Precisely Aligned Monolayer MoS2 Epitaxially Grown on h‐BN basal Plane

Control of the precise lattice alignment of monolayer molybdenum disulfide (MoS₂) on hexagonal boron nitride (h‐BN) is important for both fundamental and applied studies of this heterostructure but remains elusive. The growth of precisely aligned MoS₂ domains on the basal plane of h‐BN by a low‐pressure chemical vapor deposition technique is reported. Only relative rotation angles of 0° or 60° between MoS₂ and h‐BN basal plane are present. Domains with same orientation stitch and form single‐crystal, domains with different orientations stitch and from mirror grain boundaries. In this way, the grain boundary is minimized and a continuous film stitched by these two types of domains with only mirror grain boundaries is obtained. This growth strategy is also applicable to other 2D materials growth.     

Black‐Phosphorus‐Based Orientation‐Induced Diodes

Despite many decades of research of diodes, which are fundamental components of electronic and photoelectronic devices with p–n or Schottky junctions using bulk or 2D materials, stereotyped architectures and complex technological processing (doping and multiple material operations) have limited future development. Here, a novel rectification device, an orientation‐induced diode, assembled using only few‐layered black phosphorus (BP) is investigated. The key to its realization is to utilize the remarkable anisotropy of BP in low dimensions and change the charge‐transport conditions abruptly along the different crystal orientations. Rectification ratios of 6.8, 22, and 115 can be achieved in cruciform BP, cross‐stacked BP junctions, and BP junctions stacked with vertical orientations, respectively. The underlying physical processes and mechanisms can be explained using “orientation barrier” band theory. The theoretical results are experimentally confirmed using localized scanning photocurrent imaging. These orientation‐induced optoelectronic devices open possibilities for 2D anisotropic materials with a new degree of freedom to improve modulation in diodes.     

Aligned Growth of Millimeter‐Size Hexagonal Boron Nitride Single‐Crystal Domains on Epitaxial Nickel Thin Film

Atomically thin hexagonal boron nitride (h‐BN) is gaining significant attention for many applications such as a dielectric layer or substrate for graphene‐based devices. For these applications, synthesis of high‐quality and large‐area h‐BN layers with few defects is strongly desirable. In this work, the aligned growth of millimeter‐size single‐crystal h‐BN domains on epitaxial Ni (111)/sapphire substrates by ion beam sputtering deposition is demonstrated. Under the optimized growth conditions, single‐crystal h‐BN domains up to 0.6 mm in edge length are obtained, the largest reported to date. The formation of large‐size h‐BN domains results mainly from the reduced Ni‐grain boundaries and the improved crystallinity of Ni film. Furthermore, the h‐BN domains show well‐aligned orientation and excellent dielectric properties. In addition, the sapphire substrates can be repeatedly used with almost no limit. This work provides an effective approach for synthesizing large‐scale high‐quality h‐BN layers for electronic applications.     

Large Photothermal Effect in Sub‐40 nm h‐BN Nanostructures Patterned Via High‐Resolution Ion Beam

The controlled nanoscale patterning of 2D materials is a promising approach for engineering the optoelectronic, thermal, and mechanical properties of these materials to achieve novel functionalities and devices. Herein, high‐resolution patterning of hexagonal boron nitride (h‐BN) is demonstrated via both helium and neon ion beams and an optimal dosage range for both ions that serve as a baseline for insulating 2D materials is identified. Through this nanofabrication approach, a grating with a 35 nm pitch, individual structure sizes down to 20 nm, and additional nanostructures created by patterning crystal step edges are demonstrated. Raman spectroscopy is used to study the defects induced by the ion beam patterning and is correlated to scanning probe microscopy. Photothermal and scanning near‐field optical microscopy measure the resulting near‐field absorption and scattering of the nanostructures. These measurements reveal a large photothermal expansion of nanostructured h‐BN that is dependent on the height to width aspect ratio of the nanostructures. This effect is attributed to the large anisotropy of the thermal expansion coefficients of h‐BN and the nanostructuring implemented. The photothermal expansion should be present in other van der Waals materials with large anisotropy and can lead to applications such as nanomechanical switches driven by light.     

Thinnest Nonvolatile Memory Based on Monolayer h‐BN

2D materials have attracted much interest over the past decade in nanoelectronics. However, it was believed that the atomically thin layered materials are not able to show memristive effect in vertically stacked structure, until the recent discovery of monolayer transition metal dichalcogenide (TMD) atomristors, overcoming the scaling limit to sub‐nanometer. Herein, the nonvolatile resistance switching (NVRS) phenomenon in monolayer hexagonal boron nitride (h‐BN), a typical 2D insulator, is reported. The h‐BN atomristors are studied using different electrodes and structures, featuring forming‐free switching in both unipolar and bipolar operations, with large on/off ratio (up to 10⁷). Moreover, fast switching speed (<15 ns) is demonstrated via pulse operation. Compared with monolayer TMDs, the one‐atom‐thin h‐BN sheet reduces the vertical scaling to ≈0.33 nm, representing a record thickness for memory materials. Simulation results based on ab‐initio method reveal that substitution of metal ions into h‐BN vacancies during electrical switching is a likely mechanism. The existence of NVRS in monolayer h‐BN indicates fruitful interactions between defects, metal ions and interfaces, and can advance emerging applications on ultrathin flexible memory, printed electronics, neuromorphic computing, and radio frequency switches.     

Recent Advances in Growth of Large‐Sized 2D Single Crystals on Cu Substrates

Large‐scale and high‐quality 2D materials have been an emerging and promising choice for use in modern chemistry and physics owing to their fascinating property profile. The past few years have witnessed inspiringly progressing development in controlled fabrication of large‐sized and single‐crystal 2D materials. Among those production methods, chemical vapor deposition (CVD) has drawn the most attention because of its fine control over size and quality of 2D materials by modulating the growth conditions. Meanwhile, Cu has been widely accepted as the most popular catalyst due to its significant merit in growing monolayer 2D materials in the CVD process. Herein, very recent advances in preparing large‐sized 2D single crystals on Cu substrates by CVD are presented. First, the unique features of Cu will be given in terms of ultralow precursor solubility and feasible surface engineering. Then, scaled growth of graphene and hexagonal boron nitride (h‐BN) crystals on Cu substrates is demonstrated, wherein different kinds of Cu surfaces have been employed. Furthermore, the growth mechanism for the growth of 2D single crystals is exhibited, offering a guideline to elucidate the in‐depth growth dynamics and kinetics. Finally, relevant issues for industrial‐scale mass production of 2D single crystals are discussed and a promising future is expected.     

Nickelocene‐Precursor‐Facilitated Fast Growth of Graphene/h‐BN Vertical Heterostructures and Its Applications in OLEDs

The direct growth of high‐quality, large‐area, uniform, vertically stacked Gr/h‐BN heterostructures is of vital importance for applications in electronics and optoelectronics. However, the main challenge lies in the catalytically inert nature of the hexagonal boron nitride (h‐BN) substrates, which usually afford a rather low decomposition rate of carbon precursors, and thus relatively low growth rate of graphene. Herein, a nickelocene‐precursor‐facilitated route is developed for the fast growth of Gr/h‐BN vertical heterostructures on Cu foils, which shows much improved synthesis efficiency (8–10 times faster) and crystalline quality of graphene (large single‐crystalline domain up to ≈20 µm). The key advantage of our synthetic route is the utilization of nickel atoms that are decomposed from nickelocene molecules as the gaseous catalyst, which can decrease the energy barrier for graphene growth and facilitate the decomposition of carbon sources, according to our density functional theory calculations. The high‐quality Gr/h‐BN stacks are proved to be perfect anode/protecting layers for high‐performance organic light‐emitting diode devices. In this regard, this work offers a brand‐new route for the fast growth of Gr/h‐BN heterostructures with practical scalability and high crystalline quality, thus should propel its wide applications in transparent electrodes, high‐performance electronic devices, and energy harvesting/transition directions.     

Tunable Polarity Behavior and Self‐Driven Photoswitching in p‐WSe2/n‐WS2 Heterojunctions

Van der Waals (vdW) p–n heterojunctions consisting of various 2D layer compounds are fascinating new artificial materials that can possess novel physics and functionalities enabling the next‐generation of electronics and optoelectronics devices. Here, it is reported that the WSe₂/WS₂ p–n heterojunctions perform novel electrical transport properties such as distinct rectifying, ambipolar, and hysteresis characteristics. Intriguingly, the novel tunable polarity transition along a route of n‐“anti‐bipolar”–p‐ambipolar is observed in the WSe₂/WS₂ heterojunctions owing to the successive work of conducting channels of junctions, p‐WSe₂ and n‐WS₂ on the electrical transport of the whole systems. The type‐II band alignment obtained from first principle calculations and built‐in potential in this vdW heterojunction can also facilitate the efficient electron–hole separation, thus enabling the significant photovoltaic effect and a much enhanced self‐driven photoswitching response in this system.     

Hexagonal Boron Nitride Growth on Cu‐Si Alloy: Morphologies and Large Domains

Controllable synthesis of high‐quality hexagonal boron nitride (h‐BN) is desired toward the industrial application of 2D devices based on van der Waals heterostructures. Substantial efforts are devoted to synthesize h‐BN on copper through chemical vapor deposition, which has been successfully applied to grow graphene. However, the progress in synthesizing h‐BN has been significantly retarded, and it is still challenging to realize millimeter‐scale domains and control their morphologies reliably. Here, the nucleation density of h‐BN on Cu is successfully reduced by over two orders of magnitude by simply introducing a small amount of silicon, giving rise to large triangular domains with maximum 0.25 mm lateral size. Moreover, the domain morphologies can be modified from needles, tree patterns, and leaf darts to triangles through controlling the growth temperature. The presence of silicon alters the growth mechanism from attachment‐limited mode to diffusion‐limited mode, leading to dendrite domains that are rarely observed on pure Cu. A phase‐field model is utilized to reveal the growing dynamics regarding B‐N diffusion, desorption, flux, and reactivity variables, and explain the morphology evolution. The work sheds lights on the h‐BN growth toward large single crystals and morphology probabilities.     

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.     

Efficient Self‐Driven Photodetectors Featuring a Mixed‐Dimensional van der Waals Heterojunction Formed from a CdS Nanowire and a MoTe2 Flake

Heterojunctions formed from low‐dimensional materials can result in photovoltaic and photodetection devices displaying exceptional physical properties and excellent performance. Herein, a mixed‐dimensional van der Waals (vdW) heterojunction comprising a 1D n‐type Ga‐doped CdS nanowire and a 2D p‐type MoTe₂ flake is demonstrated; the corresponding photovoltaic device exhibits an outstanding conversion efficiency of 15.01% under illumination with white light at 650 µW cm^?2. A potential difference of 80 meV measured, using Kelvin probe force microscopy, at the CdS–MoTe₂ interface confirms the separation and accumulation of photoexcited carriers upon illumination. Moreover, the photodetection characteristics of the vdW heterojunction device at zero bias reveal a rapid response time (<50 ms) and a photoresponsivity that are linearly proportional to the power density of the light. Interestingly, the response of the vdW heterojunction device is negligible when illuminated at 580 nm; this exceptional behavior is presumably due to the rapid rate of recombination of the photoexcited carriers of MoTe₂. Such mixed‐dimensional vdW heterojunctions appear to be novel design elements for efficient photovoltaic and self‐driven photodetection devices.     

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.     

Postsynthesis of h‐BN/Graphene Heterostructures Inside a STEM

Combinations of 2D materials with different physical properties can form heterostructures with modified electrical, mechanical, magnetic, and optical properties. The direct observation of a lateral heterostructure synthesis is reported by epitaxial in‐plane graphene growth from the step‐edge of hexagonal BN (h‐BN) within a scanning transmission electron microscope chamber. Residual hydrocarbon in the chamber is the carbon source. The growth interface between h‐BN and graphene is atomically identified as largely N–C bonds. This postgrowth method can form graphene nanoribbons connecting two h‐BN domains with different twisting angles, as well as isolated carbon islands with arbitrary shapes embedded in the h‐BN layer. The electronic properties of the vertically stacked h‐BN/graphene heterostructures are investigated by electron energy‐loss spectroscopy (EELS). Low‐loss EELS analysis of the dielectric response suggests a robust coupling effect between the graphene and h‐BN layers.     

Twinned Growth of Metal‐Free,Triazine‐Based Photocatalyst Films as Mixed‐Dimensional (2D/3D) van der Waals Heterostructures

Design and synthesis of ordered, metal‐free layered materials is intrinsically difficult due to the limitations of vapor deposition processes that are used in their making. Mixed‐dimensional (2D/3D) metal‐free van der Waals (vdW) heterostructures based on triazine (C₃N₃) linkers grow as large area, transparent yellow‐orange membranes on copper surfaces from solution. The membranes have an indirect band gap (E _g,opt = 1.91 eV, E _g,elec = 1.84 eV) and are moderately porous (124 m² g^?1). The material consists of a crystalline 2D phase that is fully sp² hybridized and provides structural stability, and an amorphous, porous phase with mixed sp²–sp hybridization. Interestingly, this 2D/3D vdW heterostructure grows in a twinned mechanism from a one‐pot reaction mixture: unprecedented for metal‐free frameworks and a direct consequence of on‐catalyst synthesis. Thanks to the efficient type I heterojunction, electron transfer processes are fundamentally improved and hence, the material is capable of metal‐free, light‐induced hydrogen evolution from water without the need for a noble metal cocatalyst (34 µmol h^?1 g^?1 without Pt). The results highlight that twinned growth mechanisms are observed in the realm of “wet” chemistry, and that they can be used to fabricate otherwise challenging 2D/3D vdW heterostructures with composite properties.     

Van der Waals Integration of Bismuth Quantum Dots–Decorated Tellurium Nanotubes (Te@Bi) Heterojunctions and Plasma‐Enhanced Optoelectronic Applications

Van der Waals (vdW)‐integrated heterojunctions have been widely investigated in optoelectronics due to their superior photoelectric conversion capability. In this work, 0D bismuth quantum dots (Bi QDs)‐decorated 1D tellurium nanotubes (Te NTs) vdW heterojunctions (Te@Bi vdWHs) are constructed by a facile bottom‐up assembly process. Transient absorption spectroscopy suggests that Te@Bi vdWH is a promising candidate for new‐generation optoelectronic devices with fast response properties. The subsequent experiments and density functional theory calculations demonstrate the vdW interaction between Te NTs and Bi QDs, as well as the enhanced optoelectronic characteristics owing to the plasma effects at the interface between Te NTs and Bi QDs. Moreover, Te@Bi vdWHs‐based photodetectors show significantly improved photoresponse behavior in the ultraviolet region compared to pristine Te NTs or Bi QDs‐based photodetectors. The proposed integration of vdWHs is expected to pave the way for constructing new nanoscale heterodevices.     

Thickness‐Dependent In‐Plane Polarization and Structural Phase Transition in van der Waals Ferroelectric CuInP2S6

van der Waals (vdW) layered materials have rather weaker interlayer bonding than the intralayer bonding, therefore the exfoliation along the stacking direction enables the achievement of monolayer or few layers vdW materials with emerging novel physical properties and functionalities. The ferroelectricity in vdW materials recently attracts renewed interest for the potential use in high‐density storage devices. With the thickness becoming thinner, the competition between the surface energy, depolarization field, and interfacial chemical bonds may give rise to the modification of ferroelectricity and crystalline structure, which has limited investigations. In this work, combining the piezoresponse force microscope scanning, contact resonance imaging, the existence of the intrinsic in‐plane polarization in vdW ferroelectrics CuInP₂S₆ single crystals is reported, whereas below a critical thickness between 90 and 100 nm, the in‐plane polarization disappears. The Young's modulus also shows an abrupt stiffness at the critical thickness. Based on the density functional theory calculations, these behaviors are ascribed to a structural phase transition from monoclinic to trigonal structure, which is further verified by transmission electron microscope technique. These findings demonstrate the foundational importance of structural phase transition for enhancing the rich functionality and broad utility of vdW ferroelectrics.     

Unprecedented Centimeter‐Long Carbon Nitride Needles: Synthesis,Characterization and Applications

Free standing centimeter‐long 1D nanostructures are highly attractive for electronic and optoelectronic devices due to their unique photophysical and electrical properties. Here a simple, large‐scale synthesis of centimeter‐long 1D carbon nitride (CN) needles with tunable photophysical, electric, and catalytic properties is reported. Successful growth of ultralong needles is acquired by the utilization of 1D organic crystal precursors comprised of CN monomers as reactants. Upon calcination at high temperatures, the shape of the starting crystal is fully preserved while the CN composition and porosity, and optical and electrical properties can be easily tuned by tailoring the starting elements ratio and final calcination temperature. The facile manipulation and visualization of the CN needles endow their direct electrical measurements by placing them between two conductive probes. Moreover, the CN needles exhibit good photocatalytic activity for hydrogen production owing to their improved light harvesting properties, high surface area, and advantageous energy bands position. The new growth strategy developed here may open opportunities for a rational design of CN and other metal‐free materials with controllable directionality and tunable photophysical and electronic properties, toward their utilization in (photo)electronic devices.     

Water‐Stable Chemical‐Protective Textiles via Euhedral Surface‐Oriented 2D Cu–TCPP Metal‐Organic Frameworks

Abatement of chemical hazards using adsorptive metal‐organic frameworks (MOFs) attracts substantial attention, but material stability and crystal integration into functional systems remain key challenges. Herein, water‐stable, polymer fiber surface–oriented M–TCPP [M = Cu, Zn, and Co; H₂TCPP = 5,10,15,20‐tetrakis(4‐carboxyphenyl)porphyrin] 2D MOF crystals are fabricated using a facile hydroxy double salt (HDS) solid‐source conversion strategy. For the first time, Cu–TCPP is formed from a solid source and confirmed to be highly adsorptive for NH₃ and 2‐chloroethyl ethyl sulfide (CEES), a blistering agent simulant, in humid (80% relative humidity (RH)) conditions. Moreover, the solid HDS source is found as a unique new approach to control MOF thin‐film crystal orientation, thereby facilitating radially arranged MOF crystals on fibers. On a per unit mass of MOF basis in humid conditions, the MOF/fiber composite enhances NH₃ adsorptive capacity by a factor of 3 compared to conventionally prepared MOF powders. The synthesis route extends to other MOF/fiber composite systems, therefore providing a new route for chemically protective materials.     

Single‐Crystalline Nanobelts Composed of Transition Metal Ditellurides

Following the celebrated discovery of graphene, considerable attention has been directed toward the rich spectrum of properties offered by van der Waals crystals. However, studies have been largely limited to their 2D properties due to lack of 1D structures. Here, the growth of high‐yield, single‐crystalline 1D nanobelts composed of transition metal ditellurides at low temperatures (T ≤ 500 °C) and in short reaction times (t ≤ 10 min) via the use of tellurium‐rich eutectic metal alloys is reported. The synthesized semimetallic 1D products are highly pure, stoichiometric, structurally uniform, and free of defects, resulting in high electrical performances. Furthermore, complete compositional tuning of the ternary ditelluride nanobelts is achieved with suppressed phase separation, applicable to the creation of unprecedented low‐dimensional materials/devices. This approach may inspire new growth/fabrication strategies of 1D layered nanostructures, which may offer unique properties that are not available in other materials.     

Few‐Layer GeAs Field‐Effect Transistors and Infrared Photodetectors

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