphene, and other 2D materials are frequently in contact with stretchable polymeric substrates. The interface between 2D materials and polymers is dominated by weak van der Waals forces and can eventually degrade due to the frequent dynamic mechanical loads that these devices experience. This can lead to significant local delamination and shear fracture of the 2D materials. Using the polydimethylsiloxane (PDMS) encapsulation method, it is shown that the damage in graphene is significantly mitigated when it is capped during dynamic loading. To track the spread of damage in both encapsulated and nonencapsulated graphene, in situ, cyclic loading is performed. The fundamental process driving this substantial reduction in damage propagation in the 2D lattice is explained by the conventional shear lag model. It is also observed that softer PDMS substrate and capping layer completely mitigate the fatigue damage in graphene for 100 cycles at 10% applied fatigue strain.     

Conductivity Maximum in 3D Graphene Foams

In conventional foams, electrical properties often play a secondary role. However, this scenario becomes different for 3D graphene foams (GrFs). In fact, one of the motivations for synthesizing 3D GrFs is to inherit the remarkable electrical properties of individual graphene sheets. Despite immense experimental efforts to study and improve the electrical properties of 3D GrFs, lack of theoretical studies and understanding limits further progress. The causes to this embarrassing situation are identified as the multiple freedoms introduced by graphene sheets and multiscale nature of this problem. In this article, combined with transport modeling and coarse‐grained molecular dynamic (MD) simulations, a theoretical framework is established to systematically study the electrical conducting properties of 3D GrFs with or without deformation. In particular, through large‐scale and massive calculations, a general relation between contact area and conductance for two van der Waals bonded graphene sheets is demonstrated, in terms of which the conductivity maximum phenomenon in GrFs is first theoretically proposed and its competition mechanism is explained. Moreover, the theoretical prediction is consistent with previous experimental observations.     

Nanoscale vibration characterization of multi-layered graphene sheets embedded in an elastic medium

Detailed studies on the nanoscale vibration characteristics of multi-layered graphene sheets (MLGSs) that are embedded in an elastic medium are carried out using continuum-based modelling and Generalized Differential Quadrature (GDQ) method. Natural frequencies and their associated vibration modes of practical interest of single-layered and triple-layered graphene sheets, as well as general MLGSs that are embedded in an elastic medium are established. Numerical simulations are conducted to examine the effects of van der Waals (vdW) interactions, which are present as bonding forces between the layers, on nanoscale vibration natural frequencies and their mode shapes. The results show that for a general MLGSs embedded in an elastic medium, vibration modes can in general be classified into three families - lower classical synchronized modes which are independent of van der Waals forces and are somewhat sensitive to the surrounding elastic medium, middle van der Waals enhanced modes which are largely determined by the presence of van der Waals interactions and are hence less sensitive to the changes of the surrounding elastic medium, and higher mixed modes which are combinations of classical synchronized modes and van der Waals enhanced modes. Detailed characterizations of these modes from their derived mode shapes have been achieved for the typical case of an embedded triple-layered GSs, as well as general embedded MLGSs. Effects of Winkler modulus K_W, the shear layer modulus G_b, different boundary conditions, aspect ratio β and the number L of graphene layers on nanoscale vibration properties have been examined in detail. The results presented in this paper, for the first time, provide accurate and wholesome studies and characterizations on the interesting nanoscale vibration properties of multi-layered graphene sheets embedded in an elastic medium and the results obtained will certainly be useful to those who are concerned with the dynamics of embedded graphene sheets which are increasingly being deployed for various innovative engineering applications such as nano-electro-mechanical systems (NEMS).     

Anisotropic Magneto‐Coulomb Properties of 2D–0D Heterostructure Single Electron Device

Fabrication and spintronics properties of 2D–0D heterostructures are reported. Devices based on graphene (“Gr”)–aluminium nanoclusters heterostructures show robust and reproducible single‐electron transport features, in addition to spin‐dependent functionality when using a top magnetic electrode. The magnetic orientation of this single ferromagnetic electrode enables the modulation of the environmental charge experienced by the aluminium nanoclusters. This anisotropic magneto‐Coulomb effect, originating from spin–orbit coupling within the ferromagnetic electrode, provides tunable spin valve‐like magnetoresistance signatures without the requirement of spin coherent charge tunneling. These results extend the capability of Gr to act both as electrode and as a platform for the growth of 2D–0D mixed‐dimensional van der Waals heterostructures, providing magnetic functionalities in the Coulomb blockade regime on scalable spintronic devices. These heterostructures pave the way towards novel device architectures at the crossroads of 2D material physics and spin electronics.     

Harnessing Three Dimensional Anatomy of Graphene Foam to Induce Superior Damping in Hierarchical Polyimide Nanostructures

Graphene foam‐based hierarchical polyimide composites with nanoengineered interface are fabricated in this study. Damping behavior of graphene foam is probed for the first time. Multiscale mechanisms contribute to highly impressive damping in graphene foam. Rippling, spring‐like interlayer van der Waals interactions and flexing of graphene foam branches are believed to be responsible for damping at the intrinsic, interlayer and anatomical scales, respectively. Merely 1.5 wt% graphene foam addition to the polyimide matrix leads to as high as ≈300% improvement in loss tangent. Graphene nanoplatelets are employed to improve polymer–foam interfacial adhesion by arresting polymer shrinkage during imidization and π–π interactions between nanoplatelets and foam walls. As a result, damping behavior is further improved due to effective stress transfer from the polymer matrix to the foam. Thermo‐oxidative stability of these nanocomposites is investigated by exposing the specimens to glass transition temperature of the polyimide (≈400 °C). The composites are found to retain their damping characteristics even after being subjected to such extreme temperature, attesting their suitability in high temperature structural applications. Their unique hierarchical nanostructure provides colossal opportunity to engineer and program material properties.     

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

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

Optically Unraveling the Edge Chirality‐Dependent Band Structure and Plasmon Damping in Graphene Edges

The nontrivial topological origin and pseudospinorial character of electron wavefunctions make edge states possess unusual electronic properties. Twenty years ago, the tight‐binding model calculation predicted that zigzag termination of 2D sheets of carbon atoms have peculiar edge states, which show potential application in spintronics and modern information technologies. Although scanning probe microscopy is employed to capture this phenomenon, the experimental demonstration of its optical response remains challenging. Here, the propagating graphene plasmon provides an edge‐selective polaritonic probe to directly detect and control the electronic edge state at ambient condition. Compared with armchair, the edge‐band structure in the bandgap gives rise to additional optical absorption and strongly absorbed rim at zigzag edge. Furthermore, the optical conductivity is reconstructed and the anisotropic plasmon damping in graphene systems is revealed. The reported approach paves the way for detecting edge‐specific phenomena in other van der Waals materials and topological insulators.     

High Detectivity and Transparent Few‐Layer MoS2/Glassy‐Graphene Heterostructure Photodetectors

Layered van der Waals heterostructures have attracted considerable attention recently, due to their unique properties both inherited from individual two‐dimensional (2D) components and imparted from their interactions. Here, a novel few‐layer MoS₂/glassy‐graphene heterostructure, synthesized by a layer‐by‐layer transfer technique, and its application as transparent photodetectors are reported for the first time. Instead of a traditional Schottky junction, coherent ohmic contact is formed at the interface between the MoS₂ and the glassy‐graphene nanosheets. The device exhibits pronounced wavelength selectivity as illuminated by monochromatic lights. A responsivity of 12.3 mA W^?1 and detectivity of 1.8 × 10¹⁰ Jones are obtained from the photodetector under 532 nm light illumination. Density functional theory calculations reveal the impact of specific carbon atomic arrangement in the glassy‐graphene on the electronic band structure. It is demonstrated that the band alignment of the layered heterostructures can be manipulated by lattice engineering of 2D nanosheets to enhance optoelectronic performance.     

Noncovalent Functionalization of Pnictogen Surfaces: From Small Molecules to 2D Heterostructures

Beyond graphene, 2D pnictogen polymers are rapidly growing among the family of 2D materials. Due to their unique properties, this group has received considerable interest in recent years. Those properties include tunable electronic band gaps, high charge carrier mobility, and in‐plane anisotropic properties. This Review covers the noncovalent functionalization of pnictogen surfaces considering experimental and theoretical studies. Noncovalent functionalization is of great importance for effective modulation of the electronic structure of these materials as well as improvement of their stability toward surface oxidation. This Review highlights their noncovalent modification by organic molecules, in which enhanced surface stability of phosphorene and generated functionalized materials for applications in biomedical, supercapacitors, energy storage, and biosensors. Moreover, the noncovalent interactions with small molecules show its significance for sensing applications. Lastly, the interactions of pnictogen sheets with other 2D materials and their applications for van der Waals heterostructure formation are discussed. Current state‐of‐the‐art as well as future perspectives in this field are covered.     

Graphene in Photocatalysis: A Review

In recent years, heterogeneous photocatalysis has received much research interest because of its powerful potential applications in tackling many important energy and environmental challenges at a global level in an economically sustainable manner. Due to their unique optical, electrical, and physicochemical properties, various 2D graphene nanosheets‐supported semiconductor composite photocatalysts have been widely constructed and applied in different photocatalytic fields. In this review, fundamental mechanisms of heterogeneous photocatalysis, including thermodynamic and kinetics requirements, are first systematically summarized. Then, the photocatalysis‐related properties of graphene and its derivatives, and design rules and synthesis methods of graphene‐based composites are highlighted. Importantly, different design strategies, including doping and sensitization of semiconductors by graphene, improving electrical conductivity of graphene, increasing eloectrocatalytic active sites on graphene, strengthening interface coupling between semiconductors and graphene, fabricating micro/nano architectures, constructing multi‐junction nanocomposites, enhancing photostability of semiconductors, and utilizing the synergistic effect of various modification strategies, are thoroughly summarized. The important applications including photocatalytic pollutant degradation, H₂ production, and CO₂ reduction are also addressed. Through reviewing the significant advances on this topic, it may provide new opportunities for designing highly efficient 2D graphene‐based photocatalysts for various applications in photocatalysis and other fields, such as solar cells, thermal catalysis, separation, and purification.     

Elemental Analogues of Graphene: Silicene,Germanene, Stanene,and Phosphorene

The fascinating electronic and optoelectronic properties of free‐standing graphene has led to the exploration of alternative two‐dimensional materials that can be easily integrated with current generation of electronic technologies. In contrast to 2D oxide and dichalcogenides, elemental 2D analogues of graphene, which include monolayer silicon (silicene), are fast emerging as promising alternatives, with predictions of high degree of integration with existing technologies. This article reviews this emerging class of 2D elemental materials – silicene, germanene, stanene, and phosphorene – with emphasis on fundamental properties and synthesis techniques. The need for further investigations to establish controlled synthesis techniques and the viability of such elemental 2D materials is highlighted. Future prospects harnessing the ability to manipulate the electronic structure of these materials for nano‐ and opto‐electronic applications are identified.     

Epitaxially Grown Strained Pentacene Thin Film on Graphene Membrane

Organic‐graphene system has emerged as a new platform for various applications such as flexible organic photovoltaics and organic light emitting diodes. Due to its important implication in charge transport, the study and reliable control of molecular packing structures at the graphene–molecule interface are of great importance for successful incorporation of graphene in related organic devices. Here, an ideal membrane of suspended graphene as a molecular assembly template is utilized to investigate thin‐film epitaxial behaviors. Using transmission electron microscopy, two distinct molecular packing structures of pentacene on graphene are found. One observed packing structure is similar to the well‐known bulk‐phase, which adapts a face‐on molecular orientation on graphene substrate. On the other hand, a rare polymorph of pentacene crystal, which shows significant strain along the c‐axis, is identified. In particular, the strained film exhibits a specific molecular orientation and a strong azimuthal correlation with underlying graphene. Through ab initio electronic structure calculations, including van der Waals interactions, the unusual polymorph is attributed to the strong graphene–pentacene interaction. The observed strained organic film growth on graphene demonstrates the possibility to tune molecular packing via graphene–molecule interactions.     

Number‐Resolved Single‐Photon Detection with Ultralow Noise van der Waals Hybrid

Van der Waals hybrids of graphene and transition metal dichalcogenides exhibit an extremely large response to optical excitation, yet counting of photons with single‐photon resolution is not achieved. Here, a dual‐gated bilayer graphene (BLG) and molybdenum disulphide (MoS₂) hybrid are demonstrated, where opening a band gap in the BLG allows extremely low channel (receiver) noise and large optical gain (≈10¹⁰) simultaneously. The resulting device is capable of unambiguous determination of the Poissonian emission statistics of an optical source with single‐photon resolution at an operating temperature of 80 K, dark count rate 0.07 Hz, and linear dynamic range of ≈40 dB. Single‐shot number‐resolved single‐photon detection with van der Waals heterostructures may impact multiple technologies, including the linear optical quantum computation.     

Cross‐Plane Carrier Transport in Van der Waals Layered Materials

The mechanisms of carrier transport in the cross‐plane crystal orientation of transition metal dichalcogenides are examined. The study of in‐plane electronic properties of these van der Waals compounds has been the main research focus in recent years. However, the distinctive physical anisotropies, short‐channel physics, and tunability of cross layer interactions can make the study of their electronic properties along the out‐of‐plane crystal orientation valuable. Here, the out‐of‐plane carrier transport mechanisms in niobium diselenide and hafnium disulfide are explored as two broadly different representative materials. Temperature‐dependent current–voltage measurements are preformed to examine the mechanisms involved. First principles simulations and a tunneling model are used to understand these results and quantify the barrier height and hopping distance properties. Using Raman spectroscopy, the thermal response of the chemical bonds is directly explored and the insight into the van der Waals gap properties is acquired. These results indicate that the distinct cross‐plane carrier transport characteristics of the two materials are a result of material thermal properties and thermally mediated transport of carriers through the van der Waals gaps. Exploring the cross‐plane electron transport, the exciting physics involved is unraveled and potential new avenues for the electronic applications of van der Waals layers are inspired.