Giant two‐photon absorption in monolayer MoS2

Strong two‐photon absorption (TPA) in monolayer MoS₂ is demonstrated in contrast to saturable absorption (SA) in multilayer MoS₂ under the excitation of femtosecond laser pulses in the near‐infrared region. MoS₂ in the forms of monolayer single crystal and multilayer triangular islands are grown on either quartz or SiO₂/Si by employing the seeding method through chemical vapor deposition. The nonlinear transmission measurements reveal that monolayer MoS₂ possesses a nonsaturation TPA coefficient as high as ∼(7.62 ±0.15) ×10³ cm/GW, larger than that of conventional semiconductors by a factor of 10³. As a result of TPA, two‐photon pumped frequency upconverted luminescence is observed directly in the monolayer MoS₂. For the multilayer MoS₂, the SA response is demonstrated with the ratio of the excited‐state absorption cross section to ground‐state cross section of ∼0.18. In addition, the laser damage threshold of the monolayer MoS₂ is ∼97 GW/cm², larger than that of the multilayer MoS₂ of ∼78 GW/cm².

     

Light Auxiliary Hydrogen‐Evolution Catalyst Based on Uniformly Pt Nanoparticles Decorated Molybdenum Sulfide Hybrids

The electrocatalytic splitting of water via hydrogen evolution reaction (HER) is one of the most efficient technologies for hydrogen production, while the massive consumption of precious Pt‐based catalysts hinders its commercialization, bringing an urgent task to explore low‐cost and earth‐abundant alternatives. Herein, a cost‐efficient system composed of metal Pt/molybdenum disulphide (MoS₂) nanosheets hybrids for the HER by auxiliary of solar light is reported. The uniformly Pt nanoparticle decorated MoS₂ sheets can be easily obtained under hydrothermal condition using oleylamine as capping agent and N,N‐dimethylmethanamide (DMF) as intercalation molecule for MoS₂ exfoliation. The Pt/MoS₂ hybrid shows a significantly enhanced HER activity compared with bare MoS₂ due to enhancing conductivity and reducing overpotential by electron transport between Pt and MoS₂. As a result, a Tafel slope of 38 mV per decade is obtained, suggesting a highly efficient Volmer–Heyrovsky reaction of hydrogen evolution.     

Robust Fabrication of Quantum Dots on Few‐Layer MoS2 by Soft Hydrogen Plasma and Post‐Annealing

Apart from unique properties of layered transition‐metal dichalcogenide nanosheets like MoS₂, quantum dots (QDs) from these layered materials promise novel science and applications due to their quantum confinement effect. However, the reported fabrication techniques for such QDs all involve the use of liquid organic solvents and the final material extraction from such liquid dispersions. Here a novel and convenient dry method for the synthesis of MoS₂ quantum dots interspersed on few‐layer MoS₂ using soft hydrogen plasma treatment followed by post‐annealing is demonstrated. The size of MoS₂ nanodots can be well controlled by adjusting the working pressure of hydrogen plasma and post‐thermal annealing. This method relies on the cumulative hydrogen ion bombardment effect which can destroy the hexagonal structure of the top MoS₂ layer and disintegrate the top layer into MoS₂ nanodots and even QDs. Post‐thermal annealing can further reduce the size. Such MoS₂ quantum dots interspersed on few‐layer MoS₂ exhibit two new photoluminescence peaks at around 575 nm because of the quantum confinement effect. This dry method is versatile, scalable, and compatible with the semiconductor manufacturing processes, and can be extended to other layered materials for applications in hydrogen evolution reaction, catalysis, and energy devices.     

Electronic and optical properties of single-layer MoS<Subscript>2</Subscript>

The electronic structures of a MoS₂ monolayer are investigated with the all-electron first principle calculations based on the density functional theory (DFT) and the spin-orbital couplings (SOCs). Our results show that the monolayer MoS₂ is a direct band gap semiconductor with a band gap of 1.8 eV. The SOCs and d-electrons in Mo play a very significant role in deciding its electronic and optical properties. Moreover, electronic elementary excitations are studied theoretically within the diagrammatic self-consistent field theory. Under random phase approximation, it shows that two branches of plasmon modes can be achieved via the conduction-band transitions due to the SOCs, which are different from the plasmons in a two-dimensional electron gas and graphene owing to the quasi-linear energy dispersion in single-layer MoS₂. Moreover, the strong optical absorption up to 10⁵ cm^-1 and two optical absorption edges I and II can be observed. This study is relevant to the applications of monolayer MoS₂ as an advanced photoelectronic device.     

Enhanced Exfoliation Effect of Solid Auxiliary Agent On the Synthesis of Biofunctionalized MoS2 Using Grindstone Chemistry

Mass production and commercial availability are prerequisites for the viability and wide application of MoS₂. Here, we demonstrate enhanced grindstone chemistry for a one‐step synthesis of biofunctionalized MoS₂. By adding a SiO₂ auxiliary agent the exfoliation efficiency increases from 16.23% to 58.59% and a rapid and high‐yield exfoliation of MoS₂ is seen. SiO₂ exhibits a fragmentation effect, which reduces the lateral size and facilitates the exfoliation of MoS₂, thus inducing a high‐efficient paradigm in the top‐down fabrication of biofunctionalized MoS₂ nanosheets. The as‐prepared MoS₂‐chitosan (MoS₂‐CS) nanosheets display complete disaggregation and homogeneous dispersion, as well as a high content of chitosan (ca. 20 wt%). As a proof‐of‐concept application, the MoS₂‐CS nanosheets act as a biosorbent for Pb^II removal, exhibiting a good adsorption capacity and recyclability. This green and facile enhanced grindstone chemistry with minimal use of organic solvents and high‐throughput efficiency can be extended to the fabrication of other biocompatible inorganic 2D analogues for a variety of applications.     

Giant Three‐Photon Absorption in Monolayer MoS2 and Its Application in Near‐Infrared Photodetection

For decades, there has been extensive research on exploring fundamental physical mechanisms for strong and fast optical nonlinearities. One of the important nonlinear‐optical mechanisms is multiphoton absorption which has a wide range of photonic applications. Herein, a theoretical model is proposed for three‐photon absorption (3PA) in monolayer MoS₂. The model shows that the 3PA coefficients are on the order of 0.1 cm³/GW². As compared to bulk semiconductors, these coefficients are enhanced by several orders of magnitude due to excitonic effects. Such exciton‐enhanced 3PA is validated by light‐intensity‐dependent photocurrent measurements on a monolayer MoS₂ photodetector with femtosecond laser pulses. These results lay both theoretical and experimental foundation for developing sensitive near‐infrared MoS₂‐based three‐photon detectors.     

Templated synthesis of plate-like MoS<Subscript>2</Subscript> nanosheets assisted with HNTs and their tribological performance in oil

Two-dimensional MoS₂ nanosheets were synthesized by using halloysite nanotubes (HNTs) as template under the hydrothermal synthesis. The structure and morphology of the as-synthesized MoS₂ nanosheets were determined by a series of characterizations. The results showed that the as-synthesized MoS₂ nanosheets were of the plate-like structure with about five layers, and the basal spacing was about 0.63 nm. It was demonstrated that HNTs played a crucial template role in the formation of the plate-like MoS₂ nanosheets. The formation mechanism was proposed. Furthermore, the tribological performance of the as-prepared MoS₂ nanosheets in oil was intensively examined on the ball-on-ball wear tester. The testing results verified that the as-prepared MoS₂ nanosheets as additive could significantly improve the friction performance of oil, which exhibited the good antifriction, antiwear, and load-carrying properties.     

High-efficiency preparation of oil-dispersible MoS<Subscript>2</Subscript> nanosheets with superior anti-wear property in ultralow concentration

Molybdenum disulfide (MoS₂) nanosheets are a promising lubricant additive for enhanced engine efficiency in cars. However, high-cost production methods and poor dispersion have limited their application in industry. In this study, the ball milling process is demonstrated as a low-cost and high-efficient method for fabrication of oil-dispersible MoS₂ nanosheet, and the ball milling parameters are optimized. Moreover, the lubrication effectiveness of ball-milled MoS₂ nanosheet was also evaluated. Results indicated that well-dispersed MoS₂ nanosheets with a size of 250 nm can be manufactured with optimized surfactants of zinc dialkyldithiphosphates (ZDDP) and polyisobutylene succinimide (PIBS) after being ball milled for 36 h. Tribological results revealed that a friction coefficient of white oil with 0.25% MoS₂ nanosheets reached 0.075, much lower than that of lubricant without nanosheets (0.16). The wear scar radius of 0.015% MoS₂ nanosheets was similar with that of Hertz contact, and the wear scar radius reduction reached 20% compared with that of 1% ZDDP. In addition, EDS and XPS results indicated the formation of a MoS₂ and FeS tribofilm on the wear surface.     

Temperature dependence of the dielectric function of monolayer MoS2

An analytic expression of the dielectric function of monolayer molybdenum disulfide (MoS₂) ε?=?ε₁ + iε₂ is presented for energies from 1.4 to 6.0?eV and temperatures from 35 to 350?K. The dielectric function parametric model is used to express ε as a sum of polynomials, which naturally includes asymmetry of critical-point lineshapes. The temperature dependence is achieved by fitting model parameters. In this way, the dielectric function of MoS₂ for arbitrary temperature can be calculated. We observed the fundamental absorption peak, which occurs at the K point of the Brillouin zone. These results are expected to be useful in designing and understanding applied-device technologies based on monolayer MoS₂.     

Alkali-metal-embedded in monolayer MoS<Subscript>2</Subscript>: optical properties and work functions

Embedding alkali-metal in monolayer MoS₂ has been investigated by using first principles with density functional theory. The calculation of the electronic and optical properties indicates that alkali-metal was embedded in monolayer MoS₂ appearing almost metallic behavior, and the MoS₂ layer shows clear p-type doping behavior. The covalent bonding appears between the alkali-metal atoms and defective MoS₂. More importantly, embedding alkali-metal can increase the work function for monolayer MoS₂. Furthermore, the absorption spectrum of monolayer MoS₂ is red shifted because of alkali metal embedding. Accordingly, this study will provide the theoretical basis for producing the alkali-metal-doped monolayer MoS₂ radiation shielding and photoelectric devices.     

Photodeposition of ultrathin MoS<Subscript>2</Subscript> nanosheets onto cubic CdS for efficient photocatalytic H<Subscript>2</Subscript> evolution

In this work, the photocatalyst composed of ultrathin MoS₂ nanosheets onto the surface of cubic CdS nanoparticles with an average diameter of 7~10 nm has been successfully fabricated through a facile and mild photodeposition route. The ultrathin MoS₂ nanosheets as a cocatalyst were demonstrated to greatly boost photocatalytic H₂ evolution over cubic CdS upon visible light irradiation. It was clearly revealed that both the cubic CdS substrate and structure of ultrathin MoS₂ nanosheets play critical roles in the observed efficient H₂ evolution. The cubic CdS offers a strong adherence for ultrathin MoS₂ nanosheets to form a well contact interface, across which the photogenerated charge transfer and charge separation are achieved. The ultrathin MoS₂ nanosheets introduce a high density of unsaturated active S atoms for H₂ evolution.     

A novel optical property induced by MO,S vacancy and V-doped in monolayer MoS2

The electronic structure and optical properties of Mo, S vacancy and V doping in MoS₂ monolayer will be investigated through first-principles calculations based on the density functional theory. The results indicate that the MoS₂ with Mo, S vacancy and V doping (Mo₁₄VS₃₂, Mo₁₅VS₃₁ and Mo₁₄VS₃₁) will gain the property of magnetic semiconductor with the magnetic moment of 1 μB, 1 μB and 0.95 μB, respectively. The optical properties of these V-doped and vacancy defect structures all reflect the phenomenon of red shift. The absorption edge of pure monolayer molybdenum disulfide is 0.8 eV, whereas the absorption edges of Mo₁₄VS₃₂, Mo₁₅VS₃₁ and Mo₁₄VS₃₁ become 0 eV, 0.2 eV and 0.16 eV, respectively. As a potential material, MoS₂ is widely used in many fields such as the production of optoelectronic devices, military devices and civil devices.     

Three‐Dimensional Multilayer Assemblies of MoS2/Reduced Graphene Oxide for High‐Performance Lithium Ion Batteries

Three‐dimensional (3D) multilayer molybdenum disulfide (MoS₂)/reduced graphene oxide (RGO) nanocomposites are prepared by a solution‐processed self‐assembly based on the interaction using different sizes of MoS₂ and GO nanosheets followed by in situ chemical reduction. 3D multilayer assemblies with MoS₂ wrapped by large RGO nanosheets and good interface are observed by transmission electron microscopy. The interaction of Na⁺ ions with oxygen‐containing groups of GO is also investigated. The measurement of lithium ion batteries (LIBs) shows that MoS₂/RGO anode nanocomposite with a weight ratio of MoS₂ to GO of 3:1 exhibits an excellent rate performance of 750 mAh g^?1 at 3 A g^?1 outperforming many previous studies and a high reversible capacity up to ≈1180 mAh g^?1 after 80 cycles at 100 mA g^?1. Good rate performance and high capacity of MoS₂/RGO with 3D unique layered‐structures are attributed to the combined effects of continuous conductive networks of RGO, good interface facilitating charge transfer, and strong RGO sheets preventing the volume expansion. Results indicate that 3D multilayer MoS₂/RGO prepared by a facile solution‐processed assembly can be developed to be an excellent nanoarchitecture for high‐performance LIBs.     

Layered MoS2 grown on c ‐sapphire by pulsed laser deposition

Layered growth of molybdenum disulphide (MoS₂) was successfully achieved by pulsed laser deposition (PLD) method on c ‐plane sapphire substrate. Growth of monolayer to a few monolayer MoS₂, dependent on the pulsed number of excimer laser in PLD is demonstrated, indicating the promising controllability of layer growth. Among the samples with various pulse number deposition, the frequency difference (A_1g–E¹_2g) in Raman analysis of the 70 pulse sample is estimated as 20.11 cm^–1, suggesting a monolayer MoS₂ was obtained. Two‐dimensional (2D) layer growth of MoS₂ is confirmed by the streaky reflection high energy electron diffraction (RHEED) patterns during growth and the cross‐sectional view of transmission electron microscopy (TEM). The in‐plane relationship, (0006) sapphire//(0002)MoS₂and sapphire//MoS₂ is determined. The results imply that PLD is suitable for layered MoS₂ growth. Additionally, the oxide states of Mo 3d core level spectra of PLD grown MoS₂, analysed by X‐ray photoelectron spectroscopy (XPS), can be effectively reduced by adopting a post sulfurization process. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

The electronic properties tuned by the phase transition between the semiconducting and metallic phase of monolayer MoS2/WS2

Using first-principles methods, we systematically investigate the electronic properties and atomic mechanism of the monolayer MoS₂/WS₂ homo-junction structure, which contains different phase structures, either the semiconducting hexagonal (H) structure or metallic trigonal (T) structure. Through tuning the size of the lateral homo-junction structure of either MoS₂ or WS₂, it can produce different boundaries which induce different phase transferred styles. More interestingly, the electronic structures of homo-junction structures can also be tuned by changing the size of the armchair and zigzag shapes of nanoribbons. The homo-junction structure of either MoS₂ or WS₂ exhibits alterable band structure and band edge position with the changing of the size. The strong dependence of the band offset on the sizes of the homo-junction monolayer also implicates a possible way of patterning quantum structures with size engineering.     

One‐Pot Synthesis of Algae‐Like MoS2/PPy Nanocomposite: A Synergistic Catalyst with Superior Peroxidase‐Like Catalytic Activity for H2O2 Detection

A facile one‐pot synthetic route is reported to prepare algae‐like molybdenum disulfide/polypyrrole (MoS₂/PPy) nanocomposite through a redox reaction between ammonium tetrathiomolybdate and pyrrole monomer under a hydrothermal condition without any other templates. The as‐prepared unique algae‐like MoS₂/PPy nanocomposites are composed of few layer MoS₂ nanosheets, which are covered with PPy. Structural and morphological characterizations of this unique nanocomposite are investigated by Fourier‐transform infrared spectra, Raman spectra, X‐ray diffraction pattern, X‐ray photoelectron spectra, energy‐dispersive X‐ray spectroscopy, and transmission electron microscopy. The as‐prepared MoS₂/PPy nanocomposites exhibit an excellent peroxidase‐like catalytic activity toward the oxidation of 3,3,5,5‐tetramethylbenzidine (TMB) in the presence of hydrogen peroxide (H₂O₂) in acetate buffer solution (pH 4.0), which provides a facile strategy for the colorimetric detection of H₂O₂ with a high sensitivity.     

Simple near‐infrared photodetector based on charge transfer complexes formed in molybdenum oxide doped N,N′‐di(naphthalene‐1‐yl)‐N,N′‐diphenyl‐benzidine

We have demonstrated a simple near‐infrared (NIR) photodetector (PD) based on charge transfer complex (CTC) formed in molybdenum trioxide (MoO₃) doped N,N′‐di(naphthalene‐1‐yl)‐N,N′‐diphenyl‐benzidine (NPB), which shows a photocurrent of about 0.35 A/cm² at –3 V under 980 nm illumination. The existence of CTC formation promotes photocurrent generation which is investigated by comparison with MoO₃ doped 2‐methyl‐9,10‐di(2‐naphthyl)anthracene (MADN) film which has no CTC absorption. It can be evolved that this kind of simple‐structure photodetector has potential application in the near‐infrared (NIR) detection area. It is shown in this Letter that although both MoO₃ and NPB have larger energy gaps of about 3 eV and weak absorption in the NIR region, the charge transfer complexes formed by mixing the two materials show an extra absorption band and good photoelectric response in the NIR region.

     

Fracture‐induced nanoscrolls from CVD‐grown monolayer molybdenum disulfide

We report a simple and effective way of fabricating molybdenum disulfide (MoS₂) nanoscrolls by self‐rolling up fractured monolayer CVD‐grown MoS₂ microflakes. Morphological results reveal that MoS₂ nanoscrolls are formed only at newly formed edges, owing to an orientation‐specific fracture behavior. Using Raman spectroscopy, we show that the E¹_2g Raman peak (A_1g peak) for MoS₂ nanoscrolls significantly red‐shifts (blue‐shifts), indicating structural change. The proposed mechanism is that the newly formed edges induced by fracture behavior self‐roll up to nanoscrolls to minimize the surface free energy, meanwhile, the serious lattice contradiction of upper sulfur plane controls the rolling directions. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

UV/ozone‐treated WS2 hole‐extraction layer in organic photovoltaic cells

WS₂ nanosheets obtained through a simple sonication exfoliation method are employed as a hole‐extraction layer to improve the efficiency of organic photovoltaic cells (OPVs). A reduction in the wavenumber difference in the Raman spectra, the appearance of a UV absorption peak, and atomic force microscopy images indicate that WS₂ nanosheets are formed through the sonication method. The power conversion efficiency (PCE) values of OPVs with and without untreated WS₂ layers are both 1.84%. After performing a UV‐ozone (UVO) treatment on the WS₂ surface for 15 min, the PCE increases to 2.4%. Synchrotron radiation photoelectron spectroscopy data show that the work function of WS₂ increases from 4.9 eV to 5.1 eV upon UVO treat‐ ment, suggesting that the increase in the PCE value is caused by the band alignment. Upon inserting poly(3,4‐ethylenedioxythiophene):poly(styrene‐sulfonate) (PEDOT: PSS) between the WS₂ and the active layer, the PCE value of the OPV increases to 3.07%, which is superior to that of the device employing only PEDOT:PSS (2.87%). Therefore, it is considered that the use of UVO‐treated WS₂ is able to improve the performance of OPV cells. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Large-scale chemical vapor deposition growth of highly crystalline MoS2 thin films on various substrates and their optoelectronic properties

Large-scale growth of mostly monolayer molybdenum disulfide (MoS₂) on quartz, sapphire, SiO₂/Si, and waveguide substrates is demonstrated by chemical vapor deposition with the same growth parameters. Centimeter-scale areas with large flakes and films of MoS₂ on all the growth substrates are observed. The atomic force microscopy and Raman measurements indicate the synthesized MoS₂ is monolayer with high quality and uniformity. The MoS₂ field effect transistors based on the as-grown MoS₂ exhibit carrier mobility of 1–2 cm²V^?1s^?1 and On/Off ratio of ~10⁴ while showing large photoresponse. Our results provide a simple approach to realize MoS₂ on various substrates for electronics and optoelectronics applications.