Development of a new molecular dynamics method for tribochemical reaction and its application to formation dynamics of MoS2 tribofilm

Recently we have developed a novel molecular dynamics program NEW-RYUDO-CR, which can deal with chemical reactions. The developed method has been applied to the study of tribochemical reaction dynamics of MoS₂ tribofilm on iron surface. The initially amorphous MoS₂ layer self-organized its structure as result of the tribochemical reactions and formed layered MoS₂ tribofilm. The friction coefficient significantly decreased as the MoS₂ tribofilm was formed. Besides, sliding was observed between sulfur layers of MoS₂ tribofilms which occurred due to repulsive Coulombic interaction forces between sulfur atoms. This indicates that the formation of the layered MoS₂ tribofilm is important to achieve better lubrication properties.     

Structure and properties of DLC–MoS2 thin films synthesized by BTIBD method

Diamond-like carbon (DLC)–MoS₂ composite thin films were synthesized using a biased target ion beam deposition (BTIBD) technique in which MoS₂ was produced by sputtering a MoS₂ target using Ar ion beams while DLC was deposited by ion beam deposition with CH₄ gas as carbon source. The structure and properties of the synthesized films were characterized by X-ray diffraction, X-ray absorption near edge structure (XANES), Raman spectroscopy, nanoindentation, ball-on-disk testing, and corrosion testing. The effect of MoS₂ target bias voltage, ranging from −200 to −800 V, on the structure and properties of the DLC–MoS₂ films was further investigated. The results showed that the hardness decreases from 9.1 GPa to 7 GPa, the Young?s modulus decreases from 100 GPa to 78 GPa, the coefficient of friction (COF) increases from 0.02 to 0.17, and the specific wear rate coefficient (k) increases from 5×10⁻⁷ to 5×10⁻⁶ mm³ N⁻¹ m⁻¹, with increasing the biasing voltage from 200 V to 800 V. Also, the corrosion resistance of the DLC–MoS₂ films decreased with the raise of biasing voltage. Comparing with the pure DLC and pure MoS₂ films, the DLC–MoS₂ films deposited at low biasing voltages showed better tribological properties including lower COF and k in ambient air environment.     

Structural transformation of MoO<Subscript>3</Subscript> nanobelts into MoS<Subscript>2</Subscript> nanotubes

The structural transformation of MoO₃ nanobelts into MoS₂ nanotubes using a simple sulfur source has been reported. This transformation has been extensively investigated using electron microscopic and spectroscopic techniques including scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), electron diffraction (ED), and energy-dispersive X-ray analysis (SEM-EDAX and TEM-EDX). The method described in this report will serve as a generic route for the transformation of other oxide nanostructures into the chalcogenide nanostructures.     

Phase conversion of chemically exfoliated molybdenum disulfide

Multilayer MoS₂ is exfoliated by Li treatment. A thin film of Li-treated MoS₂ contains a large portion of 1T phases. This is attributed to the atomic structural change caused by Li insertion, which is investigated using X-ray photoelectron spectroscopy (XPS). In a phase recovery via thermal annealing at 523 K in air, we observe another phase, referred to as the relaxed 1T phase, with a slightly larger binding energy than the 1T phase. After annealing at 523 K in air, the peak intensity of the relaxed 1T phase is reduced, accompanying a strong MoO_x peak and weak S 2s peak, according to XPS. This indicates that the annealing of Li-treated MoS₂ in air yields sulfur vacancies that induce the oxidation of Mo. However, after annealing at 523 K in vacuum, no MoO_x is observed, and the considerable peak intensity of the relaxed 1T phase remains, which starkly contrasts Raman-spectroscopy results supporting a full recovery from the 1T phase to the 2H phase. The absence of a gating effect of the Li-treated MoS₂ device supports the possibility of an incomplete phase change of Li-treated MoS₂ annealed in a vacuum.     

Electronic structure of the PLD grown mixed phase MoS2/GaN interface and its thermal annealing effect

We report the electronic structure of Molybdenum disulfide (MoS₂) ultrathin 2D films grown by pulsed laser deposition (PLD) on top of GaN/c-Al₂O₃ (0001) substrates annealed up to 550 °C in an ultrahigh vacuum. Our X-ray photoemission spectroscopy (XPS) study shows that the grown films are mixed phase character with semiconducting 2H and metallic 1T phases. After ultrahigh vacuum (UHV) annealing, the 1T/2H phase ratio is significantly modified and film-substrate bonding becomes the leading factor influencing variation of mixed phase compositions. The semiconducting phase is partially transformed to metallic phase by thermal annealing; suggesting that the metallic phase observed here may indeed have more stability compared to the semiconducting phase. The notable enhancement of the 1T/2H ratio induces significant changes in Ga 3d core level spectra taken from bare GaN and MoS₂/GaN sample. The impact of S and/or Mo atoms on the Ga core level spectra is further pronounced with the thermal annealing of grown films. The analysis shows that an enhancement of 1T metallic phase with thermal annealing in MoS₂ layers is manifested by the occurrence of new spectral component in the Ga 3d core level spectra with the formation of Ga-S adlayer interaction through the Ga bonding in defect assisted GaN structure.     

Conversion behavior comparison of TFA–MOD and non-fluorine solution-deposited YBCO films

The densification behavior during conversion of YBa₂Cu₃O_7−x (YBCO) films formed by the trifluoroacetate (TFA)-based metal–organic deposition (MOD) technique was compared to a non-fluorine oxycarbonate-based MOD process and nitrate-based polymer-assisted deposition (PAD). The critical current densities obtained in all processes exceeded 10⁶ A/cm² in films at least 300 nm thick. Rapid densification of films was observed in all processes, beginning at 700 °C in the TFA and PAD processes and 650 °C in the oxycarbonate process. YBCO nucleation occurred shortly after densification began in all processes. Residual carbon measurements were performed using wavelength dispersive spectroscopy (WDS). Carbon persisted in films from all processes until after densification began, but it was reduced to background levels soon after YBCO nucleation. Film density and second phase morphology were controlled through adjustments to the ambient oxygen partial pressure. Morphological evidence of extensive transient liquid phase formation was observed in PAD films and is consistent with the densification and nucleation behavior. The common behavior between the PAD, oxycarbonate–MOD, and TFA–MOD processes suggests that a melt forms in all systems, but the extent of this melt varies.     

Effect of precursor on growth and morphology of MoS2 monolayer and multilayer

The rise of two-dimensional (2D) material is one of the results of successful efforts of researchers which laid the path to the new era of electronics. One of the most exciting materials is MoS₂. Synthesis has been always a major issue as electronic devices need reproducibility along with similar properties for mass productions. Chemical vapor deposition (CVD) is one of the successful methods for 2D materials including graphene. Furthermore, the choice of starting materials for Mo and S source is crucial. The different source has different effects on the layers and morphology of MoS₂ films. In this work, we have extensively studied the CVD technique to grow few layers of MoS₂ with two precursors MoO₃ and MoCl₅, show remarkable changes. The MoO₃ source gives a triangular shaped MoS₂ monolayer while that of MoCl₅ can achieve uniform MoS₂ without triangle. The absence of geometric shapes with MoCl₅ is poorly understood. We tried to explain with MoCl₅ precursor, the formation of continuous monolayer of MoS₂ without any triangle on the basis of chemical reaction formalism mostly due to one step reaction process and formation of MoS₂ from gas phase to the solid phase. The film synthesized by MoCl₅ is more continuous and it would be a good choice for device applications.     

Dielectric and AC ionic conductivity investigations in K3H(SeO4)2 single crystal

Optical observation under the polarizing microscope and DSC measurements on K₃H(SeO₄)₂ single crystal have been carried out in the temperature range 25-200 °C. It reveals a high-temperature structural phase transition at around 110 °C. The crystal system transformed from monoclinic to trigonal. Electrical impedance measurements of K₃H(SeO₄)₂ were performed as a function of both temperature and frequency. The electrical conduction and dielectric relaxation have been studied. The temperature dependence of electrical conductivity indicates that the sample crystal became a fast ionic conductor in the high-temperature phase. The frequency dependence of conductivity follows the Jonscher's universal dynamic law with the relation σ(ω)=σ(0)+Aωⁿ, where ω is the frequency of the AC field, and n is the exponent. The obtained n values decrease from 1.2 to 0.1 from the room temperature phase to fast ionic phase. The high ionic conductivity in the high-temperature phase is explained by the dynamical disordering of protons between the neighboring SeO₄ groups, which provide more vacant sites in the crystal.     

Decreased n-type behavior of monolayer MoS2 crystals annealed in sulfur atmosphere

Herein, we report decreased n-type behavior of mechanically exfoliated monolayer MoS₂ crystals via annealing in sulfur atmosphere. The Raman, photoluminescence, and X-ray photoelectron spectroscopy (XPS) measurements consistently suggested decreased n-type behavior of the monolayer MoS₂ crystals after an hour of thermal annealing at 200 °C in sulfur atmosphere. Such decreased n-type behavior could be attributed to the reduced concentration of sulfur vacancies after the annealing, suggested by the analysis of XPS spectra. Furthermore, after the annealing in sulfur atmosphere, the monolayer MoS₂ transistors exhibited positively shifted threshold voltages and reduced on-currents, confirming decreased n-type conduction. These results demonstrate that the reduction of the concentration of sulfur vacancies decreases n-type behavior in monolayer MoS₂, providing valuable information on understanding the effect of sulfur vacancies on the performance of monolayer MoS₂ devices.     

Magnetic transitions and structure of a NiMnGa ferromagnetic shape memory alloy prepared by melt spinning technique

A ferromagnetic shape memory alloy with nomial composition Ni_52.5Mn_24.5Ga₂₃ (at%) was developed by a melt spinning technique. The as-spun ribbon showed dominant L2₁ austenitic (cubic) structure with a splitting of the primary peak in the X-ray diffractogram indicating the existence of a martensitic feature. The quenched-in martensitic plates were revealed in transmission electron microscopy. An increase of magnetization at low temperature indicated a martensite to austenite transformation and its reverse with a drop in magnetization during the cooling cycle. Higher magnetic fields propel martensite–austenite transformation spontaneously.     

Electrochemical impedance spectroscopic study of the lithium storage mechanism in commercial molybdenum disulfide

The first lithiation and delithiation processes of commercial molybdenum disulfide (MoS₂) electrode as anode material for lithium-ion batteries were studied by electrochemical impedance spectroscopy (EIS). It is found that the typical EIS is composed of four parts, namely, high-frequency semicircle, middle-frequency semicircle, low-frequency short sloping line, and low-frequency arc in the Nyquist diagram, and they can be attributed to the solid electrolyte interphase (SEI) film and ionic resistance in pores, charge transfer step, solid state diffusion process, and phase transformation, respectively. An equivalent circuit that includes elements related to the SEI film and charge transfer process, in addition to phase transformation, is proposed to simulate the experimental EIS data. The change of kinetic parameters for lithiation and delithiation of MoS₂ electrode as a function of potential in the first charge–discharge cycle is analyzed, and the reason for the rapid degradation in capacity of the MoS₂ electrode when cycled between 3.00 and 0.01 V is discussed in detail.     

On the nature of trapped states in an MoS2 two-dimensional semiconductor with sulfur vacancies

ABSTRACT

Molybdenum disulfide (MoS₂) is a common two-dimensional semiconductor that has been highly studied as an emerging material for catalysis and electronics. The most common material defects in MoS₂ are sulfur vacancies. In order to reveal the nature of the trapped states induced by sulfur vacancies, we perform Density Functional Theory (DFT) combined with quantum dynamics calculations. According to our model, we find that the sulfur vacancies create trap states in the original band gap of monolayer MoS₂ that disrupt charge transmission through the monolayer. In addition, we did not find any resonance states among the shallow states in the conduction band continuum.     

Singularities of magnetic and elastic characteristics of La2/3Ba1/3MnO3: Analysis of martensitic kinetics

A coordinated temperature behavior of magnetic susceptibility and internal friction has been observed in the La_2/3Ba_1/3MnO₃ manganite in the temperature region of the crystal phase separation 5–340 K. Stepwise temperature behavior of the susceptibility of the single crystal sample and corresponding singular behavior of the internal friction in the polycrystalline manganite have been found. These small-scale features of the temperature dependences of the susceptibility and the internal friction are considered to be a reflection of martensitic kinetics of the structural phase transformation R3¯c↔Imma in the 200 K temperature region.     

The CO coadsorption and reactions of sulfur,hydrogen and oxygen on clean and sulfided Mo(100) and on MoS2(0001) crystal faces

The chemisorption and reactivity of O₂ and H₂ with the sulfided Mo(100) surface and the basal (0001) plane of MoS₂ have been studied by means of Thermal Desorption Spectroscopy (TDS), Auger Electron Spectroscopy (AES) and Low Energy Electron Diffraction (LEED). These studies have been carried out at both low (10^?8–10^?5Torr) and high (1 atm) pressures of O₂ and H₂. Sulfur desorbs from Mo(100) both as an atom and as a diatomic molecule. Sulfur adsorbed on Mo(100) blocks sites of hydrogen adsorption without noticeably changing the hydrogen desorption energies. TDS of ¹⁸O coadsorbed with sulfur on the Mo(100) surface produced the desorption of SO at 1150 K, and of S, S₂ and O, but not SO₂. A pressure of 1 × 10^?7 Torr of O₂ was sufficient to remove sulfur from Mo(100) at temperatures over 1100 K. The basal plane of MoS₂ was unreactive in the presence of 1 atm of O₂ at temperatures of 520 K. Sputtering of the MoS₂ produced a marked uptake of oxygen and the removal of sulfur under the same conditions.     

MoO2@MoS2 Nanoarchitectures for High‐Loading Advanced Lithium‐Ion Battery Anodes

The capacity loading per unit area is of importance as specific capacity while evaluating the lithium‐ion battery anode. However, the low conductivity of several advanced anode materials (such as molybdenum sulfide, MoS₂) prohibits the wide application of materials. Nanostructural engineering becomes a key to overcome the obstacles. A one‐step in situ conversion reaction is employed to synthesize molybdenum oxide (MoO₂)–MoS₂ core–shell nanoarchitectures (MoO₂@MoS₂) by partially sulfiding MoO₂ into MoS₂ using sulfur. The MoO₂@MoS₂ displays a 3D architecture constructed by hundreds of MoS₂ ultrathin sheets with several layers arranged and fixed to an MoO₂ particle vertically with the size in the range of 200–500 nm. MoO₂ acts as the molybdenum source for the synthesis of MoS₂, as well as the conductive substrate. The designed 3D architectures with empty space between MoS₂ layers can prevent the damage originated from volume change of MoS₂ undergoing charge/discharge process. The lithium storage capacities of the MoO₂@MoS₂ 3D architectures are higher and the stability has been significantly improved compared to pure MoS₂. 4 mAh cm^?2 capacity loading of MoO₂@MoS₂ has been achieved with a specific capacity of more than 1000 mAh g^?1.     

Characterization of K2CO3/Co–MoS2 catalyst by XRD,XPS, SEM,and EDS

MoS₂, Co–MoS₂ and K₂CO₃/Co–MoS₂ catalysts have been characterized by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). XRD analysis indicates that Co–MoS₂ is a primary phase in K₂CO₃/Co–MoS₂ catalyst and the diffraction lines of Co–MoS₂ are not changed by the addition of K₂CO₃. Co₉S₈ phase is not present at Co/Mo mole ratio of 0.5 using a co-precipitation method for preparation of cobalt–molybdenum catalyst. The binding energies (BEs) of chemical species present on the surface of the catalysts are compared through the course of catalyst preparation. K₂CO₃/Co–MoS₂ catalyst has been investigated as a function of dispersion of K on the surface and exposure to a mixture of carbon monoxide and hydrogen (syngas) by scanning electron microscopy (SEM), and energy dispersive X-ray spectroscopy (EDS). The distribution of potassium on the surface of the K-promoted catalyst is not uniform.     

Stress-induced cubic-tetragonal transformation in partially stabilized ZrO2: Raman spectroscopy study

Regularities of the cubic-tetragonal transformation (C→t′) in partially stabilized zirconia were studied with Raman spectroscopy and high-temperature Raman spectroscopy techniques. New ‘low temperature’ mechanism of tetragonal nanoparticles formation in a volume of cubic solid solution was revealed in ZrO₂-Gd₂O₃ (Eu₂O₃) (6-8 mol%) single crystals. This mechanism includes nucleation of the tetragonal nanoparticles due to diffusionless C→t′ phase transformation at the first stage and gradual decrease of the stabilizer concentration inside t′-domains after subsequent low-temperature annealing. Predominant orientation of tetragonal domains due to the stress-induced C→t′ transformation was registered in ZrO₂-Gd₂O₃ (8 mol%) single crystals.     

Electronic and magnetic phase transitions in (Sm0.65Sr0.35)MnO3 induced by temperature and magnetic field

Temperature (4.2–260 K) and magnetic field (0–50 kOe) dependencies of the DC electrical resistance, DC magnetization, and AC magnetic susceptibility of (Sm_0.65Sr_0.35)MnO₃ prepared from high purity components have been studied. (Sm_0.65Sr_0.35)MnO₃ undergoes a temperature-induced transition between low-temperature ferromagnetic metallic and high-temperature paramagnetic insulating-like states. A magnetic field strongly affects this transition resulting in a metallic state and “colossal” magnetoresistance in the vicinity of the metal↔insulator transition. Magnetic and electric properties of (Sm_0.65Sr_0.35)MnO₃ are different compared to those reported earlier for similar composition, which is attributable to the purity of the starting materials and/or different process of synthesis. The character of phase transformations observed in (Sm_0.65Sr_0.35)MnO₃ is compared to that reported for Gd₅(Si_xGe_4−x) intermetallic alloys with a true first order phase transition.     

Density functional theory study of 3R- and 2H-CuAlO2 in tensile stress

We report a direct computational result of a phase transformation from the 3R phase to the 2H phase in CuAlO₂ with the application of tensile stress using the first-principles density functional theory calculations. The calculations of enthalpy variation with tensile stress indicates the 3R-to-2H phase transformation is expected to occur around −26.0 GPa. As the applied tensile stress increases, the independent elastic constants of 3R- and 2H-CuAlO₂ show the presences of mechanical instability at −27.5 and −27.6 GPa, which are possibly related with the ideal tensile strength.