High-Sulfur-Vacancy Amorphous Molybdenum Sulfide as a High Current Electrocatalyst in Hydrogen Evolution.

The remote hydrogen plasma is able to create abundant S-vacancies on amorphous molybdenum sulfide (a-MoSx ) as active sites for hydrogen evolution. The results demonstrate that the plasma-treated a-MoSx exhibits superior performance and higher stability than Pt in a proton exchange membrane based electrolyzers measurement as a proof-of-concept of industrial application.

Direct imaging of band profile in single layer MoS2 on graphite: quasiparticle energy gap, metallic edge states, and edge band bending.

Using scanning tunneling microscopy and spectroscopy, we probe the electronic structures of single layer MoS2 on graphite. The apparent quasiparticle energy gap of single layer MoS2 is measured to be 2.15 ± 0.06 eV at 77 K, albeit a higher second conduction band threshold at 0.2 eV above the apparent conduction band minimum is also observed. Combining it with photoluminescence studies, we deduce an exciton binding energy of 0.22 ± 0.1 eV (or 0.42 eV if the second threshold is use), a value that is lower than current theoretical predictions. Consistent with theoretical predictions, we directly observe metallic edge states of single layer MoS2. In the bulk region of MoS2, the Fermi level is located at 1.8 eV above the valence band maximum, possibly due to the formation of a graphite/MoS2 heterojunction. At the edge, however, we observe an upward band bending of 0.6 eV within a short depletion length of about 5 nm, analogous to the phenomena of Fermi level pinning of a 3D semiconductor by metallic surface states.

Three-dimensional molybdenum sulfide sponges for electrocatalytic water splitting.

Electroactive MoSx catalysts on porous 3D sponges synthezied by a simple and scalable thermolysis process are proposed. Although no conducting materials are used to host the MoSx catalysts, they still serve as efficient electrodes for hydrogen evolution. The high current density of the MoSx-coated sponges are attributed to the large electrochemical surface area and their S-rich chemical structure.

One-step formation of a single atomic-layer transistor by the selective fluorination of a graphene film.

In this study, the scalable and one-step fabrication of single atomic-layer transistors is demonstrated by the selective fluorination of graphene using a low-damage CF4 plasma treatment, where the generated F-radicals preferentially fluorinated the graphene at low temperature (<200 °C) while defect formation was suppressed by screening out the effect of ion damage. The chemical structure of the C-F bonds is well correlated with their optical and electrical properties in fluorinated graphene, as determined by X-ray photoelectron spectroscopy, Raman spectroscopy, and optical and electrical characterizations. The electrical conductivity of the resultant fluorinated graphene (F-graphene) was demonstrated to be in the range between 1.6 kΩ/sq and 1 MΩ/sq by adjusting the stoichiometric ratio of C/F in the range between 27.4 and 5.6, respectively. Moreover, a unique heterojunction structure of semi-metal/semiconductor/insulator can be directly formed in a single layer of graphene using a one-step fluorination process by introducing a Au thin-film as a buffer layer. With this heterojunction structure, it would be possible to fabricate transistors in a single graphene film via a one-step fluorination process, in which pristine graphene, partial F-graphene, and highly F-graphene serve as the source/drain contacts, the channel, and the channel isolation in a transistor, respectively. The demonstrated graphene transistor exhibits an on-off ratio above 10, which is 3-fold higher than that of devices made from pristine graphene. This efficient transistor fabrication method produces electrical heterojunctions of graphene over a large area and with selective patterning, providing the potential for the integration of electronics down to the single atomic-layer scale.

Photoluminescence Enhancement and Structure Repairing of Monolayer MoSe2 by Hydrohalic Acid Treatment.

Atomically thin two-dimensional transition-metal dichalcogenides (TMDCs) have attracted much attention recently due to their unique electronic and optical properties for future optoelectronic devices. The chemical vapor deposition (CVD) method is able to generate TMDCs layers with a scalable size and a controllable thickness. However, the TMDC monolayers grown by CVD may incorporate structural defects, and it is fundamentally important to understand the relation between photoluminescence and structural defects. In this report, point defects (Se vacancies) and oxidized Se defects in CVD-grown MoSe2 monolayers are identified by transmission electron microscopy and X-ray photoelectron spectroscopy. These defects can significantly trap free charge carriers and localize excitons, leading to the smearing of free band-to-band exciton emission. Here, we report that the simple hydrohalic acid treatment (such as HBr) is able to efficiently suppress the trap-state emission and promote the neutral exciton and trion emission in defective MoSe2 monolayers through the p-doping process, where the overall photoluminescence intensity at room temperature can be enhanced by a factor of 30. We show that HBr treatment is able to activate distinctive trion and free exciton emissions even from highly defective MoSe2 layers. Our results suggest that the HBr treatment not only reduces the n-doping in MoSe2 but also reduces the structural defects. The results provide further insights of the control and tailoring the exciton emission from CVD-grown monolayer TMDCs.

Large-area synthesis of highly crystalline WSe(2) monolayers and device applications.

The monolayer transition metal dichalcogenides have recently attracted much attention owing to their potential in valleytronics, flexible and low-power electronics, and optoelectronic devices. Recent reports have demonstrated the growth of large-size two-dimensional MoS2 layers by the sulfurization of molybdenum oxides. However, the growth of a transition metal selenide monolayer has still been a challenge. Here we report that the introduction of hydrogen in the reaction chamber helps to activate the selenization of WO3, where large-size WSe2 monolayer flakes or thin films can be successfully grown. The top-gated field-effect transistors based on WSe2 monolayers using ionic gels as the dielectrics exhibit ambipolar characteristics, where the hole and electron mobility values are up to 90 and 7 cm(2)/Vs, respectively. These films can be transferred onto arbitrary substrates, which may inspire research efforts to explore their properties and applications. The resistor-loaded inverter based on a WSe2 film, with a gain of ∼13, further demonstrates its applicability for logic-circuit integrations.

Enhanced electrocatalytic activity of MoS(x) on TCNQ-treated electrode for hydrogen evolution reaction.

Molybdenum sulfide has recently attracted much attention because of its low cost and excellent catalytical effects in the application of hydrogen evolution reaction (HER). To improve the HER efficiency, many researchers have extensively explored various avenues such as material modification, forming hybrid structures or modifying geometric morphology. In this work, we reported a significant enhancement in the electrocatalytic activity of the MoSx via growing on Tetracyanoquinodimethane (TCNQ) treated carbon cloth, where the MoSx was synthesized by thermolysis from the ammonium tetrathiomolybdate ((NH4)2MoS4) precursor at 170 °C. The pyridinic N- and graphitic N-like species on the surface of carbon cloth arising from the TCNQ treatment facilitate the formation of Mo(5+) and S2(2-) species in the MoSx, especially with S2(2-) serving as an active site for HER. In addition, the smaller particle size of the MoSx grown on TCNQ-treated carbon cloth reveals a high ratio of edge sites relative to basal plane sites, indicating the richer effective reaction sites and superior electrocatalytic characteristics. Hence, we reported a high hydrogen evolution rate for MoSx on TCNQ-treated carbon cloth of 6408 mL g(-1) cm(-2) h(-1) (286 mmol g(-1) cm(-2) h(-1)) at an overpotential of V = 0.2 V. This study provides the fundamental concepts useful in the design and preparation of transition metal dichalcogenide catalysts, beneficial in the development in clean energy.

Monolayer MoSe2 grown by chemical vapor deposition for fast photodetection.

Monolayer molybdenum disulfide (MoS2) has become a promising building block in optoelectronics for its high photosensitivity. However, sulfur vacancies and other defects significantly affect the electrical and optoelectronic properties of monolayer MoS2 devices. Here, highly crystalline molybdenum diselenide (MoSe2) monolayers have been successfully synthesized by the chemical vapor deposition (CVD) method. Low-temperature photoluminescence comparison for MoS2 and MoSe2 monolayers reveals that the MoSe2 monolayer shows a much weaker bound exciton peak; hence, the phototransistor based on MoSe2 presents a much faster response time (<25 ms) than the corresponding 30 s for the CVD MoS2 monolayer at room temperature in ambient conditions. The images obtained from transmission electron microscopy indicate that the MoSe exhibits fewer defects than MoS2. This work provides the fundamental understanding for the differences in optoelectronic behaviors between MoSe2 and MoS2 and is useful for guiding future designs in 2D material-based optoelectronic devices.

Highly efficient electrocatalytic hydrogen production by MoS(x) grown on graphene-protected 3D Ni foams.

A three-dimensional Ni foam deposited with graphene layers on surfaces is used as a conducting solid support to load MoS(x) catalysts for electrocatalytic hydrogen evolution. The graphene sheets grown on Ni foams provide robust protection and efficiently increase the stability in acid. The superior performance of hydrogen evolution is attributed to the relatively high catalyst loading weight as well as its relatively low resistance.

Self-assembly of hierarchical MoSx/CNT nanocomposites (2

Two dimension (2D) layered molybdenum disulfide (MoS2) has emerged as a promising candidate for the anode material in lithium ion batteries (LIBs). Herein, 2D MoSx (2 ≤ x ≤ 3) nanosheet-coated 1D multiwall carbon nanotubes (MWNTs) nanocomposites with hierarchical architecture were synthesized via a high-throughput solvent thermal method under low temperature at 200°C. The unique hierarchical nanostructures with MWNTs backbone and nanosheets of MoSx have significantly promoted the electrode performance in LIBs. Every single MoSx nanosheet interconnect to MWNTs centers with maximized exposed electrochemical active sites, which significantly enhance ion diffusion efficiency and accommodate volume expansion during the electrochemical reaction. A remarkably high specific capacity (i.e., > 1000 mAh/g) was achieved at the current density of 50 mA g(-1), which is much higher than theoretical numbers for either MWNTs or MoS2 along (~372 and ~670 mAh/g, respectively). We anticipate 2D nanosheets/1D MWNTs nanocomposites will be promising materials in new generation practical LIBs.

Label-free detection of DNA hybridization using transistors based on CVD grown graphene.

The high transconductance and low noise of graphene-based field-effect transistors based on large-area monolayer graphene produced by chemical vapor deposition are used for label-free electrical detection of DNA hybridization. The gate materials, buffer concentration and surface condition of graphene have been optimized to achieve the DNA detection sensitivity as low as 1 pM (10(-12) M), which is more sensitive than the existing report based on few-layer graphene. The graphene films obtained using conventional PMMA-assisted transfer technique exhibits PMMA residues, which degrade the sensing performance of graphene. We have demonstrated that the sensing performance of the graphene samples prepared by gold-transfer is largely enhanced (by 125%).

Layer-by-layer graphene/TCNQ stacked films as conducting anodes for organic solar cells.

Large-area graphene grown by chemical vapor deposition (CVD) is a promising candidate for transparent conducting electrode applications in flexible optoelectronic devices such as light-emitting diodes or organic solar cells. However, the power conversion efficiency (PCE) of the polymer photovoltaic devices using a pristine CVD graphene anode is still not appealing due to its much lower conductivity than that of conventional indium tin oxide. We report a layer-by-layer molecular doping process on graphene for forming sandwiched graphene/tetracyanoquinodimethane (TCNQ)/graphene stacked films for polymer solar cell anodes, where the TCNQ molecules (as p-dopants) were securely embedded between two graphene layers. Poly(3-hexylthiophene)/phenyl-C61-butyric acid methyl ester (P3HT/PCBM) bulk heterojunction polymer solar cells based on these multilayered graphene/TCNQ anodes are fabricated and characterized. The P3HT/PCBM device with an anode structure composed of two TCNQ layers sandwiched by three CVD graphene layers shows optimum PCE (∼2.58%), which makes the proposed anode film quite attractive for next-generation flexible devices demanding high conductivity and transparency.