Determining the Optimized Interlayer Separation Distance in Vertical Stacked 2D WS2:hBN:MoS2 Heterostructures for Exciton Energy Transfer

The 2D semiconductor monolayer transition metal dichalcogenides, WS₂ and MoS₂, are grown by chemical vapor deposition (CVD) and assembled by sequential transfer into vertical layered heterostructures (VLHs). Insulating hBN, also produced by CVD, is utilized to control the separation between WS₂ and MoS₂ by adjusting the layer number, leading to fine‐scale tuning of the interlayer interactions within the VLHs. The interlayer interactions are studied by photoluminescence (PL) spectroscopy and are demonstrated to be highly sensitive to the input excitation power. For thin hBN separators (one to two layers), the total PL emission switches from quenching to enhancement by increasing the laser power. Femtosecond broadband transient absorption measurements demonstrate that the increase in PL quantum yield results from Förster energy transfer from MoS₂ to WS₂. The PL signal is further enhanced at cryogenic temperatures due to the suppressed nonradiative decay channels. It is shown that (4 ± 1) layers of hBN are optimum for obtaining PL enhancement in the VLHs. Increasing thickness beyond this causes the enhancement factor to diminish, with the WS₂ and MoS₂ then behaving as isolated noninteracting monolayers. These results indicate how controlling the exciton generation rate influences energy transfer and plays an important role in the properties of VLHs.     

Recent Progress in CVD Growth of 2D Transition Metal Dichalcogenides and Related Heterostructures

In recent years, 2D layered materials have received considerable research interest on account of their substantial material systems and unique physicochemical properties. Among them, 2D layered transition metal dichalcogenides (TMDs), a star family member, have already been explored over the last few years and have exhibited excellent performance in electronics, catalysis, and other related fields. However, to fulfill the requirement for practical application, the batch production of 2D TMDs is essential. Recently, the chemical vapor deposition (CVD) technique was considered as an elegant alternative for successfully growing 2D TMDs and their heterostructures. The latest research advances in the controllable synthesis of 2D TMDs and related heterostructures/superlattices via the CVD approach are illustrated here. The controlled growth behavior, preparation strategies, and breakthroughs on the synthesis of new 2D TMDs and their heterostructures, as well as their unique physical phenomena, are also discussed. Recent progress on the application of CVD‐grown 2D materials is revealed with particular attention to electronics/optoelectronic devices and catalysts. Finally, the challenges and future prospects are considered regarding the current development of 2D TMDs and related heterostructures.     

Unveiling the Superior Optical Properties of Novel Melamine-Based Nonlinear Optical Material with Strong Second-Harmonic Generation and Giant Optical Anisotropy

Two melamine-based metal halides, (C₃N₆H₇)(C₃N₆H₆)HgCl₃ (I) and (C₃N₆H₇)₃HgCl₅ (II), are synthesized by incorporating the heavy d¹⁰ cation, Hg²⁺, and the halide anion, Cl⁻. The noncentrosymmetric structure of I results from two unique attributes: large asymmetric secondary building units produced by direct covalent coordination of melamine to Hg²⁺ and a small dihedral angle between melamine molecules. The former makes inorganic modules locally acentric, while the latter prevents planar organic groups from forming deleterious antiparallel arrangement. The unique coordination in I results in an enlarged band gap of 4.40 eV. Due to the large polarizability of the heavy Hg²⁺ cation and the π-conjugated system of melamine, I exhibits a strong second-harmonic generation efficiency of 5 × KH₂PO₄, larger than any reported melamine-based nonlinear optical materials to date. Density functional theory calculations indicate that I possesses giant optical anisotropy, with a birefringence of 0.246@1064 nm.     

YCOB晶体生长与激光倍频性能研究

坩埚下降法沿＜０１０＞和＜００１＞方向生长了直径达到２５ｍｍ的完整透明的Ｃａ４ＹＯ（ＢＯ３）３ （ＹＣＯＢ）晶体．化学腐蚀结果表明，所生长晶体无孪晶或亚晶界等缺陷，晶体尾部的位错密度 不超过１８００／ｃｍ２测量了ＹＣＯＢ的透射光谱，其截止波长为２００ｎｍ进行了ＹＣＯＢ晶体对 Ｎｄ：ＹＡＧ激光的二次倍频实验．通过与ＫＤＰ晶体对比，计算出ＹＣＯＢ晶体的有效非线性系数 在Ⅰ型相位匹配方向（θ，φ）＝（６６．３°，１４３．５°）和（６５．９°，３６．５°）上分别为１．４５ｐｍ／Ｖ和０．９１ｐｍ／Ｖ； 大于ＫＤＰ和 ＬＢＯ晶体．在脉冲宽度１０ｎｓ的 Ｎｄ：ＹＡＧ激光单脉冲辐射下ＹＣＯＢ晶体出现体 损伤的激光损伤阈值不低于８５ＧＷ／ｃｍ２．     

Edge‐Epitaxial Growth of 2D NbS2‐WS2 Lateral Metal‐Semiconductor Heterostructures

2D metal‐semiconductor heterostructures based on transition metal dichalcogenides (TMDs) are considered as intriguing building blocks for various fields, such as contact engineering and high‐frequency devices. Although, a series of p–n junctions utilizing semiconducting TMDs have been constructed hitherto, the realization of such a scheme using 2D metallic analogs has not been reported. Here, the synthesis of uniform monolayer metallic NbS₂ on sapphire substrate with domain size reaching to a millimeter scale via a facile chemical vapor deposition (CVD) route is demonstrated. More importantly, the epitaxial growth of NbS₂‐WS₂ lateral metal‐semiconductor heterostructures via a “two‐step” CVD method is realized. Both the lateral and vertical NbS₂‐WS₂ heterostructures are achieved here. Transmission electron microscopy studies reveal a clear chemical modulation with distinct interfaces. Raman and photoluminescence maps confirm the precisely controlled spatial modulation of the as‐grown NbS₂‐WS₂ heterostructures. The existence of the NbS₂‐WS₂ heterostructures is further manifested by electrical transport measurements. This work broadens the horizon of the in situ synthesis of TMD‐based heterostructures and enlightens the possibility of applications based on 2D metal‐semiconductor heterostructures.     

Tunable Ferromagnetism and Thermally Induced Spin Flip in Vanadium-Doped Tungsten Diselenide Monolayers at Room Temperature

The outstanding optoelectronic and valleytronic properties of transition metal dichalcogenides (TMDs) have triggered intense research efforts by the scientific community. An alternative to induce long-range ferromagnetism (FM) in TMDs is by introducing magnetic dopants to form a dilute magnetic semiconductor. Enhancing ferromagnetism in these semiconductors not only represents a key step toward modern TMD-based spintronics, but also enables exploration of new and exciting dimensionality-driven magnetic phenomena. To this end, tunable ferromagnetism at room temperature and a thermally induced spin flip (TISF) in monolayers of V-doped WSe₂ are shown. As vanadium concentration increases, the saturation magnetization increases, which is optimal at ≈4 at% vanadium; the highest doping level ever achieved for V-doped WSe₂ monolayers. The TISF occurs at ≈175 K and becomes more pronounced upon increasing the temperature toward room temperature. The TISF can be manipulated by changing the vanadium concentration. The TISF is attributed to the magnetic-field- and temperature-dependent flipping of the nearest W-site magnetic moments that are antiferromagnetically coupled to the V magnetic moments in the ground state. This is fully supported by a recent spin-polarized density functional theory study. The findings pave the way for the development of novel spintronic and valleytronic nanodevices and stimulate further research.     

PtTe2‐Based Type‐II Dirac Semimetal and Its van der Waals Heterostructure for Sensitive Room Temperature Terahertz Photodetection

Recent years have witnessed rapid progresses made in the photoelectric performance of two‐dimensional materials represented by graphene, black phosphorus, and transition metal dichalcogenides. Despite significant efforts, a photodetection technique capable for longer wavelength, higher working temperature as well as fast responsivity, is still facing huge challenges due to a lack of best among bandgap, dark current, and absorption ability. Exploring topological materials with nontrivial band transport leads to peculiar properties of quantized phenomena such as chiral anomaly, and magnetic‐optical effect, which enables a novel feasibility for an advanced optoelectronic device working at longer wavelength. In this work, the direct generation of photocurrent at low energy terahertz (THz) band at room temperature is implemented in a planar metal–PtTe₂–metal structure. The results show that the THz photodetector based on PtTe₂ with bow‐tie‐type planar contacts possesses a high photoresponsivity (1.6 A W^?1 without bias voltage) with a response time less than 20 µs, while the PtTe₂–graphene heterostructure‐based detector can reach responsivity above 1.4 kV W^?1 and a response time shorter than 9 µs. Remarkably, it is already exploitable for large area imaging applications. These results suggest that topological semimetals such as PtTe₂ can be ideal materials for implementation in a high‐performing photodetection system at THz band.     

Rational Kinetics Control toward Universal Growth of 2D Vertically Stacked Heterostructures

The rational control of the nucleation and growth kinetics to enable the growth of 2D vertical heterostructure remains a great challenge. Here, an in‐depth study is provided toward understanding the growth mechanism of transition metal dichalcogenides (TMDCs) vertical heterostructures in terms of the nucleation and kinetics, where active clusters with a high diffusion barrier will induce the nucleation on top of the TMDC templates to realize vertical heterostructures. Based on this mechanism, in the experiment, through rational control of the metal/chalcogenide ratio in the vapor precursors, effective manipulation of the diffusion barrier of the active clusters and precise control of the heteroepitaxy direction are realized. In this way, a family of vertical TMDCs heterostructures is successfully designed. Optical studies and scanning transmission electron microscopy investigations exhibit that the resulting heterostructures possess atomic sharp interfaces without apparent alloying and defects. This study provides a deep understanding regarding the growth mechanism in terms of the nucleation and kinetics and the robust growth of 2D vertical heterostructures, defining a versatile material platform for fundamental studies and potential device applications.     

Visualizing the Anomalous Charge Density Wave States in Graphene/NbSe2 Heterostructures

Metallic layered transition metal dichalcogenides (TMDs) host collective many-body interactions, including the competing superconducting and charge density wave (CDW) states. Graphene is widely employed as a heteroepitaxial substrate for the growth of TMD layers and as an ohmic contact, where the graphene/TMD heterostructure is naturally formed. The presence of graphene can unpredictably influence the CDW order in 2D CDW conductors. This work reports the CDW transitions of 2H-NbSe₂ layers in graphene/NbSe₂ heterostructures. The evolution of Raman spectra demonstrates that the CDW phase transition temperatures (T_CDW) of NbSe₂ are dramatically decreased when capped by graphene. The induced anomalous short-range CDW state is confirmed by scanning tunneling microscopy measurements. The findings propose a new criterion to determine the T_CDW through monitoring the line shape of the A_1g mode. Meanwhile, the 2D band is also discovered as an indicator to observe the CDW transitions. First-principles calculations imply that interfacial electron doping suppresses the CDW states by impeding the lattice distortion of 2H-NbSe₂. The extraordinary random CDW lattice suggests deep insight into the formation mechanism of many collective electronic states and possesses great potential in modulating multifunctional devices.     

Dark‐Exciton‐Mediated Fano Resonance from a Single Gold Nanostructure on Monolayer WS2 at Room Temperature

Strong spatial confinement and highly reduced dielectric screening provide monolayer transition metal dichalcogenides with strong many‐body effects, thereby possessing optically forbidden excitonic states (i.e., dark excitons) at room temperature. Herein, the interaction of surface plasmons with dark excitons in hybrid systems consisting of stacked gold nanotriangles and monolayer WS₂ is explored. A narrow Fano resonance is observed when the hybrid system is surrounded by water, and the narrowing of the spectral Fano linewidth is attributed to the plasmon‐enhanced decay of dark K‐K excitons. These results reveal that dark excitons in monolayer WS₂ can strongly modify Fano resonances in hybrid plasmon–exciton systems and can be harnessed for novel optical sensors and active nanophotonic devices.     

Spatial Mapping of Hot‐Spots at Lateral Heterogeneities in Monolayer Transition Metal Dichalcogenides

Lateral heterogeneities in atomically thin 2D materials such as in‐plane heterojunctions and grain boundaries (GBs) provide an extrinsic knob for manipulating the properties of nano‐ and optoelectronic devices and harvesting novel functionalities. However, these heterogeneities have the potential to adversely affect the performance and reliability of the 2D devices through the formation of nanoscopic hot‐spots. In this report, scanning thermal microscopy (SThM) is utilized to map the spatial distribution of the temperature rise within monolayer transition metal dichalcogenide (TMD) devices upon dissipating a high electrical power through a lateral interface. The results directly demonstrate that lateral heterojunctions between MoS₂ and WS₂ do not largely impact the distribution of heat dissipation, while GBs of MoS₂ appreciably localize heating in the device. High‐resolution scanning transmission electron microscopy reveals that the atomic structure is nearly flawless around heterojunctions but can be quite defective near GBs. The results suggest that the interfacial atomic structure plays a crucial role in enabling uniform charge transport without inducing localized heating. Establishing such structure–property‐processing correlation provides a better understanding of lateral heterogeneities in 2D TMD systems which is crucial in the design of future all‐2D electronic circuitry with enhanced functionalities, lifetime, and performance.     

Emergence of the Vortex State in Confined Ferroelectric Heterostructures

The manipulation of charge and lattice degrees of freedom in atomically precise, low‐dimensional ferroelectric superlattices can lead to exotic polar structures, such as a vortex state. The role of interfaces in the evolution of the vortex state in these superlattices (and the associated electrostatic and elastic boundary conditions they produce) has remained unclear. Here, the toroidal state, arranged in arrays of alternating clockwise/counterclockwise polar vortices, in a confined SrTiO₃/PbTiO₃/SrTiO₃ trilayer is investigated. By utilizing a combination of transmission electron microscopy, synchrotron‐based X‐ray diffraction, and phase‐field modeling, the phase transition as a function of layer thickness (number of unit cells) demonstrates how the vortex state emerges from the ferroelectric state by varying the thickness of the confined PbTiO₃ layer. Intriguingly, the vortex state arises at head‐to‐head domain boundaries in ferroelectric a₁/a₂ twin structures. In turn, by varying the total number of PbTiO₃ layers (moving from trilayer to superlattices), it is possible to manipulate the long‐range interactions among multiple confined PbTiO₃ layers to stabilize the vortex state. This work provides a new understanding of how the different energies work together to produce this exciting new state of matter and can contribute to the design of novel states and potential memory applications.     

A General Strategy for Synthesis of Binary Transition Metal Phosphides Hollow Sandwich Heterostructures

The hollow sandwich core–shell micro-nanomaterials are widely used in materials, chemistry, and medicine, but their fabrication, particularly for transition metal phosphides (TMPs), remains a great challenge. Herein, a general synthesis strategy is presented for binary TMPs hollow sandwich heterostructures with vertically interconnected nanosheets on the inside and outside surfaces of polyhedron FeCoP_x/C, demonstrated by a variety of transition metals (including Co, Fe, Cd, Mn, Cu, Cr, and Ni). Density functional theory (DFT) calculation reveals the process and universal mechanism of layered double hydroxide (LDH) growth on Prussian blue analog (PBA) surface in detail for the first time, which provides the theoretical foundations for feasibility and rationality of the synthesis strategy. This unique structure exhibits a vertical nanosheet-shell-vertical nanosheet configuration combining the advantages of sandwich, hollow and vertical heterostructures, effectively achieving their synergistic effect. As a proof-of-concept of their applications, the CoNiP_x@FeCoP_x/C@CoNiP_x hollow sandwich polyhedron architectures (representative samples) show excellent catalytic performance for the oxygen evolution reaction (OER) in alkaline electrolytes. This work provides a general method for constructing hollow-sandwich micro-nanostructures, which provides more ideas and directions for design of micro-nano materials with special geometric topology.     

Large‐Area Atomic Layers of the Charge‐Density‐Wave Conductor TiSe2

Layered transition metal (Ti, Ta, Nb, etc.) dichalcogenides are important prototypes for the study of the collective charge density wave (CDW). Reducing the system dimensionality is expected to lead to novel properties, as exemplified by the discovery of enhanced CDW order in ultrathin TiSe₂. However, the syntheses of monolayer and large‐area 2D CDW conductors can currently only be achieved by molecular beam epitaxy under ultrahigh vacuum. This study reports the growth of monolayer crystals and up to 5 × 10⁵ µm² large films of the typical 2D CDW conductor—TiSe₂—by ambient‐pressure chemical vapor deposition. Atomic resolution scanning transmission electron microscopy indicates the as‐grown samples are highly crystalline 1T‐phase TiSe₂. Variable‐temperature Raman spectroscopy shows a CDW phase transition temperature of 212.5 K in few layer TiSe₂, indicative of high crystal quality. This work not only allows the exploration of many‐body state of TiSe₂ in 2D limit but also offers the possibility of utilizing large‐area TiSe₂ in ultrathin electronic devices.     

Controlling Photoluminescence Enhancement and Energy Transfer in WS2:hBN:WS2 Vertical Stacks by Precise Interlayer Distances

2D semiconducting transition metal dichalcogenides (TMDs) are endowed with fascinating optical properties especially in their monolayer limit. Insulating hBN films possessing customizable thickness can act as a separation barrier to dictate the interactions between TMDs. In this work, vertical layered heterostructures (VLHs) of WS₂:hBN:WS₂ are fabricated utilizing chemical vapor deposition (CVD)‐grown materials, and the optical performance is evaluated through photoluminescence (PL) spectroscopy. Apart from the prohibited indirect optical transition due to the insertion of hBN spacers, the variation in the doping level of WS₂ drives energy transfer to arise from the layer with lower quantum efficiency to the other layer with higher quantum efficiency, whereby the total PL yield of the heterosystem is increased and the stack exhibits a higher PL intensity compared to the sum of those in the two WS₂ constituents. Such doping effects originate from the interfaces that WS₂ monolayers reside on and interact with. The electron density in the WS₂ is also controlled and subsequent modulation of PL in the heterostructure is demonstrated by applying back‐gated voltages. Other influential factors include the strain in WS₂ and temperature. Being able to tune the energy transfer in the VLHs may expand the development of photonic applications in 2D systems.     

Carbon‐MEMS‐Based Alternating Stacked MoS2@rGO‐CNT Micro‐Supercapacitor with High Capacitance and Energy Density

A novel process to fabricate a carbon‐microelectromechanical‐system‐based alternating stacked MoS₂@rGO–carbon‐nanotube (CNT) micro‐supercapacitor (MSC) is reported. The MSC is fabricated by successively repeated spin‐coating of MoS₂@rGO/photoresist and CNT/photoresist composites twice, followed by photoetching, developing, and pyrolysis. MoS₂@rGO and CNTs are embedded in the carbon microelectrodes, which cooperatively enhance the performance of the MSC. The fabricated MSC exhibits a high areal capacitance of 13.7 mF cm^?2 and an energy density of 1.9 µWh cm^?2 (5.6 mWh cm^?3), which exceed many reported carbon‐ and MoS₂‐based MSCs. The MSC also retains 68% of capacitance at a current density of 2 mA cm^?2 (5.9 A cm^?3) and an outstanding cycling performance (96.6% after 10 000 cycles, at a scan rate of 1 V s^?1). Compared with other MSCs, the MSC in this study is fabricated by a low‐cost and facile process, and it achieves an excellent and stable electrochemical performance. This approach could be highly promising for applications in integration of micro/nanostructures into microdevices/systems.