Spatial Control of Substitutional Dopants in Hexagonal Monolayer WS2: The Effect of Edge Termination

The ability to control the density and spatial distribution of substitutional dopants in semiconductors is crucial for achieving desired physicochemical properties. Substitutional doping with adjustable doping levels has been previously demonstrated in 2D transition metal dichalcogenides (TMDs); however, the spatial control of dopant distribution remains an open field. In this work, edge termination is demonstrated as an important characteristic of 2D TMD monocrystals that affects the distribution of substitutional dopants. Particularly, in chemical vapor deposition (CVD)-grown monolayer WS₂, it is found that a higher density of transition metal dopants is always incorporated in sulfur-terminated domains when compared to tungsten-terminated domains. Two representative examples demonstrate this spatial distribution control, including hexagonal iron- and vanadium-doped WS₂ monolayers. Density functional theory (DFT) calculations are further performed, indicating that the edge-dependent dopant distribution is due to a strong binding of tungsten atoms at tungsten-zigzag edges, resulting in the formation of open sites at sulfur-zigzag edges that enable preferential dopant incorporation. Based on these results, it is envisioned that edge termination in crystalline TMD monolayers can be utilized as a novel and effective knob for engineering the spatial distribution of substitutional dopants, leading to in-plane hetero-/multi-junctions that display fascinating electronic, optoelectronic, and magnetic properties.     

Phase Engineering of Transition Metal Dichalcogenides with Unprecedentedly High Phase Purity,Stability, and Scalability via Molten-Metal-Assisted Intercalation

The crystalline phase of layered transition metal dichalcogenides (TMDs) directly determines their material property. The most thermodynamically stable phase structures in TMDs are the semiconducting 2H and metastable metallic 1T phases. To overcome the low phase purity and instability of 1T-TMDs, which limits the utilization of their intrinsic properties, various synthesis strategies for 1T-TMDs have been proposed in phase-engineering studies. Herein, a facile and scalable synthesis of 1T-phase molybdenum disulfide (MoS₂) via the molten-metal-assisted intercalation (MMI) approach is introduced, which exploits the capillary action of molten potassium and the difference between the electron affinity of MoS₂ and the ionization potential of potassium. Highly reactive molten potassium metal can readily intercalate into the MoS₂ interlayers, inducing an efficient phase transition from the 2H to 1T crystal structure. The ionic bonding between the intercalated potassium and sulfur lowers the energy barrier of the 1T-phase transition, enhancing the phase stability of the 1T crystals. Owing to the high purity and stability of the 1T phase, the electrocatalytic performance for the hydrogen evolution reaction is significantly higher in 1T-MoS₂ (MMI) than in 2H-MoS₂ and even in 1T-MoS₂ synthesized using n-butyllithium.     

Potential 2D Materials with Phase Transitions: Structure,Synthesis, and Device Applications

Layered materials with phase transitions, such as charge density wave (CDW) and magnetic and dipole ordering, have potential to be exfoliated into monolayers and few‐layers and then become a large and important subfamily of two‐dimensional (2D) materials. Benefitting from enriched physical properties from the collective interactions, long‐range ordering, and related phase transitions, as well as the atomic thickness yet having nondangling bonds on the surface, 2D phase‐transition materials have vast potential for use in new‐concept and functional devices. Here, potential 2D phase‐transition materials with CDWs and magnetic and dipole ordering, including transition metal dichalcogenides, transition metal halides, metal thio/selenophosphates, chromium silicon/germanium tellurides, and more, are introduced. The structures and experimental phase‐transition properties are summarized for the bulk materials and some of the obtained monolayers. In addition, recent experimental progress on the synthesis and measurement of monolayers, such as 1T‐TaS₂, CrI₃, and Cr₂Ge₂Te₆, is reviewed.     

One‐Step Solution Phase Growth of Transition Metal Dichalcogenide Thin Films Directly on Solid Substrates

Ultrathin transition metal dichalcogenides (TMDs) have exotic electronic properties. With success in easy synthesis of high quality TMD thin films, the potential applications will become more viable in electronics, optics, energy storage, and catalysis. Synthesis of TMD thin films has been mostly performed in vacuum or by thermolysis. So far, there is no solution phase synthesis to produce large‐area thin films directly on target substrates. Here, this paper reports a one‐step quick synthesis (within 45–90 s) of TMD thin films (MoS₂, WS₂, MoSe₂, WSe₂, etc.) on solid substrates by using microwave irradiation on a precursor‐containing electrolyte solution. The numbers of the quintuple layers of the TMD thin films are precisely controllable by varying the precursor's concentration in the electrolyte solution. A photodetector made of MoS₂ thin film comprising of small size grains shows near‐IR absorption, supported by the first principle calculation, exhibits a high photoresponsivity (>300 mA W^?1) and a fast response (124 µs). This study paves a robust way for the synthesis of various TMD thin films in solution phases.     

Transient Absorption Measurements on Anisotropic Monolayer ReS2

Anisotropic optical and transport properties of monolayer ReS₂ fabricated by mechanical exfoliation are reported. Transient absorption measurements with different polarization configurations and sample orientations reveal that the absorption coefficient and transient absorption are both anisotropic, with maximal and minimal values occurring when the light polarization is parallel and perpendicular to the Re atomic chains, respectively. The maximal values are about a factor of 2.5 of the minimal values. By resolving the spatiotemporal dynamics of excitons, it is found that the diffusion coefficient of excitons moving along Re atomic chains is about 16 cm² s⁻¹ at room temperature, which is about a factor of three larger than those moving perpendicular to that direction. An exciton lifetime of 40 ps is also extracted. These findings establish monolayer ReS₂ as an anisotropic 2D transition metal dichalcogenide.     

现代连续相变理论在玻璃分相中的应用

玻璃分相区中存在一临界点,在此临界点的转变属于连续相变范畴。通过本文的讨论表明。对二组元玻璃系统的分相,可以用现代连续相变理论描述。在临界点附近区域内,其分相曲线为以临界点为界,以两曲线方程:(x~l-x_c)/x_c=A[(T_c-T)/T_c]~(1/3),(x~(l′)-x_c)/x_c=A′[(T_c-T)/T_c]~(1/3)来表达。这里 A、A′为二组元系统分相曲线的普适常数。本文中对 Li_2O-SiO_2,Na_2O-SiO_2,BaO-SiO_2系统分相实验值的拟合结果是 A=-1.8305;A′=2.3551。相应的计算曲线与实验值符合较好。     

Controllable,Wide‐Ranging n‐Doping and p‐Doping of Monolayer Group 6 Transition‐Metal Disulfides and Diselenides

Developing processes to controllably dope transition‐metal dichalcogenides (TMDs) is critical for optical and electrical applications. Here, molecular reductants and oxidants are introduced onto monolayer TMDs, specifically MoS₂, WS₂, MoSe₂, and WSe₂. Doping is achieved by exposing the TMD surface to solutions of pentamethylrhodocene dimer as the reductant (n‐dopant) and “Magic Blue,” [N(C₆H₄‐p‐Br)₃]SbCl₆, as the oxidant (p‐dopant). Current–voltage characteristics of field‐effect transistors show that, regardless of their initial transport behavior, all four TMDs can be used in either p‐ or n‐channel devices when appropriately doped. The extent of doping can be controlled by varying the concentration of dopant solutions and treatment time, and, in some cases, both nondegenerate and degenerate regimes are accessible. For all four TMD materials, the photoluminescence intensity; for all four materials the PL intensity is enhanced with p‐doping but reduced with n‐doping. Raman and X‐ray photoelectron spectroscopy (XPS) also provide insight into the underlying physical mechanism by which the molecular dopants react with the monolayer. Estimates of changes of carrier density from electrical, PL, and XPS results are compared. Overall a simple and effective route to tailor the electrical and optical properties of TMDs is demonstrated.     

Synthesis of In‐Plane Artificial Lattices of Monolayer Multijunctions

Recently, monolayers of van der Waals materials, including transition metal dichalcogenides (TMDs), are considered ideal building blocks for constructing 2D artificial lattices and heterostructures. Heterostructures with multijunctions of more than two monolayer TMDs are intriguing for exploring new physics and materials properties. Obtaining in‐plane heterojunctions of monolayer TMDs with atomically sharp interfaces is very significant for fundamental research and applications. Currently, multistep synthesis for more than two monolayer TMDs remains a challenge because decomposition or compositional alloying is thermodynamically favored at the high growth temperature. Here, a multistep chemical vapor deposition (CVD) synthesis of the in‐plane multijunctions of monolayer TMDs is presented. A low growth temperature synthesis is developed to avoid compositional fluctuations of as‐grown TMDs, defects formations, and interfacial alloying for high heterointerface quality and thermal stability of monolayer TMDs. With optimized parameters, atomically sharp interfaces are successfully achieved in the synthesis of in‐plane artificial lattices of the WS₂/WSe₂/MoS₂ at reduced growth temperatures. Growth behaviors as well as the heterointerface quality are carefully studied in varying growth parameters. Highly oriented strain patterns are found in the second harmonic generation imaging of the TMD multijunctions, suggesting that the in‐plane heteroepitaxial growth may induce distortion for unique material symmetry.     

High-Throughput Growth of Wafer-Scale Monolayer Transition Metal Dichalcogenide via Vertical Ostwald Ripening

For practical device applications, monolayer transition metal dichalcogenide (TMD) films must meet key industry needs for batch processing, including the high-throughput, large-scale production of high-quality, spatially uniform materials, and reliable integration into devices. Here, high-throughput growth, completed in 12 min, of 6-inch wafer-scale monolayer MoS₂ and WS₂ is reported, which is directly compatible with scalable batch processing and device integration. Specifically, a pulsed metal–organic chemical vapor deposition process is developed, where periodic interruption of the precursor supply drives vertical Ostwald ripening, which prevents secondary nucleation despite high precursor concentrations. The as-grown TMD films show excellent spatial homogeneity and well-stitched grain boundaries, enabling facile transfer to various target substrates without degradation. Using these films, batch fabrication of high-performance field-effect transistor (FET) arrays in wafer-scale is demonstrated, and the FETs show remarkable uniformity. The high-throughput production and wafer-scale automatable transfer will facilitate the integration of TMDs into Si-complementary metal-oxide-semiconductor platforms.     

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.     

Room‐Temperature Active Modulation of Valley Dynamics in a Monolayer Semiconductor through Chiral Purcell Effects

Spin‐dependent contrasting phenomena at K and K′ valleys in monolayer semiconductors have led to addressable valley degree of freedom, which is the cornerstone for emerging valleytronic applications in information storage and processing. Tunable and active modulation of valley dynamics in a monolayer WSe₂ is demonstrated at room temperature through controllable chiral Purcell effects in plasmonic chiral metamaterials. The strong spin‐dependent modulation on the spontaneous decay of valley excitons leads to tunable handedness and spectral shift of valley‐polarized emission, which is analyzed and predicted by an advanced theoretical model and further confirmed by experimental measurements. Moreover, large active spectral tuning (≈24 nm) and reversible ON/OFF switching of circular polarization of emission are achieved by the solvent‐controllable thickness of the dielectric spacer in the metamaterials. With the on‐demand and active tunability in valley‐polarized emission, chiral Purcell effects can provide new strategies to harness valley excitons for applications in ultrathin valleytronic devices.     

钠镁铝硅系统微晶玻璃的分相成核行为

本文以20Na2O、4CaO、12MgO、22Al2O3、4TiO2、38SiO2(重量百分比)组成玻璃为基础,制备了具有快速微晶化特性的钠镁铝硅系统微晶玻璃。分别采用差热分析技术(DTA)、X射线衍射技术(XRD)研究了不同热处理条件下玻璃分相成核的动力学、热力学和它们之间的依存关系。玻璃分相成核最大速率时的温度接近于923K。在成核温度的热处理对分相的放热行为有影响,成核导致系统自由能的降低与分相峰面积和峰值温度变化有关。用差热分析仪测量的玻璃分相的放热效应,是快速微晶化玻璃的重要特征,用XRD证实分相放热过程中没有微晶相产生。玻璃的分相过程为成核生长机理,采用修正kissinger方程求得玻璃分相活化能为310.445KJ/mol。     

Composition and Interface Engineering of Alloyed MoS2xSe2(1–x) Nanotubes for Enhanced Hydrogen Evolution Reaction Activity

Hierarchical MoS_2xSe_2(1?x) nanotubes assembled from several‐layered nanosheets featuring tunable chalcogen compositions, expanded interlayer spacing and carbon modification, are synthesized for enhanced electrocatalytic hydrogen evolution reaction (HER). The chalcogen compositions of the MoS_2xSe_2(1?x) nanotubes are controllable by adjusting the selenization temperature and duration while the expanded (002) interlayer spacing varies from 0.98 to 0.68 nm. It is found that the MoS_2xSe_2(1?x) (x = 0.54) nanotubes with expanded interlayer spacing of 0.98 nm exhibit the highest electrocatalytic HER activity with a low onset potential of 101 mV and a Tafel slope of 55 mV dec^?1. The improved electrocatalytic performance is attributed to the chalcogen composition tuning and the interlayer distance expansion to achieve benefitting hydrogen adsorption energy. The present work suggests a potential way to design advanced HER electrocatalysts through modulating their compositions and interlayer distances.