Controllable synthesis of MoS<Subscript>2</Subscript> nanostructures from monolayer flakes,few-layer pyramids to multilayer blocks by catalyst-assisted thermal evaporation

Molybdenum disulfide (MoS₂), as a representative of two-dimensional layered materials, has been extensively investigated due to their unique structure and interesting electronic and optical properties. However, the controllable synthesis of monolayer and pyramidal MoS₂ nanostructures needs improvement, and their growth mechanism requires more investigations. Here, uniform MoS₂ nanostructures from monolayer flakes, few-layer pyramids to multilayer blocks were successfully fabricated by a catalyst-assisted thermal-evaporation-based chemical vapor deposition method via simply adjusting the carrier Ar gas flow rate. After the comprehensive characterization on the obtained materials, their nucleation and growth mechanisms were proposed with specifically highlighting the influence of the carrier gas flow rate, which might also be of help to understand the synthesis processes of other two-dimensional semiconducting transition metal dichalcogenides by similar method.     

Contact‐Engineered Electrical Properties of MoS2 Field‐Effect Transistors via Selectively Deposited Thiol‐Molecules

Although 2D molybdenum disulfide (MoS₂) has gained much attention due to its unique electrical and optical properties, the limited electrical contact to 2D semiconductors still impedes the realization of high‐performance 2D MoS₂‐based devices. In this regard, many studies have been conducted to improve the carrier‐injection properties by inserting functional paths, such as graphene or hexagonal boron nitride, between the electrodes and 2D semiconductors. The reported strategies, however, require relatively time‐consuming and low‐yield transfer processes on sub‐micrometer MoS₂ flakes. Here, a simple contact‐engineering method is suggested, introducing chemically adsorbed thiol‐molecules as thin tunneling barriers between the metal electrodes and MoS₂ channels. The selectively deposited thiol‐molecules via the vapor‐deposition process provide additional tunneling paths at the contact regions, improving the carrier‐injection properties with lower activation energies in MoS₂ field‐effect transistors. Additionally, by inserting thiol‐molecules at the only one contact region, asymmetric carrier‐injection is feasible depending on the temperature and gate bias.     

Au NPs@MoS2 Sub‐Micrometer Sphere‐ZnO Nanorod Hybrid Structures for Efficient Photocatalytic Hydrogen Evolution with Excellent Stability

MoS₂ shows promising applications in photocatalytic water splitting, owing to its uniquely optical and electric properties. However, the insufficient light absorption and lack of performance stability are two crucial issues for efficient application of MoS₂ nanomaterials. Here, Au nanoparticles (NPs)@MoS₂ sub‐micrometer sphere‐ZnO nanorod (Au NPs@MoS₂‐ZnO) hybrid photocatalysts have been successfully synthesized by a facile process combining the hydrothermal method and seed‐growth method. Such photocatalysts exhibit high efficiency and excellent stability for hydrogen production via multiple optical‐electrical effects. The introduction of Au NPs to MoS₂ sub‐micrometer spheres forming a core–shell structure demonstrates strong plasmonic absorption enhancement and facilitates exciton separation. The incorporation of ZnO nanorods to the Au NPs@MoS₂ hybrids further extends the light absorption to a broader wavelength region and enhances the exciton dissociation. In addition, mutual contacts between Au NPs (or ZnO nanorods) and the MoS₂ spheres effectively protect the MoS₂ nanosheets from peeling off from the spheres. More importantly, efficiently multiple exciton separations help to restrain the MoS₂ nanomaterials from photocorrosion. As a result, the Au@MoS₂‐ZnO hybrid structures exhibit an excellent hydrogen gas evolution (3737.4 μmol g^?1) with improved stability (91.9% of activity remaining) after a long‐time test (32 h), which is one of the highest photocatalytic activities to date among the MoS₂ based photocatalysts.     

Epitaxial Single‐Layer MoS2 on GaN with Enhanced Valley Helicity

Engineering the substrate of 2D transition metal dichalcogenides can couple the quasiparticle interaction between the 2D material and substrate, providing an additional route to realize conceptual quantum phenomena and novel device functionalities, such as realization of a 12‐time increased valley spitting in single‐layer WSe₂ through the interfacial magnetic exchange field from a ferromagnetic EuS substrate, and band‐to‐band tunnel field‐effect transistors with a subthreshold swing below 60 mV dec⁻¹ at room temperature based on bilayer n‐MoS₂ and heavily doped p‐germanium, etc. Here, it is demonstrated that epitaxially grown single‐layer MoS₂ on a lattice‐matched GaN substrate, possessing a type‐I band alignment, exhibits strong substrate‐induced interactions. The phonons in GaN quickly dissipate the energy of photogenerated carriers through electron–phonon interaction, resulting in a short exciton lifetime in the MoS₂/GaN heterostructure. This interaction enables an enhanced valley helicity at room temperature (0.33 ± 0.05) observed in both steady‐state and time‐resolved circularly polarized photoluminescence measurements. The findings highlight the importance of substrate engineering for modulating the intrinsic valley carriers in ultrathin 2D materials and potentially open new paths for valleytronics and valley‐optoelectronic device applications.     

Transient SHG Imaging on Ultrafast Carrier Dynamics of MoS2 Nanosheets

Understanding the collaborative behaviors of the excitons and phonons that result from light–matter interactions is important for interpreting and optimizing the underlying fundamental physics at work in devices made from atomically thin materials. In this study, the generation of exciton‐coupled phonon vibration from molybdenum disulfide (MoS₂) nanosheets in a pre‐excitonic resonance condition is reported. A strong rise‐to‐decay profile for the transient second‐harmonic generation (TSHG) of the probe pulse is achieved by applying substantial (20%) beam polarization normal to the nanosheet plane, and tuning the wavelength of the pump beam to the absorption of the A‐exciton. The time‐dependent TSHG signals clearly exhibit acoustic phonon generation at vibration modes below 10 cm^?1 (close to the Γ point) after the photoinduced energy is transferred from exciton to phonon in a nonradiative fashion. Interestingly, by observing the TSHG signal oscillation period from MoS₂ samples of varying thicknesses, the speed of the supersonic waves generated in the out‐of‐plane direction (Mach 8.6) is generated. Additionally, TSHG microscopy reveals critical information about the phase and amplitude of the acoustic phonons from different edge chiralities (armchair and zigzag) of the MoS₂ monolayers. This suggests that the technique could be used more broadly to study ultrafast physics and chemistry in low‐dimensional materials and their hybrids with ultrahigh fidelity.     

Tuning Excitonic Properties of Monolayer MoS2 with Microsphere Cavity by High‐Throughput Chemical Vapor Deposition Method

Tuning the optical properties of 2D direct bandgap semiconductors is crucial for applications in photonic light source, optical communication, and sensing. In this work, the excitonic properties of molybdenum disulphide (MoS₂) are successfully tuned by directly depositing it onto silica microsphere resonators using chemical vapor deposition method. Multiple whispering gallery mode (WGM) peaks in the emission wavelength range of ≈650–750 nm are observed under continuous wave excitation at room temperature. Time‐resolved photoluminescence (TRPL) and femtosecond transient absorption (TA) spectroscopy are conducted to study light‐matter interaction dynamics of the MoS₂ microcavities. TRPL study suggests radiative recombination rate of carrier‐phonon scattering and interband transition processes in MoS₂ is enhanced by a factor of ≈1.65 due to Purcell effect in microcavities. TA spectroscopy study shows modulation of the interband transition process mainly occurs at PB‐A band with an estimated F ≈ 1.60. Furthermore, refractive index sensing utilizing WGM peaks of MoS₂ is established with sensitivity up to ≈150 nm per refractive index unit. The present work provides a large‐scale and straightforward method for coupling atomically thin 2D gain media with cavities for high‐performance optoelectronic devices and sensors.     

Polaronic Trions at the MoS2/SrTiO3 Interface

The reduced electrical screening in 2D materials provides an ideal platform for realization of exotic quasiparticles, that are robust and whose functionalities can be exploited for future electronic, optoelectronic, and valleytronic applications. Recent examples include an interlayer exciton, where an electron from one layer binds with a hole from another, and a Holstein polaron, formed by an electron dressed by a sea of phonons. Here, a new quasiparticle is reported, “polaronic trion” in a heterostructure of MoS₂/SrTiO₃ (STO). This emerges as the Fröhlich bound state of the trion in the atomically thin monolayer of MoS₂ and the very unique low energy soft phonon mode (≤7 meV, which is temperature and field tunable) in the quantum paraelectric substrate STO, arising below its structural antiferrodistortive (AFD) phase transition temperature. This dressing of the trion with soft phonons manifests in an anomalous temperature dependence of photoluminescence emission leading to a huge enhancement of the trion binding energy (≈70 meV). The soft phonons in STO are sensitive to electric field, which enables field control of the interfacial trion–phonon coupling and resultant polaronic trion binding energy. Polaronic trions could provide a platform to realize quasiparticle‐based tunable optoelectronic applications driven by many body effects.     

Broadband Extrinsic Self‐Trapped Exciton Emission in Sn‐Doped 2D Lead‐Halide Perovskites

As emerging efficient emitters, metal‐halide perovskites offer the intriguing potential to the low‐cost light emitting devices. However, semiconductors generally suffer from severe luminescence quenching due to insufficient confinement of excitons (bound electron–hole pairs). Here, Sn‐triggered extrinsic self‐trapping of excitons in bulk 2D perovskite crystal, PEA₂PbI₄ (PEA = phenylethylammonium), is reported, where exciton self‐trapping never occurs in its pure state. By creating local potential wells, isoelectronic Sn dopants initiate the localization of excitons, which would further induce the large lattice deformation around the impurities to accommodate the self‐trapped excitons. With such self‐trapped states, the Sn‐doped perovskites generate broadband red‐to‐near‐infrared (NIR) emission at room temperature due to strong exciton–phonon coupling, with a remarkable quantum yield increase from 0.7% to 6.0% (8.6 folds), reaching 42.3% under a 100 mW cm^?2 excitation by extrapolation. The quantum yield enhancement stems from substantial higher thermal quench activation energy of self‐trapped excitons than that of free excitons (120 vs 35 meV). It is further revealed that the fast exciton diffusion involves in the initial energy transfer step by transient absorption spectroscopy. This dopant‐induced extrinsic exciton self‐trapping approach paves the way for extending the spectral range of perovskite emitters, and may find emerging application in efficient supercontinuum sources.     

Probing Defect‐Induced Midgap States in MoS2 Through Graphene–MoS2 Heterostructures

Crystalline defects in MoS₂ may induce midgap states, resulting in low carrier mobility. These midgap states are usually difficult to probe by conventional transport measurement. The quantum capacitance of single‐layer graphene is sensitive to defect‐induced states near the Dirac point, at which the density of states is extremely low. It is reported that the hexagonal‐boron nitride/graphene/MoS₂ sandwich structure facilitates the exploration of the properties of those midgap states in MoS₂. Comparative results of the quantum capacitance of pristine graphene indicate the presence of several midgap states with distinct features. Some of these states donate electrons while some states lead to localization of electrons. It is believed that these midgap states originate from intrinsic point defects such as sulfur vacancies, which have a significant impact on the property of the MoS₂/graphene interface. They are responsible for the contact problems of metal/MoS­₂ interfaces.     

Electrically Pumped White‐Light‐Emitting Diodes Based on Histidine‐Doped MoS2 Quantum Dots

MoS₂ quantum dots (QDs)‐based white‐light‐emitting diodes (QD‐WLEDs) are designed, fabricated, and demonstrated. The highly luminescent, histidine‐doped MoS₂ QDs synthesized by microwave induced fragmentation of 2D MoS₂ nanoflakes possess a wide distribution of available electronic states as inferred from the pronounced excitation‐wavelength‐dependent emission properties. Notably, the histidine‐doped MoS₂ QDs show a very strong emission intensity, which exceeds seven times of magnitude larger than that of pristine MoS₂ QDs. The strongly enhanced emission is mainly attributed to nitrogen acceptor bound excitons and passivation of defects by histidine‐doping, which can enhance the radiative recombination drastically. The enabled electroluminescence (EL) spectra of the QD‐WLEDs with the main peak around 500 nm are found to be consistent with the photoluminescence spectra of the histidine‐doped MoS₂ QDs. The enhanced intensity of EL spectra with the current increase shows the stability of histidine‐doped MoS₂ based QD‐WLEDs. The typical EL spectrum of the novel QD‐WLEDs has a Commission Internationale de l'Eclairage chromaticity coordinate of (0.30, 0.36) exhibiting an intrinsic broadband white‐light emission. The unprecedented and low‐toxicity QD‐WLEDs based on a single light‐emitting material can serve as an excellent alternative for using transition metal dichalcogenides QDs as next generation optoelectronic devices.     

Continuous Low‐Bias Switching of Superconductivity in a MoS2 Transistor

Engineering the properties of quantum electron systems, e.g., tuning the superconducting phase using low driving bias within an easily accessible temperature range, is of great interest for exploring exotic physical phenomena as well as achieving real applications. Here, the realization of continuous field‐effect switching between superconducting and non‐superconducting states in a few‐layer MoS₂ transistor is reported. Ionic‐liquid gating induces the superconducting state close to the quantum critical point on the top surface of the MoS₂, and continuous switching between the super/non‐superconducting states is achieved by HfO₂ back gating. The superconducting transistor works effectively in the helium‐4 temperature range and requires a gate bias as low as ≈10 V. The dual‐gate device structure and strategy presented here can be easily generalized to other systems, opening new opportunities for designing high‐performance 2D superconducting transistors.     

Controllable defects implantation in MoS<Subscript>2</Subscript> grown by chemical vapor deposition for photoluminescence enhancement

Photoluminescence (PL) of transition metal dichalcogenides (TMDs) can be engineered by controlling the density of defects, which provide active sites for electron-hole recombination, either radiatively or non-radiatively. However, the implantation of defects by external stimulation, such as uniaxial tension and irradiation, tends to introduce local damages or structural non-homogeneity, which greatly degrades their luminescence properties and impede their applicability in constructing optoelectronic devices. In this paper, we present a strategy to introduce a controllable level of defects into the MoS₂ monolayers by adding a hydrogen flow during the chemical vapor deposition, without sacrificing their luminescence characteristics. The density of the defect is controlled directly by the concentration of hydrogen. For an appropriate hydrogen flux, the monolayer MoS₂ sheets have three times stronger PL emission at the excitonic transitions, compared with those samples with nearly perfect crystalline structure. The defect-bounded exciton transitions at lower energies arising in the defective samples and are maximized when the total PL is the strongest. However, the B exciton, exhibits a monotonic decline as the defect density increases. The Raman spectra of the defective MoS₂ reveal a redshift (blueshift) of the in-plane (out-of-plane) vibration modes as the hydrogen flux increases. All the evidence indicates that the generated defects are in the form of sulfur vacancies. This study renders the high-throughput synthesis of defective MoS₂ possible for catalysis or light emitting applications.

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Enhanced Field‐Emission Behavior of Layered MoS2 Sheets

Field emission studies are reported for the first time on layered MoS₂ sheets at the base pressure of ～1 × 10^?8 mbar. The turn‐on field required to draw a field emission current density of 10 μA/cm² is found to be 3.5 V/μm for MoS₂ sheets. The turn‐on values are found to be significantly lower than the reported MoS₂ nanoflowers, graphene, and carbon nanotube‐based field emitters due to the high field enhancement factor (～1138) associated with nanometric sharp edges of MoS₂ sheet emitter surface. The emission current–time plots show good stability over a period of 3 h. Owing to the low turn‐on field and planar (sheetlike) structure, the MoS₂ could be utilized for future vacuum microelectronics/nanoelectronic and flat panel display applications.     

Tunneling Photocurrent Assisted by Interlayer Excitons in Staggered van der Waals Hetero‐Bilayers

Vertically stacked van der Waals (vdW) heterostructures have been suggested as a robust platform for studying interfacial phenomena and related electric/optoelectronic devices. While the interlayer Coulomb interaction mediated by the vdW coupling has been extensively studied for carrier recombination processes in a diode transport, its correlation with the interlayer tunneling transport has not been elucidated. Here, a contrast is reported between tunneling and drift photocurrents tailored by the interlayer coupling strength in MoSe₂/MoS₂ hetero‐bilayers (HBs). The interfacial coupling modulated by thermal annealing is identified by the interlayer phonon coupling in Raman spectra and the emerging interlayer exciton peak in photoluminescence spectra. In strongly coupled HBs, positive photocurrents are observed owing to the inelastic band‐to‐band tunneling assisted by interlayer excitons that prevail over exciton recombinations. By contrast, weakly coupled HBs exhibit a negative photovoltaic diode behavior, manifested as a drift current without interlayer excitonic emissions. This study sheds light on tailoring the tunneling transport for numerous optoelectronic HB devices.     

A Novel and Facile Route to Synthesize Atomic‐Layered MoS2 Film for Large‐Area Electronics

High‐quality and large‐area molybdenum disulfide (MoS₂) thin film is highly desirable for applications in large‐area electronics. However, there remains a challenge in attaining MoS₂ film of reasonable crystallinity due to the absence of appropriate choice and control of precursors, as well as choice of suitable growth substrates. Herein, a novel and facile route is reported for synthesizing few‐layered MoS₂ film with new precursors via chemical vapor deposition. Prior to growth, an aqueous solution of sodium molybdate as the molybdenum precursor is spun onto the growth substrate and dimethyl disulfide as the liquid sulfur precursor is supplied with a bubbling system during growth. To supplement the limiting effect of Mo (sodium molybdate), a supplementary Mo is supplied by dissolving molybdenum hexacarbonyl (Mo(CO)₆) in the liquid sulfur precursor delivered by the bubbler. By precisely controlling the amounts of precursors and hydrogen flow, full coverage of MoS₂ film is readily achievable in 20 min. Large‐area MoS₂ field effect transistors (FETs) fabricated with a conventional photolithography have a carrier mobility as high as 18.9 cm² V^?1 s^?1, which is the highest reported for bottom‐gated MoS₂‐FETs fabricated via photolithography with an on/off ratio of ≈10⁵ at room temperature.     

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.     

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.     

In Situ Synthesis of Few‐Layered g‐C3N4 with Vertically Aligned MoS2 Loading for Boosting Solar‐to‐Hydrogen Generation

In artificial photocatalytic hydrogen evolution, effective incident photon absorption and a high‐charge recombination rate are crucial factors influencing the overall efficiency. Herein, a traditional solid‐state synthesis is used to obtain, for the first time, novel samples of few‐layered g‐C₃N₄ with vertically aligned MoS₂ loading (MoS₂/C₃N₄). Thiourea and layered MoO₃ are chosen as precursors, as they react under nitrogen atmosphere to in situ produce the products. According to the quasi‐Fourier transform infrared reflectance and X‐ray diffraction measurements, the detailed reaction process is determined to proceed through the confirmed formation pathway. The two precursor units MoS₂ and C₃N₄ are linked by Mo? N bonds, which act as electronic receivers/conductors and hydrogen‐generation sites. Density functional theory is also carried out, which determines that the interface sites act as electron‐accumulation regions. According to the photoelectrochemical results, MoS₂/C₃N₄ can achieve a current of 0.05 mA cm^?2, which is almost ten times higher than that of bare g‐C₃N₄ or the MoS₂/C₃N₄‐R reference samples. The findings in the present work pave the way to not only synthesize a series of designated samples but also thoroughly understand the solid‐state reaction.     

Preparation of MoS2‐Polyvinylpyrrolidone Nanocomposites for Flexible Nonvolatile Rewritable Memory Devices with Reduced Graphene Oxide Electrodes

A facile method for exfoliation and dispersion of molybdenum disulfide (MoS₂) with the aid of polyvinylpyrrolidone (PVP) is proposed. The resultant PVP‐coated MoS₂ nanosheets, i.e., MoS₂‐PVP nanocomposites, are well dispersed in the low‐boiling ethanol solvent, facilitating their thin film preparation and the device fabrication by solution processing technique. As a proof of concept, a flexible memory diode with the configuration of reduced graphene oxide (rGO)/MoS₂‐PVP/Al exhibited a typical bistable electrical switching and nonvolatile rewritable memory effect with the function of flash. These experimental results prove that the electrical transition is due to the charge trapping and detrapping behavior of MoS₂ in the PVP dielectric material. This study paves a way of employing two‐dimensional nanomaterials as both functional materials and conducting electrodes for the future flexible data storage.     

High pressure and time resolved luminescence spectra of Gd3Ga5O12:Pr crystal

Luminescence spectra and time resolved luminescence spectra of GGG crystal doped with Pr³⁺ were measured at high hydrostatic pressure from ambient to 220 kbar. Effect of pressure results in the red shift of all luminescence lines related to Pr³⁺ ion emission equals from −0.32 to −1.02 cm⁻¹/kbar and in the diminishing of the luminescence lifetimes. The luminescence decay related to emission from ³P₀ state was single-exponential and diminished with pressure from 23 μs at ambient pressure to 6.5 μs at 165 kbar. Luminescence decay related to transition form ¹D₂ state was two-exponential with longer decay equal to 162 μs at ambient pressure and 120 μs at 165 kbar. We discussed effect of pressure on the ¹D₂ → ³H₄ luminescence and emission from ³P₀ state in the context of non-radiative processes that depopulate the ³P₀ and populate the ¹D₂ state, considering mainly multiphonon relaxation processes and depopulation via the praseodymium trapped exciton state.