No abstract

Molybdenum disulfide (MoS2) is back in the spotlight because of the indirect-to-direct bandgap tunability and valley related physics emerging in the monolayer regime. However, rigorous control of the monolayer thickness is still a huge challenge for commonly utilized physical exfoliation and chemical synthesis methods. Herein, we have successfully grown predominantly monolayer MoS2 on an inert and nearly lattice-matching mica substrate by using a low-pressure chemical vapor deposition method. The growth is proposed to be mediated by an epitaxial mechanism, and the epitaxial monolayer MoS2 is intrinsically strained on mica due to a small adlayer-substrate lattice mismatch (~2.7%). Photoluminescence (PL) measurements indicate strong single-exciton emission in as-grown MoS2 and room-temperature PL helicity (circular polarization ~0.35) on transferred samples, providing straightforward proof of the high quality of the prepared monolayer crystals. The homogeneously strained high-quality monolayer MoS2 prepared in this study could competitively be exploited for a variety of future applications.

As an inorganic cousin of graphene, MoS2 monolayer has attracted considerable attention. However, a full understanding of its structure and stability is still lacking due to its dependence on experimental synthesis conditions. Using first-principle calculations combined with Boltzmann transport equation, we have extensively studied the geometry, energetics, electronic structure, optical absorption, and carrier mobility of various phases of MoS2. We have not only identified the stable phases of a MoS2 monolayer, but also clarified the specific conditions under which different phases are formed. The possible pathways for transitions among different phases are also discussed.

We performed a nanoscale confocal absorption spectral imaging to obtain the full absorption spectra (over the range 1.5-3.2 eV) within regions having different numbers of layers and studied the variation of optical transition depending on the atomic thickness of the MoS2 film. Three distinct absorption bands corresponding to A and B excitons and a high-energy background (BG) peak at 2.84 eV displayed a gradual redshift as the MoS2 film thickness increased from the monolayer, to the bilayer, to the bulk MoS2 and this shift was attributed to the reduction of the gap energy in the Brillouin zone at the K-point as the atomic thickness increased. We also performed n-type chemical doping of MoS2 films using reduced benzyl viologen (BV) and the confocal absorption spectra modified by the doping showed a strong dependence on the atomic thickness: A and B exciton peaks were greatly quenched in the monolayer MoS2 while much less effect was shown in larger thickness and the BG peak either showed very small quenching for 1 L MoS2 or remained constant for larger thicknesses. Our results indicate that confocal absorption spectral imaging can provide comprehensive information on optical transitions of microscopic size intrinsic and doped two-dimensional layered materials.

Monolayer MoS2 prepared by chemical vapor deposition (CVD) has a highly polycrystalline nature largely because of the coalescence of misoriented domains, which severely hinders its future applications. Identifying and even controlling the orientations of individual domains and understanding their merging behavior therefore hold fundamental significance. In this work, by using single-crystalline sapphire (0001) substrates, we designed the CVD growth of monolayer MoS2 triangles and their polycrystalline aggregates for such purposes. The obtained triangular MoS2 domains on sapphire were found to distributively align in two directions, which, as supported by density functional theory calculations, should be attributed to the relatively small fluctuations of the interface binding energy around the two primary orientations. Using dark-field transmission electron microscopy, we further imaged the grain boundaries of the aggregating domains and determined their prevalent armchair crystallographic orientations with respect to the adjacent MoS2 lattice. The coalescence of individual triangular flakes governed by unique kinetic processes is proposed for the polycrystal formation. These findings are expected to shed light on the controlled MoS2 growth toward predefined domain orientation and large domain size, thus enabling its versatile applications in next-generation nanoelectronics and optoelectronics.

The Mn atom, because of its special electronic configuration of 3d(5)4s(2), has been widely used as a dopant in various two-dimensional (2D) monolayers such as graphene, BN, silicene and transition metal dichalcogenides (TMDs). The distributions of doped Mn atoms in these systems are highly sensitive to the synthesis process and conditions, thus suffering from problems of low solubility and surface clustering. Here we show for the first time that the MnO2 monolayer, synthetized 10 years ago, where Mn ions are individually held at specific sites, exhibits intrinsic ferromagnetism with a Curie temperature of 140 K, comparable to the highest TC value achieved experimentally for Mn-doped GaAs. The well-defined atomic configuration and the intrinsic ferromagnetism of the MnO2 monolayer suggest that it is superior to other magnetic monolayer materials.

Using density functional theory combined with Monte Carlo (MC) simulations, we show that the two dimensional (2D) MnS2 and MnSe2 sheets are ideal magnetic semiconductors with long-range magnetic ordering and high magnetic moments (3 μB per unit cell), where all the Mn atoms are ferromagnetically coupled, and the Curie temperatures (TC) estimated for MnS2 and MnSe2 by the MC simulations are 225 and 250 K, respectively, which can be further increased to 330 K and 375 K by applying 5% biaxial tensile strains.

The phase stability and phase transition of transition metal dichalcogenide (TMD) monolayer materials have attracted tremendous attention due to their attractive diverse potential applications. Here, first-principles calculations based on density-functional theory are carried out to study the newly synthesized MoTe2 monolayer. A phase different from the semiconducting trigonal prismatic structure and octahedral coordinated structure is found to be stable at room temperature in a free standing state, as evidenced by phonon spectrum analysis and molecular dynamic simulation. Raman vibrations of all the possible phases are calculated to provide additional information for the distinction of different phases in the experiment.