Single atom doping in 2D layered MoS2 from a periodic table perspective

Molybdenum Disulfide (MoS₂) is a well-known transition metal dichalcogenide with a hexagonal structure arrangement analogous to graphene. Two dimensional (2D) MoS₂ has attracted wide attention in various applications such as energy storage, catalysis, sensing, energy conversion and optoelectronics due to its unique properties including tunable bandgap, substantial carrier mobility, outstanding mechanical strength and dangling-bond free basal surface. Moreover, MoS₂ has shown an excellent capability to be a host for foreign atoms which tune its physicochemical properties. Herein, currently known structural changes in the MoS₂ crystals introduced by various single atom dopants coming from all over the chemical table of elements are reviewed. Accompanying electrical, optical and magnetic properties of such structures are discussed in detail. Potential applications of the doped MoS₂ are introduced briefly as well. The review concentrates on the recent state-of-the-art results obtained mostly by the high resolution scanning transmission electron microscopy (STEM), such as high angle annular dark field (HAADF) imaging as well as scanning probe microscopy (SPM) such as scanning tunneling microscopy (STM). These techniques have been used to decipher dopant positions and other sub-atomic structural changes introduced to the MoS₂ structure by isolated dopants.     

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.     

Surface electromigration of Au ultrathin film on MoS2

The mass transport of Au ultrathin film on a semiconductor MoS₂ was investigated by atomic force microscopy (AFM) and scanning Auger microscopy (SAM). The surface electromigration of the Au film was found when a dc current was passed through the MoS₂ substrate. The Au ultrathin film on MoS₂ grew in a typical Volmer–Weber (V–W) growth mode, The AFM measurements indicated that the distribution of the Au islands exhibited clearly a preferential lateral spread towards the cathode, that is, the surface electromigration took place. The direction of the surface electromigration on MoS₂ is opposite to that of the Au electromigration on Si.     

Molecular beam epitaxy of GaN on a substrate of MoS2 layered compound

The feasibility of MoS₂ layered compound as a substrate for GaN growth was investigated. GaN films were successfully grown on MoS₂ by plasma-enhanced molecular beam epitaxy and the crystal quality of GaN on MoS₂ was compared with that on Al₂O₃. For GaN grown on MoS₂ substrate, it was found that the surface flatness observed by atomic force microscopy, stress in the film measured by Raman spectroscopy, optical properties measured by photoluminescence spectroscopy, and threading dislocation density observed by transmission electron microscopy show superior properties compared with that grown on Al₂O₃. These results suggest the layered compound such as MoS₂, which has no dangling bonds on the surface and has lattice mismatching of 0.9% to GaN, has high potential for a substrate of GaN growth. Received: 1 March 1999 / Accepted: 8 March 1999 / Published online: 26 May 1999     

Direct observation of the hysteretic Fermi level modulation in monolayer MoS2 field effect transistors

The hysteresis in the transfer curve of MoS₂ has significant impact on the device performance. However, the hysteresis mechanism is still not clear. Here, we investigate the hysteresis of the monolayer MoS₂ by probing the local Fermi level variations as a function of the back gate voltage in different atmosphere using the Kelvin probe microscopy. While the Fermi level of the MoS₂ in air is much lower than that in vacuum, both the MoS₂ devices in vacuum and air show large Fermi level hysteresis. The Fermi level hysteresis direction is clock-wise, identical to that observed in the transfer curves. Both the hysteresis in Fermi level and transfer curve can be explained consistently by taking into account the charge trapping. Our findings confirm that carrier density modulation in MoS₂ plays a vital role in the hysteresis, and provide insight into the hysteresis mechanism for the optimization of the device performance.     

Controlled exfoliation of molybdenum disulfide for developing thin film humidity sensor

We report a facile, size-controllable exfoliation process using an ultrasound-assisted liquid method to fabricate few-layer molybdenum disulfide (MoS₂) nanosheets. The morphology, structure and size distribution of the nanosheets processed with different ultrasonic powers were examined by atomic force microscopy, Raman spectroscopy and dynamic light scattering. It was revealed that the size of nanosheets reduces and final yield increases with elevating ultrasonic power. Bulk and exfoliated MoS₂ based thin film sensors are fabricated by a simple drop casting method on alumina substrates. Our sensors exhibit excellent sensitivity with very quick response and recovery speed to humidity gas. Comparative studies are carried out to draw up the size or ultrasonic power dependent sensing behavior.     

水热法合成纳米花状二硫化钼及其微观结构表征

本文以钼酸钠、硫代乙酰胺为前驱体, 硅钨酸为添加剂, 成功用水热法合成高纯度纳米花状二硫化钼. 产物特性用X射线衍射(XRD)、能量色散谱(EDS)、扫描电子显微镜(SEM)进行表征. XRD和EDS图显示实验产物为二硫化钼, 且其结晶度和层状堆垛良好. SEM图谱则表明二硫化钼为纳米花状结构, 颗粒直径300 nm左右, 由几十上百片花瓣组成, 每片花瓣厚度十个纳米左右. 通过以硅钨酸为变量的梯度实验, 研究发现, 硅钨酸对于纳米花状MoS₂的形成具有重要作用, 不添加硅钨酸, 无法形成纳米花状MoS₂, 此外, 硅钨酸的剂量会影响合成MoS₂的大小和形貌. 本文还对纳米花状二硫化钼的形成机理做了初步的讨论.     

Characteristics of a type-II n-MoS2/p-Ge van der Waals heterojunction

A few-atomic-layer molybdenum disulfide (MoS₂) film on Si/SiO₂ substrates grown by metal-organic chemical vapor deposition was investigated. The few-atomic-layer MoS₂ film was subsequently transferred onto a (100) p-Ge substrate to build a van der Waals n-p heterojunction. The as-grown few-atomic-layer MoS₂ film and the MoS₂/Ge heterostructure were characterized atomic force microscopy, spectroscopic ellipsometry, high-resolution scanning transmission electron microscopy, Raman spectroscopy analyses, photoluminescence (PL) measurements at room temperature (RT, 300 K), and type-II band alignment of the heterostructure determined by ultraviolet photoelectron spectroscopy. The RT-PL measurements showed dominant peaks at 1.96 and 1.8 eV for the as-grown MoS₂ and red-shifted PL peaks for that transferred onto Ge. We examined the electrical characteristics of the few-atomic-layer MoS₂ by forming a type-II band alignment van der Waals heterojunction with a highly doped p-Ge. The heterojunction solar cell exhibited an open-circuit voltage of 0.15 V and a short-circuit current density of 45.26 μA/cm². The external quantum efficiency measurements showed a spectral response up to approximately 500 nm owing to the absorption by the few-atomic-layer MoS₂ film.     

Structure of van der Waals bound hybrids of organic semiconductors and transition metal dichalcogenides: the case of acene films on MoS2

Transition metal dichalcogenides (TMDC) are important representatives in the emerging field of two‐dimensional materials. At present their combination with molecular films is discussed as it enables the realization of van der Waals bound organic/inorganic hybrids which are of interest in future device architectures. Here, we discuss the potential use of molybdenum disulfide (MoS₂) as supporting substrate for the growth of well‐defined, crystalline organic adlayers. By this means, hybrid systems between the TMDC surface and organic compounds can be prepared, allowing for the profound investigation of mutual optical and electronic coupling mechanisms. As model system, we choose pentacene and perfluoropentacene as prototypical organic semiconductors and analyze their film formation on MoS₂(001) surfaces. In both cases, we observe smooth, crystalline film growth in lying molecular configuration, hence enabling the preparation of well‐defined hybrid systems. By contrast, on defective MoS₂ surfaces both materials adopt an upright molecular orientation and exhibit distinctly different film morphologies. This emphasizes the importance of highly ordered TMDC surfaces with low defect density for the fabrication of well‐defined hybrid systems.     

Emission properties of sequentially deposited ultrathin CH3NH3PbI3/MoS2 heterostructures

Hybrid organic-inorganic perovskite materials have obtained considerable attention due to their exotic optoelectronic properties and extraordinarily high performance in photovoltaic devices. Herein, we successively converted the ultrathin PbI₂/MoS₂ into the CH₃NH₃PbI₃/MoS₂ heterostructures via CH₃NH₃I vapor processing. Atomic force microscopy (AFM)、Scanning electron microscopy (SEM) and X-ray photoemission spectroscopy (XPS) measurements prove the high-quality of the converted CH₃NH₃PbI₃/MoS₂. Both MoS₂ and CH₃NH₃PbI₃ related photoluminescence (PL) intensity quenching in CH₃NH₃PbI₃/MoS₂ implies a Type-II energy level alignment at the interface. Temperature-dependent PL measurements show that the emission peak position shifting trend of CH₃NH₃PbI₃ is opposite to that of MoS₂ (traditional semiconductors) due to the thermal expansion and electron-phonon coupling effects. The CH₃NH₃PbI₃/TMDC heterostructures are useful in fabricating innovative devices for wider optoelectronic applications.     

Composition and structure-property relationships of chromium-diboride/molybdenum-disulphide PVD nanocomposite hard coatings deposited by pulsed magnetron sputtering

The composition and structure-property relationships of physical vapour deposited coatings containing mixtures of CrB₂ and MoS₂ are reported. The coatings were produced by pulsed magnetron sputtering of loosely-packed powder targets formed from a blend of chromium and boron powders, alloyed with 12.8, 18.9 and 24.0 atom percent MoS₂. Results of coating characterisation (by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Auger electron spectroscopy and nanoindentation measurement of hardness and elastic modulus) revealed that increasing amounts of MoS₂ produced the following effects: frustration of crystallisation and phase separation; a decrease in average grain sizes (from ∼5.5 to ∼ 4.3 nm) and a decrease in coating hardness (from ∼15 to ∼ 10 GPa). Scratch testing also showed that the load-bearing capability of coatings was altered; coatings possessing an intermediate concentration of MoS₂ exhibited the best behaviour with no failure observed in mechanical testing, due to an optimal nanocomposite structure. The corrosion resistance (investigated by potentiodynamic polarisation tests) however tended to improve as more MoS₂ was introduced. An investigation of the effects of generating an amorphous structure by adding Ti and C into Cr-B-MoS₂ coatings revealed improved corrosion behaviour, which significantly exceeded that of uncoated stainless steel and CrB₂-coated samples. PACS 68.37.Lp; 68.55.A-; 68.55.Ln; 68.55.Nq; 68.60.Bs     

Doping of Fullerene‐Like MoS2 Nanoparticles with Minute Amounts of Niobium

Inorganic fullerene‐like closed‐cage nanoparticles of MoS₂ and WS₂ (IF‐MoS₂; IF‐WS₂), are synthesized in substantial amounts and their properties are widely studied. Their superior tribological properties led to large scale commercial applications as solid lubricants in numerous products and technologies. Doping of these nanoparticles can be used to tune their physical properties. In the current work, niobium (Nb) doping of the nanoparticles is accomplished to an unprecedented low level (≤0.1 at%), which allows controlling the work function and the band gap. The Nb contributes a positive charge, which partially compensates the negative surface charge induced by the intrinsic defects (sulfur vacancies). The energy diagram and position of the Fermi level on the nanoparticles surface is determined by Kelvin probe microscopy and optical measurements. Some potential applications of these nanoparticles are briefly discussed.     

A facile sonochemical route for the synthesis of MoS2/Pd composites for highly efficient oxygen reduction reaction

For the alkaline fuel cell cathode reaction, it is very essential to develop novel catalysts with superior catalytic properties. Here, we report the synthesis of highly active and stable MoS₂/Pd composites for the oxygen reduction reaction (ORR), via a simple, eco-friendly sonochemical method. The bulk MoS₂ was first transformed into single and few layers MoS₂ nanosheets through ultrasonic exfoliation. Then the exfoliated MoS₂ nanosheets served as supporting materials for the nucleation and further in-situ growth of Pd nanoparticles to form MoS₂/Pd composites via ultrasonic irradiation. Cyclic voltammetry and rotating disk voltammetry measurements demonstrate that as-prepared MoS₂/Pd composites which provides a direct four-electron pathway for the ORR, have better electrocatalytic activity, long-term operation stability than commercial Pt/C catalyst. We expect that the present work would provide a promising strategy for the development of efficient oxygen reduction electrocatalyst. In addition, this study can also be extended to the preparation of other hybrid with desirable morphologies and functions.     

Nanocomposite TiN films with embedded MoS2 inorganic fullerenes produced by combining supersonic cluster beam deposition with cathodic arc reactive evaporation

We report the production and characterization of nanocomposite thin films consisting of a titanium nitride matrix with embedded molybdenum disulphide fullerene-like nanoparticles. This was achieved by combining a cluster source generating a pulsed supersonic beam of MoS₂ clusters with an industrial cathodic arc reactive evaporation apparatus used for TiN deposition. Cluster-assembled films show the presence of MoS₂ nanocages and nanostructures and the survival of such structures dispersed in the TiN matrix in the co-deposited samples. Nanotribological characterization by atomic force microscopy shows that the presence of MoS₂ nanoparticles even in very low concentration modifies the behaviour of the TiN matrix. PACS 62.20.Qp; 62.23.Pq; 68.55.-a; 81.07.-b     

Enhanced lithium-ion storage and hydrogen evolution reaction catalysis of MoS<Subscript>2</Subscript>/graphene nanoribbons hybrids with loose interlaced three-dimension structure

Molybdenum disulfide hybridized with graphene nanoribbon (MoS₂/GNR) was prepared by mild method. MoS₂/GNR hybrids interlace loosely into a three-dimension structure. GNR hybridization can improve the dispersity of MoS₂, reduce the grain size of MoS₂ to 3–6 nm, increase the specific surface area, and broaden the interlamellar spacing of MoS₂ (002) plane to 0.67–0.73 nm, which facilitates the transportation of Li⁺ ions for lithium-ion battery. MoS₂/GNR hybrids have better cyclic durability, higher specific discharge capacity, and superior rate performance than MoS₂. The electrocatalytic activity in hydrogen evolution reaction shows that MoS₂/GNR hybrids have the lower overpotential and the larger current density with a negligible current loss after 2000 cycles. Hybridizing with GNRs enhances both the lithium-ion electrochemical storage and the electrocatalytic activity of MoS₂.

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Graphical abstract MoS₂/GNR hybrid prepared by a mild method is interlaced loosely into a three-dimension structure. Superior electrochemical performances of MoS₂/GNR hybrids than MoS₂ have been highlighted for the potential application for long- term durability energy-storage devices and HER electrocatalytic materials.

     

Effect of nanostructured MoS2 morphology on the glucose sensing of electrochemical biosensors

In this study, the effects of the morphological characteristics of MoS₂ nanomaterials on the glucose sensing of electrochemical biosensors were explored. Nanostructured MoS₂ materials, including nanoparticles (NPs), nanoflowers (NFs), and nanoplatelets (NPLs), were prepared via a simple hydrothermal method. The structure and morphological characteristics of MoS₂ nanomaterials were examined through X-ray diffraction, field emission scanning electron microscopy, and Raman spectroscopy. Electrochemical properties were analyzed through cyclic voltammetry. Results showed that the obtained sensitivity was 64, 68.7, and 77.6 μAmM⁻¹ cm⁻² for MoS₂ NP-, MoS₂ NF-, and MoS₂ NPL-based biosensors, respectively. The limit of detection (LOD) of all MoS₂-based glucose biosensors was 0.081 mM. In addition, the pH, temperature, glucose oxidase (GOx) concentration, reproducibility, specificity, and stability of glucose biosensors with different MoS₂ morphologies were also investigated and indicated the oxidation current response of the MoS₂ NPL-based glucose biosensor was higher than that of MoS₂ NF- and NP-based biosensors.     

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)     

Optically probing the interaction between monolayer MoS<Subscript>2</Subscript> and single-wall carbon nanotube

Owing to outstandingly tunable optoelectronic properties, hybrid materials consisting of atomic scale thickness of two dimensional (2D) transition metal dichalcogenides (TMDs) and one dimensional (1D) nanowires have been attracting steady interests over the last several years. In this research for the first time we report optically probing the interaction between monolayer MoS₂ and single-wall carbon nanotube (SWCNT). By using Raman and photoluminescence measurements, we found the charge transfer between MoS₂ and SWCNT is sensitive to the intensity of light field. We also demonstrate that SWCNT acts as p-type dopants at physical contact with monolayer MoS₂. Our study gives new insight into the interaction between monolayer MoS₂ and SWCNT, which may allow new phenomena and ideas for novel low dimensional hybrid materials.     

A new approach to modelling Kelvin probe force microscopy of hetero-structures in the dark and under illumination

A numerical method is proposed to model Kelvin probe force microscopy of hetero-structures in the dark and under illumination. It is applied to FTO/TiO₂ and FTO/TiO₂/MAPbI₃ structures. The presence of surface states on the top of the TiO₂ layers are revealed by combining theoretical computation and experimental results. Basic features of Kelvin probe force microscopy under illumination, namely surface photovoltage, are simulated as well. The method paves the way toward further investigations of more complicated optoelectronic devices.     

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.