Due to the recent expanding interest in two-dimensional layered materials, molybdenum disulfide (MoS2) has been receiving much research attention. Having an ultrathin layered structure and an appreciable direct band gap of 1.9 eV in the monolayer regime, few-layer MoS2 has good potential applications in nanoelectronics, optoelectronics, and flexible devices. In addition, the capability of controlling spin and valley degrees of freedom makes it a promising material for spintronic and valleytronic devices. In this review, we attempt to provide an overview of the research relevant to the structural and physical properties, fabrication methods, and electronic devices of few-layer MoS2. Recent developments and advances in studying the material are highlighted.

Few-Layer MoS2: A Promising Layered Semiconductor

Two-dimensional (2D) transition metal dichalcogenide (TMD) nanosheets exhibit remarkable electronic and optical properties. The 2D features, sizable bandgaps and recent advances in the synthesis, characterization and device fabrication of the representative MoS2, WS2, WSe2 and MoSe2 TMDs make TMDs very attractive in nanoelectronics and optoelectronics. Similar to graphite and graphene, the atoms within each layer in 2D TMDs are joined together by covalent bonds, while van der Waals interactions keep the layers together. This makes the physical and chemical properties of 2D TMDs layer-dependent. In this review, we discuss the basic lattice vibrations of 2D TMDs from monolayer, multilayer to bulk material, including high-frequency optical phonons, interlayer shear and layer breathing phonons, the Raman selection rule, layer-number evolution of phonons, multiple phonon replica and phonons at the edge of the Brillouin zone. The extensive capabilities of Raman spectroscopy in investigating the properties of TMDs are discussed, such as interlayer coupling, spin–orbit splitting and external perturbations. The interlayer vibrational modes are used in rapid and substrate-free characterization of the layer number of multilayer TMDs and in probing interface coupling in TMD heterostructures. The success of Raman spectroscopy in investigating TMD nanosheets paves the way for experiments on other 2D crystals and related van der Waals heterostructures.

Phonon and Raman scattering of two-dimensional transition metal dichalcogenides from monolayer, multilayer to bulk material

We study the environmental instability of mechanically exfoliated few-layer black phosphorus (BP). From continuous measurements of flake topography over several days, we observe an increase of over 200% in volume due to the condensation of moisture from air. We find that long term exposure to ambient conditions results in a layer-by-layer etching process of BP flakes. Interestingly, flakes can be etched down to single layer (phosphorene) thicknesses. BP's strong affinity for water greatly modifies the performance of fabricated field-effect transistors (FETs) measured in ambient conditions. Upon exposure to air, we differentiate between two timescales for doping of BP FET transfer characterisitcs: a short timescale (minutes) in which a shift in the threshold voltage occurs due to physisorbed oxygen and nitrogen, and a long timescale (hours) in which p-type doping occurs from water absorption. Continuous measurements of BP FETs in air reveal eventual degradation and break-down of the channel material after several days due to the layer-by-layer etching process.

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Environmental instability of few-layer black phosphorus

Phosphorene is a new family member of two-dimensional materials. We observed strong and highly layer-dependent photoluminescence in few-layer phosphorene (two to five layers). The results confirmed the theoretical prediction that few-layer phosphorene has a direct and layer-sensitive band gap. We also demonstrated that few-layer phosphorene is more sensitive to temperature modulation than graphene and MoS2 in Raman scattering. The anisotropic Raman response in few-layer phosphorene has enabled us to use an optical method to quickly determine the crystalline orientation without tunneling electron microscopy or scanning tunneling microscopy. Our results provide much needed experimental information about the band structures and exciton nature in few-layer phosphorene.

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Extraordinary Photoluminescence and Strong Temperature/Angle-Dependent Raman Responses in Few-Layer Phosphorene

Phosphorene, the single- or few-layer form of black phosphorus, was recently rediscovered as a two-dimensional layered material holding great promise for applications in electronics and optoelectronics. Research into its fundamental properties and device applications has since seen exponential growth. In this Perspective, we review recent progress in phosphorene research, touching upon topics on fabrication, properties, and applications; we also discuss challenges and future research directions. We highlight the intrinsically anisotropic electronic, transport, optoelectronic, thermoelectric, and mechanical properties of phosphorene resulting from its puckered structure in contrast to those of graphene and transition-metal dichalcogenides. The facile fabrication and novel properties of phosphorene have inspired design and demonstration of new nanodevices; however, further progress hinges on resolutions to technical obstructions like surface degradation effects and nonscalable fabrication techniques. We also briefly describe the latest developments of more sophisticated design concepts and implementation schemes that address some of the challenges in phosphorene research. It is expected that this fascinating material will continue to offer tremendous opportunities for research and development for the foreseeable future.

Phosphorene: Fabrication, Properties, and Applications.

We report on the temperature dependence of in-plane E2g and out-of-plane A1g Raman modes in high-quality few-layer MoS2 (FLMS) prepared using a high-temperature vapor-phase method. The materials obtained were investigated using transmission electron microscopy. The frequencies of these two phonon modes were found to vary linearly with temperature. The first-order temperature coefficients for E12g and A1g modes were found to be (1.32 and 1.23) × 10–2 cm–1/K, respectively. The thermal conductivity of the suspended FLMS at room temperature was estimated to be ∼52 W/mK.

Temperature-Dependent Raman Studies and Thermal Conductivity of Few-Layer MoS2

MoS2 is an important member of the transition metal dichalcogenides that is emerging as a potential 2D atomically thin layered material for low power electronic and optoelectronic applications. However, for MoS2 a critical fundamental question of significant importance is how the surface energy and hence the wettability is altered at the nanoscale in particular, the role of crystallinity and orientation. This work reports on the synthesis of large area MoS2 thin films on insulating substrates (SiO2/Si and Al2O3) with different surface morphology via vapor phase deposition by varying the growth temperatures. The samples were examined using transmission electron microscopy and Raman spectroscopy. From contact angle measurements, it is possible to correlate the wettability with crystallinity at the nanoscale. The specific surface energy for few layers MoS2 is estimated to be about 46.5 mJ/m2. Moreover a layer thickness-dependent wettability study suggests that the lower the thickness is, the higher the conta...

Surface energy engineering for tunable wettability through controlled synthesis of MoS2

Efficiency of hydrogen evolution via water electrolysis is mainly impeded by the kinetically sluggish oxygen evolution reaction (OER). Thus, it is of great significance to develop highly active and stable OER catalyst for alkaline water electrolysis or to substitute the more kinetically demanding acidic OER with a facile electron-donating reaction such that OER is no longer the bottleneck half-reaction for either acidic or alkaline water electrolysis. Herein, the hierarchical Fe–Ni phosphide shelled with ultrathin carbon networks on Ni foam (FeNiP@C) is reported and shows exceptional OER activity and enhanced chemical stability in 1 M KOH. This unique electrode provides large active sites, facile electron transport pathways, and rapid gas release, resulting in a remarkable OER activity that delivers a current density of 100 mA/cm2 at an overpotential of 182 mV with a Tafel slope of 56 mV/dec. Combining the hydrogen evolution reaction with organic pollutant (methylene blue) oxidation, a multifunctional ele...

Hierarchical FeNiP@Ultrathin Carbon Nanoflakes as Alkaline Oxygen Evolution and Acidic Hydrogen Evolution Catalyst for Efficient Water Electrolysis and Organic Decomposition

We report on the temperature dependence of in-plane E2g and out of plane A1g Raman modes in high quality few layers MoS2 (FLMS) prepared using a high temperature vapor-phase method. The materials obtained were investigated using transmission electron microscopy. The frequencies of these two phonon modes were found to vary linearly with temperature. The first order temperature coefficients for E2g and A1g modes were found to be 1.32*10-2 and 1.23*10-2 cm-1/K, respectively. The thermal conductivity of the suspended FLMS at room temperature was estimated to be about 52 W/mK.

Temperature Dependent Raman Studies and Thermal Conductivity of Few Layer MoS2

Atomically thin layers of 2D WS2 offer a realization of novel valley-selective electronics and power-efficient optoelectronic device fabrication due to large spin splitting at the top of the valence band and high quantum efficiency. However, the synthesis of the large-area monolayer WS2 film through chemical vapor deposition (CVD) method is in a rudimentary stage. Here we report a modified CVD method to synthesize high-crystalline monolayer WS2 (1L) with uniform size distribution over a large area. The intensity of the second-order Raman modes in 1L WS2 is enhanced, particularly the overtone of the acoustic mode LA(M), when the excitation wavelength is in the vicinity of B exciton. The variation in the intensity profile of the first-order Raman modes for 1L and bulk WS2 in (laser-energy-dependent) resonant Raman scattering processes is discussed within the third-order perturbation theory.

Anand P. S. Gaur

Papers

Temperature-Dependent Raman Studies and Thermal Conductivity of Few-Layer MoS2

Surface energy engineering for tunable wettability through controlled synthesis of MoS2

Hierarchical FeNiP@Ultrathin Carbon Nanoflakes as Alkaline Oxygen Evolution and Acidic Hydrogen Evolution Catalyst for Efficient Water Electrolysis and Organic Decomposition

Temperature Dependent Raman Studies and Thermal Conductivity of Few Layer MoS2

Electron–Phonon Interaction and Double-Resonance Raman Studies in Monolayer WS2