Molecular Nanowire Bonding to Epitaxial Single‐Layer MoS2 by an On‐Surface Ullmann Coupling Reaction

Lateral heterostructures consisting of 2D transition metal dichalcogenides (TMDCs) directly interfaced with molecular networks or nanowires can be used to construct new hybrid materials with interesting electronic and spintronic properties. However, chemical methods for selective and controllable bond formation between 2D materials and organic molecular networks need to be developed. As a demonstration of a self‐assembled organic nanowire‐TMDC system, a method to link and interconnect epitaxial single‐layer MoS₂ flakes with organic molecules is demonstrated. Whereas pristine epitaxial single‐layer MoS₂ has no affinity for molecular attachment, it is found that single‐layer MoS₂ will selectively bind the organic molecule 2,8‐dibromodibenzothiophene (DBDBT) in a surface‐assisted Ullmann coupling reaction when the MoS₂ has been activated by pre‐exposing it to hydrogen. Atom‐resolved scanning tunneling microscopy (STM) imaging is used to analyze the bonding of the nanowires, and thereby it is revealed that selective bonding takes place on a specific S atom at the corner site between the two types of zig‐zag edges available in a hexagonal single layer MoS₂ sheet. The method reported here successfully combining synthesis of epitaxial TMDCs and Ullmann coupling reactions on surfaces may open up new synthesis routes for 2D organic‐TMDC hybrid materials.     

Atomic‐Level Customization of 4 in. Transition Metal Dichalcogenide Multilayer Alloys for Industrial Applications

Despite many encouraging properties of transition metal dichalcogenides (TMDs), a central challenge in the realm of industrial applications based on TMD materials is to connect the large‐scale synthesis and reproducible production of highly crystalline TMD materials. Here, the primary aim is to resolve simultaneously the two inversely related issues through the synthesis of MoS_{2(1?x )}Se_2x ternary alloys with customizable bichalcogen atomic (S and Se) ratio via atomic‐level substitution combined with a solution‐based large‐area compatible approach. The relative concentration of bichalcogen atoms in the 2D alloy can be effectively modulated by altering the selenization temperature, resulting in 4 in. scale production of MoS_1.62Se_0.38, MoS_1.37Se_0.63, MoS_1.15Se_0.85, and MoS_0.46Se_1.54 alloys, as well as MoS₂ and MoSe₂. Comprehensive spectroscopic evaluations for vertical and lateral homogeneity in terms of heteroatom distribution in the large‐scale 2D TMD alloys are implemented. Se‐stimulated strain effects and a detailed mechanism for the Se substitution in the MoS₂ crystal are further explored. Finally, the capability of the 2D alloy for industrial application in nanophotonic devices and hydrogen evolution reaction (HER) catalysts is validated. Substantial enhancements in the optoelectronic and HER performances of the 2D ternary alloy compared with those of its binary counterparts, including pure‐phase MoS₂ and MoSe₂, are unambiguously achieved.     

Combining MoS<Subscript>2</Subscript> or MoSe<Subscript>2</Subscript> nanoflakes with carbon by reacting Mo(CO)<Subscript>6</Subscript> with S or Se under their autogenic pressure at elevated temperature

This paper describes a non-aqueous, solvent-free, environmentally friendly, one-pot facile reaction to synthesize inorganic materials inclusion with carbon (MoS₂ or MoSe₂/C) at low temperatures. Nanoflakes of MoS₂ and MoSe₂ inclusion with carbon are prepared by a thermal (750 °C) reaction between Mo(CO)₆ and S or Se at their autogenic pressure in a closed reactor under inert atmosphere. Elemental sulfur or selenium powders are chosen in order to avoid the use of highly toxic H₂S and H₂Se gases. Without further processing of the as-prepared MoS₂/C or MoSe₂/C products, their compositional, morphological and structural characterization are carried out. The possibility of hydrogen storage in as-synthesized MoS₂/C or MoSe₂/C products is examined. A probable reaction mechanism for the formation of MoS₂ or MoSe₂ nanoflakes inclusion with C is discussed.     

Phase Modulation of (1T‐2H)‐MoSe2/TiC‐C Shell/Core Arrays via Nitrogen Doping for Highly Efficient Hydrogen Evolution Reaction

Tailoring molybdenum selenide electrocatalysts with tunable phase and morphology is of great importance for advancement of hydrogen evolution reaction (HER). In this work, phase‐ and morphology‐modulated N‐doped MoSe₂/TiC‐C shell/core arrays through a facile hydrothermal and postannealing treatment strategy are reported. Highly conductive TiC‐C nanorod arrays serve as the backbone for MoSe₂ nanosheets to form high‐quality MoSe₂/TiC‐C shell/core arrays. Impressively, continuous phase modulation of MoSe₂ is realized on the MoSe₂/TiC‐C arrays. Except for the pure 1T‐MoSe₂ and 2H‐MoSe₂, mixed (1T‐2H)‐MoSe₂ nanosheets are achieved in the N‐MoSe₂ by N doping and demonstrated by spherical aberration electron microscope. Plausible mechanism of phase transformation and different doping sites of N atom are proposed via theoretical calculation. The much smaller energy barrier, longer H? Se bond length, and diminished bandgap endow N‐MoSe₂/TiC‐C arrays with substantially superior HER performance compared to 1T and 2H phase counterparts. Impressively, the designed N‐MoSe₂/TiC‐C arrays exhibit a low overpotential of 137 mV at a large current density of 100 mA cm^?2, and a small Tafel slope of 32 mV dec^?1. Our results pave the way to unravel the enhancement mechanism of HER on 2D transition metal dichalcogenides by N doping.     

Anisotropic MoS2 Nanosheets Grown on Self‐Organized Nanopatterned Substrates

Manipulating the anisotropy in 2D nanosheets is a promising way to tune or trigger functional properties at the nanoscale. Here, a novel approach is presented to introduce a one‐directional anisotropy in MoS₂ nanosheets via chemical vapor deposition (CVD) onto rippled patterns prepared on ion‐sputtered SiO₂/Si substrates. The optoelectronic properties of MoS₂ are dramatically affected by the rippled MoS₂ morphology both at the macro‐ and the nanoscale. In particular, strongly anisotropic phonon modes are observed depending on the polarization orientation with respect to the ripple axis. Moreover, the rippled morphology induces localization of strain and charge doping at the nanoscale, thus causing substantial redshifts of the phonon mode frequencies and a topography‐dependent modulation of the MoS₂ workfunction, respectively. This study paves the way to a controllable tuning of the anisotropy via substrate pattern engineering in CVD‐grown 2D nanosheets.     

Coupled Biphase (1T‐2H)‐MoSe2 on Mold Spore Carbon for Advanced Hydrogen Evolution Reaction

Performance breakthrough of MoSe₂‐based hydrogen evolution reaction (HER) electrocatalysts largely relies on sophisticated phase modulation and judicious innovation on conductive matrix/support. In this work the controllable synthesis of phosphate ion (PO₄^3?) intercalation induced‐MoSe₂ (P‐MoSe₂) nanosheets on N‐doped mold spore carbon (N‐MSC) forming P‐MoSe₂/N‐MSC composite electrocatalysts is realized. Impressively, a novel conductive N‐MSC matrix is constructed by a facile mold fermentation method. Furthermore, the phase of MoSe₂ can be modulated by a simple phosphorization strategy to realize the conversion from 2H‐MoSe₂ to 1T‐MoSe₂ to produce biphase‐coexisted (1T‐2H)‐MoSe₂ by PO₄^3‐ intercalation (namely, P‐MoSe₂), confirmed by synchrotron radiation technology and spherical aberration‐corrected TEM (SACTEM). Notably, higher conductivity, lower bandgap and adsorption energy of H⁺ are verified for the P‐MoSe₂/N‐MSC with the help of density functional theory (DFT) calculation. Benefiting from these unique advantages, the P‐MoSe₂/N‐MSC composites show superior HER performance with a low Tafel slope (≈51 mV dec^‐1) and overpotential (≈126 mV at 10 mA cm^‐1) and excellent electrochemical stability, better than 2H‐MoSe₂/N‐MSC and MoSe₂/carbon nanosphere (MoSe₂/CNS) counterparts. This work demonstrates a new kind of carbon material via biological cultivation, and simultaneously unravels the phase transformation mechanism of MoSe₂ by PO₄^3‐ intercalation.     

Lowering the Schottky Barrier Height by Graphene/Ag Electrodes for High‐Mobility MoS2 Field‐Effect Transistors

2D transition metal dichalcogenides (TMDCs) have emerged as promising candidates for post‐silicon nanoelectronics owing to their unique and outstanding semiconducting properties. However, contact engineering for these materials to create high‐performance devices while adapting for large‐area fabrication is still in its nascent stages. In this study, graphene/Ag contacts are introduced into MoS₂ devices, for which a graphene film synthesized by chemical vapor deposition (CVD) is inserted between a CVD‐grown MoS₂ film and a Ag electrode as an interfacial layer. The MoS₂ field‐effect transistors with graphene/Ag contacts show improved electrical and photoelectrical properties, achieving a field‐effect mobility of 35 cm² V^?1 s^?1, an on/off current ratio of 4 × 10⁸, and a photoresponsivity of 2160 A W^?1, compared to those of devices with conventional Ti/Au contacts. These improvements are attributed to the low work function of Ag and the tunability of graphene Fermi level; the n‐doping of Ag in graphene decreases its Fermi level, thereby reducing the Schottky barrier height and contact resistance between the MoS₂ and electrodes. This demonstration of contact interface engineering with CVD‐grown MoS₂ and graphene is a key step toward the practical application of atomically thin TMDC‐based devices with low‐resistance contacts for high‐performance large‐area electronics and optoelectronics.     

Edge‐Riched MoSe2/MoO2 Hybrid Electrocatalyst for Efficient Hydrogen Evolution Reaction

Molybdenum diselenide (MoSe₂) is widely considered as one of the most promising catalysts for the hydrogen evolution reaction (HER). However, the absence of active sites and poor conductivity of MoSe₂ severely restrict its HER performance. By introducing a layer of MoO₂ on Mo foil, MoSe₂/MoO₂ hybrid nanosheets with an abundant edge and high electrical conductivity can be synthesized on the surface of Mo foil. Metallic MoO₂ can improve the charge transport efficiency of MoSe₂/MoO₂, thereby enhancing the overall HER performance. MoSe₂/MoO₂ exhibits fast hydrogen evolution kinetics with a small overpotential of 142 mV versus RHE at a current density of 10 mA cm^?2 and Tafel slope of 48.9 mV dec^?1.     

Directional Construction of Vertical Nitrogen‐Doped 1T‐2H MoSe2/Graphene Shell/Core Nanoflake Arrays for Efficient Hydrogen Evolution Reaction

The low utilization of active sites and sluggish reaction kinetics of MoSe₂ severely impede its commercial application as electrocatalyst for hydrogen evolution reaction (HER). To address these two issues, the first example of introducing 1T MoSe₂ and N dopant into vertical 2H MoSe₂/graphene shell/core nanoflake arrays that remarkably boost their HER activity is herein described. By means of the improved conductivity, rich catalytic active sites and highly accessible surface area as a result of the introduction of 1T MoSe₂ and N doping as well as the unique structural features, the N‐doped 1T‐2H MoSe₂/graphene (N‐MoSe₂/VG) shell/core nanoflake arrays show substantially enhanced HER activity. Remarkably, the N‐MoSe₂/VG nanoflakes exhibit a relatively low onset potential of 45 mV and overpotential of 98 mV (vs RHE) at 10 mA cm^?2 with excellent long‐term stability (no decay after 20 000 cycles), outperforming most of the recently reported Mo‐based electrocatalysts. The success of improving the electrochemical performance via the introduction of 1T phase and N dopant offers new opportunities in the development of high‐performance MoSe₂‐based electrodes for other energy‐related applications.     

Dual‐Native Vacancy Activated Basal Plane and Conductivity of MoSe2 with High‐Efficiency Hydrogen Evolution Reaction

Although transition metal dichalcogenide MoSe₂ is recognized as one of the low‐cost and efficient electrocatalysts for the hydrogen evolution reaction (HER), its thermodynamically stable basal plane and semiconducting property still hamper the electrocatalytic activity. Here, it is demonstrated that the basal plane and edges of 2H‐MoSe₂ toward HER can be activated by introducing dual‐native vacancy. The first‐principle calculations indicate that both the Se and Mo vacancies together activate the electrocatalytic sites in the basal plane and edges of MoSe₂ with the optimal hydrogen adsorption free energy (ΔG_H*) of 0 eV. Experimentally, 2D MoSe₂ nanosheet arrays with a large amount of dual‐native vacancies are fabricated as a catalytic working electrode, which possesses an overpotential of 126 mV at a current density of 100 mV cm^?2, a Tafel slope of 38 mV dec^?1, and an excellent long‐term durability. The findings pave a rational pathway to trigger the activity of inert MoSe₂ toward HER and also can be extended to other layered dichalcogenide.     

Interstitial Mo‐Assisted Photovoltaic Effect in Multilayer MoSe2 Phototransistors

Thin‐film transistors (TFTs) based on multilayer molybdenum diselenide (MoSe₂) synthesized by modified atmospheric pressure chemical vapor deposition (APCVD) exhibit outstanding photoresponsivity (103.1 A W^?1), while it is generally believed that optical response of multilayer transition metal dichalcogenides (TMDs) is significantly limited due to their indirect bandgap and inefficient photoexcitation process. Here, the fundamental origin of such a high photoresponsivity in the synthesized multilayer MoSe₂ TFTs is sought. A unique structural characteristic of the APCVD‐grown MoSe₂ is observed, in which interstitial Mo atoms exist between basal planes, unlike usual 2H phase TMDs. Density functional theory calculations and photoinduced transfer characteristics reveal that such interstitial Mo atoms form photoreactive electronic states in the bandgap. Models indicate that huge photoamplification is attributed to trapped holes in subgap states, resulting in a significant photovoltaic effect. In this study, the fundamental origin of high responsivity with synthetic MoSe₂ phototransistors is identified, suggesting a novel route to high‐performance, multifunctional 2D material devices for future wearable sensor applications.     

Point‐Defect‐Passivated MoS2 Nanosheet‐Based High Performance Piezoelectric Nanogenerator

In this work, a sulfur (S) vacancy passivated monolayer MoS₂ piezoelectric nanogenerator (PNG) is demonstrated, and its properties before and after S treatment are compared to investigate the effect of passivating S vacancy. The S vacancies are effectively passivated by using the S treatment process on the pristine MoS₂ surface. The S vacancy site has a tendency to covalently bond with S functional groups; therefore, by capturing free electrons, a S atom will form a chemisorbed bond with the S vacancy site of MoS₂. S treatment reduces the charge‐carrier density of the monolayer MoS₂ surface, thus the screening effect of piezoelectric polarization charges by free carrier is significantly prevented. As a result, the output peak current and voltage of the S‐treated monolayer MoS₂ nanosheet PNG are increased by more than 3 times (100 pA) and 2 times (22 mV), respectively. Further, the S treatment increases the maximum power by almost 10 times. The results suggest that S treatment can reduce free‐charge carrier by sulfur S passivation and efficiently prevent the screening effect. Thus, the piezoelectric output peaks of current, voltage, and maximum power are dramatically increased, as compared with the pristine MoS₂.     

Temperature‐Related Morphological Evolution of MoS2 Domains on Graphene and Electron Transfer within Heterostructures

Other than the well‐known sulfurization of molybdate compound to synthesize molybdenum disulfide (MoS₂) layers, the dynamic process in the whole crystalline growth from nuclei to triangular domains has been rarely experimentally explored. Here, a competing sulfur‐capture principle jointly with strict epitaxial mechanism is first proposed for the initial topography evolution and the final intrinsic highly oriented growth of triangular MoS₂ domains with Mo or S terminations on the graphene (Gr) template. Additionally, potential distributions on MoS₂ domains and bare Gr are presented to be different due to the charge transfer within heterostructures. The findings offer the mechanism of templated growth of 2D transition metal dichalcogenides, and provide general principles in syntheses of vertical 2D heterostructures that can be applied to electronics.     

Highly Robust Non‐Noble Alkaline Hydrogen‐Evolving Electrocatalyst from Se‐Doped Molybdenum Disulfide Particles on Interwoven CoSe2 Nanowire Arrays

Developing efficient non‐noble and earth‐abundant hydrogen‐evolving electrocatalysts is highly desirable for improving the energy efficiency of water splitting in base. Molybdenum disulfide (MoS₂) is a promising candidate, but its catalytic activity is kinetically retarded in alkaline media due to the unfavorable water adsorption and dissociation feature. A heterogeneous electrocatalyst is reported that is constructed by selenium‐doped MoS₂ (Se‐MoS₂) particles on 3D interwoven cobalt diselenide (CoSe₂) nanowire arrays that drives the hydrogen evolution reaction (HER) with fast reaction kinetics in base. The resultant Se‐MoS₂/CoSe₂ hybrid exhibits an outstanding catalytic HER performance with extremely low overpotentials of 30 and 93 mV at 10 and 100 mA cm^–2 in base, respectively, which outperforms most of the inexpensive alkaline HER catalysts, and is among the best alkaline catalytic activity reported so far. Moreover, this hybrid catalyst shows exceptional catalytic performance with very low overpotentials of 84 and 95 mV at 10 mA cm^–2 in acidic and neutral electrolytes, respectively, implying robust pH universality of this hybrid catalyst. This work may provide new inspirations for the development of high‐performance MoS₂‐based HER electrocatalysts in unfavorable basic media for promising catalytic applications.     

Thermal stability of sputtered Mo/polyimide films and formation of MoSe2 and MoS2 layers for application in flexible Cu(In,Ga)(Se,S)2 based solar cells

Molybdenum (Mo) films with a thickness of about 800 nm were room temperature sputtered onto flexible polymeric substrates. Upilex® films were chosen as substrates on the basis of their high thermal endurance and reduced coefficient of thermal expansion. Thermal stability of Mo films has been proved by heat treatment of the Mo/Upilex® structures at a temperature comparable to that used in the preparation of the Cu(In,Ga)(Se,S)₂ absorber layer. A combination of high optical reflectance (maximum values of 75-80%), low electrical resistivity (about 30 μΩ cm) and a smooth surface free of cracks for heated films highlights their good thermal stability. The formation of MoSe₂ and MoS₂ layers, after selenization/sulfurization of the Mo/Upilex® structures, has been further investigated in view of their application as back contact layers in flexible CIGS based solar cells.     

Temperature‐Triggered Sulfur Vacancy Evolution in Monolayer MoS2/Graphene Heterostructures

The existence of defects in 2D semiconductors has been predicted to generate unique physical properties and markedly influence their electronic and optoelectronic properties. In this work, it is found that the monolayer MoS₂ prepared by chemical vapor deposition is nearly defect‐free after annealing under ultrahigh vacuum conditions at ≈400 K, as evidenced by scanning tunneling microscopy observations. However, after thermal annealing process at ≈900 K, the existence of dominant single sulfur vacancies and relatively rare vacancy chains (2S, 3S, and 4S) is convinced in monolayer MoS₂ as‐grown on Au foils. Of particular significance is the revelation that the versatile vacancies can modulate the band structure of the monolayer MoS₂, leading to a decrease of the bandgap and an obvious n‐doping effect. These results are confirmed by scanning tunneling spectroscopy data as well as first‐principles theoretical simulations of the related morphologies and the electronic properties of the various defect types. Briefly, this work should pave a novel route for defect engineering and hence the electronic property modulation of three‐atom‐thin 2D layered semiconductors.     

Water-Assisted Growth of Twisted 3R-Stacked MoSe2 Spirals and Its Dramatically Enhanced Second Harmonic Generations

Enhanced second-harmonic generation (SHG) responses are reported in monolayer transition metal dichalcogenides (e.g., MX₂, M: Mo, W; X: S, Se) due to the broken symmetries. The 3R-like stacked MX₂ spiral structures possessing the similar broken inversion symmetry should present dramatically enhanced SHG responses, thus providing great flexibility in designing miniaturized on-chip nonlinear optical devices. To achieve this, the first direct synthesis of twisted 3R-stacked chiral molybdenum diselenide (MoSe₂) spiral structures with specific screw dislocations (SD) arms is reported, via designing a water-assisted chemical vapor transport (CVT) approach. The study also clarifies the formation mechanism of the MoSe₂ spiral structures, by precisely regulating the precursor supply accompanying with multiscale characterizations. Significantly, an up to three orders of magnitude enhancement of the SHG responses in twisted 3R stacked MoSe₂ spirals is demonstrated, which is proposed to arise from the synergistic effects of broken inversion symmetry, strong light–matter interaction, and band nesting effects. Briefly, the work provides an efficient synthetic route for achieving the 3R-stacked TMDCs spirals, which can serve as perfect platforms for promoting their applications in on-chip nonlinear optical devices.     

Efficient Hydrogen Evolution Reaction Catalysis in Alkaline Media by All‐in‐One MoS2 with Multifunctional Active Sites

MoS₂ becomes an efficient and durable nonprecious‐metal electrocatalyst for the hydrogen evolution reaction (HER) when it contains multifunctional active sites for water splitting derived from 1T‐phase, defects, S vacancies, exposed Mo edges with expanded interlayer spacings. In contrast to previously reported MoS₂‐based catalysts targeting only a single or few of these characteristics, the all‐in‐one MoS₂ catalyst prepared herein features all of the above active site types. During synthesis, the intercalation of in situ generated NH₃ molecules into MoS₂ sheets affords ammoniated MoS₂ (A‐MoS₂) that predominantly comprises 1T‐MoS₂ and exhibits an expanded interlayer spacing. The subsequent reduction of A‐MoS₂ results in the removal of intercalated NH₃ and H₂S to form an all‐in‐one MoS₂ with multifunctional active sites mentioned above (R‐MoS₂) that exhibits electrocatalytic HER performance in alkaline media superior to those of all previously reported MoS₂‐based electrocatalysts. In particular, a hybrid MoS₂/nickel foam catalyst outperforms commercial Pt/C in the practically meaningful high‐current region (>25 mA cm^?2), demonstrating that R‐MoS₂‐based materials can potentially replace Pt catalysts in practical alkaline HER systems.     

In Situ Fabrication of Vertical Multilayered MoS2/Si Homotype Heterojunction for High‐Speed Visible–Near‐Infrared Photodetectors

c2D transition metal dichalcogenides (TMDCs)‐based heterostructures have been demonstrated to achieve superior light absorption and photovoltaic effects theoretically and experimentally, making them extremely attractive for realizing optoelectronic devices. In this work, a vertical multilayered n‐MoS₂/n‐silicon homotype heterojunction is fabricated, which takes advantage of multilayered MoS₂ grown in situ directly on plane silicon. Electrical characterization reveals that the resultant device exhibits high sensitivity to visible–near‐infrared light with responsivity up to 11.9 A W^–1. Notably, the photodetector shows high‐speed response time of ≈30.5 µs/71.6 µs and capability to work under higher pulsed light irradiation approaching 100 kHz. The high response speed could be attributed to a good quality of the multilayer MoS₂, as well as in situ device fabrication process. These findings suggest that the multilayered MoS₂/Si homotype heterojunction have great potential application in the field of visible–near‐infrared detection and might be used as elements for construction of high‐speed integrated optoelectronic sensor circuitry.     

Wafer‐Scale Synthesis of Reliable High‐Mobility Molybdenum Disulfide Thin Films via Inhibitor‐Utilizing Atomic Layer Deposition

A reliable and rapid manufacturing process of molybdenum disulfide (MoS₂) with atomic‐scale thicknesses remains a fundamental challenge toward its successful incorporation into high‐performance nanoelectronics. It is imperative to achieve rapid and scalable production of MoS₂ exhibiting high carrier mobility and excellent on/off current ratios simultaneously. Herein, inhibitor‐utilizing atomic layer deposition (iALD) is presented as a novel method to meet these requirements at the wafer scale. The kinetics of the chemisorption of Mo precursors in iALD is governed by the reaction energy and the steric hindrance of inhibitor molecules. By optimizing the inhibition of Mo precursor absorption, the nucleation on the substrate in the initial stage can be spontaneously tailored to produce iALD‐MoS₂ thin films with a significantly increased grain size and surface coverage (>620%). Moreover, highly crystalline iALD‐MoS₂ thin films, with thicknesses of only a few layers, excellent room temperature mobility (13.9 cm² V^?1 s^?1), and on/off ratios (>10⁸), employed as the channel material in field effect transistors on 6″ wafers, are successfully prepared.