Kunttal Keyshar

Chemical Vapor Deposition Growth of Crystalline Monolayer MoSe2

Recently, two-dimensional layers of transition metal dichalcogenides, such as MoS2, WS2, MoSe2, and WSe2, have attracted much attention for their potential applications in electronic and optoelectronic devices. The selenide analogues of MoS2 and WS2 have smaller band gaps and higher electron mobilities, making them more appropriate for practical devices. However, reports on scalable growth of high quality transition metal diselenide layers and studies of their properties have been limited. Here, we demonstrate the chemical vapor deposition (CVD) growth of uniform MoSe2 monolayers under ambient pressure, resulting in large single crystalline islands. The photoluminescence intensity and peak position indicates a direct band gap of 1.5 eV for the MoSe2 monolayers. A back-gated field effect transistor based on MoSe2 monolayer shows n-type channel behavior with average mobility of 50 cm(2) V(-1) s(-1), a value much higher than the 4-20 cm(2) V(-1) s(-1) reported for vapor phase grown MoS2.

Two-Step Growth of Two-Dimensional WSe2/MoSe2 Heterostructures

Two dimensional (2D) materials have attracted great attention due to their unique properties and atomic thickness. Although various 2D materials have been successfully synthesized with different optical and electrical properties, a strategy for fabricating 2D heterostructures must be developed in order to construct more complicated devices for practical applications. Here we demonstrate for the first time a two-step chemical vapor deposition (CVD) method for growing transition-metal dichalcogenide (TMD) heterostructures, where MoSe2 was synthesized first and followed by an epitaxial growth of WSe2 on the edge and on the top surface of MoSe2. Compared to previously reported one-step growth methods, this two-step growth has the capability of spatial and size control of each 2D component, leading to much larger (up to 169 μm) heterostructure size, and cross-contamination can be effectively minimized. Furthermore, this two-step growth produces well-defined 2H and 3R stacking in the WSe2/MoSe2 bilayer regions and much sharper in-plane interfaces than the previously reported MoSe2/WSe2 heterojunctions obtained from one-step growth methods. The resultant heterostructures with WSe2/MoSe2 bilayer and the exposed MoSe2 monolayer display rectification characteristics of a p-n junction, as revealed by optoelectronic tests, and an internal quantum efficiency of 91% when functioning as a photodetector. A photovoltaic effect without any external gates was observed, showing incident photon to converted electron (IPCE) efficiencies of approximately 0.12%, providing application potential in electronics and energy harvesting.

Liquid Phase Exfoliation of Two-Dimensional Materials by Directly Probing and Matching Surface Tension Components

Exfoliation of two-dimensional (2D) materials into mono- or few layers is of significance for both fundamental studies and potential applications. In this report, for the first time surface tension components were directly probed and matched to predict solvents with effective liquid phase exfoliation (LPE) capability for 2D materials such as graphene, h-BN, WS2, MoS2, MoSe2, Bi2Se3, TaS2, and SnS2. Exfoliation efficiency is enhanced when the ratios of the surface tension components of the applied solvent is close to that of the 2D material in question. We enlarged the library of low-toxic and common solvents for LPE. Our study provides distinctive insight into LPE and has pioneered a rational strategy for LPE of 2D materials with high yield.

Facile Synthesis of Single Crystal Vanadium Disulfide Nanosheets by Chemical Vapor Deposition for Efficient Hydrogen Evolution Reaction

A facile chemical vapor deposition method to prepare single-crystalline VS2 nanosheets for the hydrogen evolution reaction is reported. The electrocatalytic hydrogen evolution reaction (HER) activities of VS2 show an extremely low overpotential of -68 mV at 10 mA cm(-2), small Tafel slopes of ≈34 mV decade(-1), as well as high stability, demonstrating its potential as a candidate non-noble-metal catalyst for the HER.

Chemical Vapor Deposition of Monolayer Rhenium Disulfide (ReS2)

The direct synthesis of monolayer and multilayer ReS2 by chemical vapor deposition at a low temperature of 450 °C is reported. Detailed characterization of this material is performed using various spectroscopy and microscopy methods. Furthermore initial field-effect transistor characteristics are evaluated, which highlight the potential in being used as an n-type semiconductor.

CoMoO4 Nanoparticles Anchored on Reduced Graphene Oxide Nanocomposites as Anodes for Long-Life Lithium-Ion Batteries

A self-assembled CoMoO4 nanoparticles/reduced graphene oxide (CoMoO4NP/rGO), was prepared by a hydrothermal method to grow 3-5 nm sized CoMoO4 particles on reduced graphene oxide sheets and used as an anode material for lithium-ion batteries. The specific capacity of CoMoO4NP/rGO anode can reach up to 920 mAh g(-1) at a current rate of 74 mA g(-1) in the voltage range between 3.0 and 0.001 V, which is close to the theoretical capacity of CoMoO4 (980 mAh g(-1)). The fabricated half cells also show good rate capability and impressive cycling stability with 8.7% capacity loss after 600 cycles under a high current density of 740 mA g(-1). The superior electrochemical performance of the synthesized CoMoO4NP/rGO is attributed to the synergetic chemical coupling effects between the conductive graphene networks and the high lithium-ion storage capability of CoMoO4 nanoparticles.

Self-optimizing, highly surface-active layered metal dichalcogenide catalysts for hydrogen evolution

Hydrogen is a promising energy carrier and key agent for many industrial chemical processes 1 . One method for generating hydrogen sustainably is via the hydrogen evolution reaction (HER), in which electrochemical reduction of protons is mediated by an appropriate catalyst—traditionally, an expensive platinum-group metal. Scalable production requires catalyst alternatives that can lower materials or processing costs while retaining the highest possible activity. Strategies have included dilute alloying of Pt 2 or employing less expensive transition metal alloys, compounds or heterostructures (e.g., NiMo, metal phosphides, pyrite sulfides, encapsulated metal nanoparticles) 3-5 . Recently, low-cost, layered transition-metal dichalcogenides (MX2) 6 based on molybdenum and tungsten have attracted substantial interest as alternative HER catalysts 7-11 . These materials have high intrinsic per-site HER activity; however, a significant challenge is the limited density of active sites, which are concentrated at the layer edges. 8,10,11 . Here we use theory to unravel electronic factors underlying catalytic activity on MX2 surfaces, and leverage the understanding to report group-5 MX2 (H-TaS2 and H-NbS2) electrocatalysts whose performance instead derives from highly active basal-plane sites. Beyond excellent catalytic activity, they are found to exhibit an unusual ability to optimize their morphology for enhanced charge transfer and accessibility of active sites as the HER proceeds. This leads to long cycle life and practical advantages for scalable processing. The resulting performance is comparable to Pt and exceeds all reported MX2 candidates.

Scalable Transfer of Suspended Two-Dimensional Single Crystals.

Large-scale suspended architectures of various two-dimensional (2D) materials (MoS2, MoSe2, WS2, and graphene) are demonstrated on nanoscale patterned substrates with different physical and chemical surface properties, such as flexible polymer substrates (polydimethylsiloxane), rigid Si substrates, and rigid metal substrates (Au/Ag). This transfer method represents a generic, fast, clean, and scalable technique to suspend 2D atomic layers. The underlying principle behind this approach, which employs a capillary-force-free wet-contact printing method, was studied by characterizing the nanoscale solid-liquid-vapor interface of 2D layers with respect to different substrates. As a proof-of-concept, a photodetector of suspended MoS2 has been demonstrated with significantly improved photosensitivity. This strategy could be extended to several other 2D material systems and open the pathway toward better optoelectronic and nanoelectromechnical systems.

Experimental Determination of the Ionization Energies of MoSe2, WS2, and MoS2 on SiO2 Using Photoemission Electron Microscopy

The values of the ionization energies of transition metal dichalcogenides (TMDs) are needed to assess their potential usefulness in semiconductor heterojunctions for high-performance optoelectronics. Here, we report on the systematic determination of ionization energies for three prototypical TMD monolayers (MoSe2, WS2, and MoS2) on SiO2 using photoemission electron microscopy with deep ultraviolet illumination. The ionization energy displays a progressive decrease from MoS2, to WS2, to MoSe2, in agreement with predictions of density functional theory calculations. Combined with the measured energy positions of the valence band edge at the Brillouin zone center, we deduce that, in the absence of interlayer coupling, a vertical heterojunction comprising any of the three TMD monolayers would form a staggered (type-II) band alignment. This band alignment could give rise to long-lived interlayer excitons that are potentially useful for valleytronics or efficient electron-hole separation in photovoltaics.

Photoemission Electron Microscopy as a New Tool to Study the Electronic Properties of 2D Crystals and Inhomogeneous Semiconductors

1. Sandia National Laboratories, Albuquerque, New Mexico, United States. 2. Center for Integrated Nanotechnologies, Sandia National Laboratories, Albuquerque, New Mexico, United States. 3. Department of Materials Science and Nanoengineering, Rice University, Houston, Texas, United States. 4. Los Alamos National Laboratory, Los Alamos, New Mexico, United States. 5. Department of Mechanical Engineering, Colorado State University, Fort Collins, Colorado, United States. 6. Center for Integrated Nanotechnologies, Los Alamos National Laboratory, Los Alamos, New Mexico, United States.