The band offsets and heterostructures of monolayer and few-layer transition-metal dichalcogenides MX 2 (M ¼ Mo, W; X ¼ S, Se, Te) are investigated from first principles calculations. The band alignments between different MX 2 monolayers are calculated using the vacuum level as reference, and a simple model is proposed to explain the observed chemical trends. Some of the monolayers and their heterostructures show band alignments suitable for potential applications in spontaneous water splitting, photovoltaics, and optoelectronics. The strong dependence of the band offset on the number of layers also implicates a possible way of patterning quantum structures with thickness engineering. V

Semiconducting transition metal dichalcogenides consist of monolayers held together by weak forces where the layers are electronically and vibrationally coupled. Isolated monolayers show changes in electronic structure and lattice vibration energies, including a transition from indirect to direct bandgap. Here we present a new member of the family, rhenium disulphide (ReS 2 ), where such variation is absent and bulk behaves as electronically and vibrationally decoupled monolayers stacked together. From bulk to monolayers, ReS 2 remains direct bandgap and its Raman spectrum shows no dependence on the number of layers. Interlayer decoupling is further demonstrated by the insensitivity of the optical absorption and Raman spectrum to interlayer distance modulated by hydrostatic pressure. Theoretical calculations attribute the decoupling to Peierls distortion of the 1T structure of ReS 2 , which prevents ordered stacking and minimizes the interlayer overlap of wavefunctions. Such vanishing interlayer coupling enables probing of two-dimensional-like systems without the need for monolayers.

Layered semiconductors based on transition-metal chalcogenides usually cross from indirect bandgap in the bulk limit over to direct bandgap in the quantum (2D) limit. Such a crossover can be achieved by peeling off a multilayer sample to a single layer. For exploration of physical behavior and device applications, it is much desired to reversibly modulate such crossover in a multilayer sample. Here we demonstrate that, in a few-layer sample where the indirect bandgap and direct bandgap are nearly degenerate, the temperature rise can effectively drive the system toward the 2D limit by thermally decoupling neighboring layers via interlayer thermal expansion. Such a situation is realized in few-layer MoSe 2 , which shows stark contrast from the well-explored MoS 2 where the indirect and direct bandgaps are far from degenerate. Photoluminescence of few-layer MoSe 2 is much enhanced with the temperature rise, much like the way that the photoluminescence is enhanced due to the bandgap crossover going from the bulk to the quantum limit, offering potential applications involving external modulation of optical properties in 2D semiconductors. The direct bandgap of MoSe 2 , identified at 1.55 eV, may also promise applications in energy conversion involving solar spectrum, as it is close to the optimal bandgap value of single-junction solar cells and photoelechemical devices. KEYWORDS: 2D-Semiconductors, MoSe 2 , MoS 2 , photoluminescence, bandgap, temperature dependence T wo-dimensional (2D) materials have attracted much interest mainly owing to their exotic physical properties that are strikingly different from their three-dimensional (bulk) counterparts. Even though graphene, the most famous member of the 2D material family, possesses extraordinary properties 1 and is readily integrated in various applications, 2−4 the lack of a native bandgap in graphene has led to a broad search for other 2D semiconducting materials. More recently, the transitionmetal dichalcogenide (TMD) semiconductor MoS 2 has been focused on and has shown great potential in the field; singlelayer MoS 2 has been used as an integral part of transistors, 5−8 sensors, 9 and magnetic materials. 10 However, beyond MoS 2 , other layered TMDs offer a large variety of 2D materials with distinct properties.In this work we studied, for the first time, single-layer MoSe 2 mechanically exfoliated onto SiO 2 /Si. 11 Single-layer MoSe 2 displays good thermal stability with a 1.55 eV direct bandgap as determined from photoluminescence (PL) measurements. The PL peak intensity is enhanced dramatically from few-layer to single-layer as a result of the crossover from indirect bandgap in the bulk limit to direct bandgap in the quantum (2D) limit, similar to the behavior of MoS 2 . 12−14 More interestingly, we find that few-layer MoSe 2 flakes posssess a nearly degenerate indirect and direct bandgap, and an increase in temperature can effectively push the system toward the quasi-2D limit by thermally reducing the coupling between the layers. This response in f...

The development of colloidal quantum dots has led to practical applications of quantum confinement, such as in solution-processed solar cells, lasers and as biological labels. Further scientific and technological advances should be achievable if these colloidal quantum systems could be electronically coupled in a general way. For example, this was the case when it became possible to couple solid-state embedded quantum dots into quantum dot molecules. Similarly, the preparation of nanowires with linear alternating compositions--another form of coupled quantum dots--has led to the rapid development of single-nanowire light-emitting diodes and single-electron transistors. Current strategies to connect colloidal quantum dots use organic coupling agents, which suffer from limited control over coupling parameters and over the geometry and complexity of assemblies. Here we demonstrate a general approach for fabricating inorganically coupled colloidal quantum dots and rods, connected epitaxially at branched and linear junctions within single nanocrystals. We achieve control over branching and composition throughout the growth of nanocrystal heterostructures to independently tune the properties of each component and the nature of their interactions. Distinct dots and rods are coupled through potential barriers of tuneable height and width, and arranged in three-dimensional space at well-defined angles and distances. Such control allows investigation of potential applications ranging from quantum information processing to artificial photosynthesis.

Point defects in semiconductors can trap free charge carriers and localize excitons. The interaction between these defects and charge carriers becomes stronger at reduced dimensionalities, and is expected to greatly influence physical properties of the hosting material. We investigated effects of anion vacancies in monolayer transition metal dichalcogenides as two-dimensional (2D) semiconductors where the vacancies density is controlled by α-particle irradiation or thermal-annealing. We found a new, sub-bandgap emission peak as well as increase in overall photoluminescence intensity as a result of the vacancy generation. Interestingly, these effects are absent when measured in vacuum. We conclude that in opposite to conventional wisdom, optical quality at room temperature cannot be used as criteria to assess crystal quality of the 2D semiconductors. Our results not only shed light on defect and exciton physics of 2D semiconductors, but also offer a new route toward tailoring optical properties of 2D semiconductors by defect engineering.

In the monolayer limit, transition metal dichalcogenides become direct-bandgap, light-emitting semiconductors. The quantum yield of light emission is low and extremely sensitive to the substrate used, while the underlying physics remains elusive. In this work, we report over 100 times modulation of light emission efficiency of these two-dimensional semiconductors by physical adsorption of O2 and/or H2O molecules, while inert gases do not cause such effect. The O2 and/or H2O pressure acts quantitatively as an instantaneously reversible "molecular gating" force, providing orders of magnitude broader control of carrier density and light emission than conventional electric field gating. Physi-sorbed O2 and/or H2O molecules electronically deplete n-type materials such as MoS2 and MoSe2, which weakens electrostatic screening that would otherwise destabilize excitons, leading to the drastic enhancement in photoluminescence. In p-type materials such as WSe2, the molecular physisorption results in the opposite effect. Unique and universal in two-dimensional semiconductors, the effect offers a new mechanism for modulating electronic interactions and implementing optical devices.

Band offsets between different monolayer transition metal dichalcogenides are expected to efficiently separate charge carriers or rectify charge flow, offering a mechanism for designing atomically thin devices and probing exotic two-dimensional physics. However, developing such large-area heterostructures has been hampered by challenges in synthesis of monolayers and effectively coupling neighboring layers. Here, we demonstrate large-area (>tens of micrometers) heterostructures of CVD-grown WS2 and MoS2 monolayers, where the interlayer interaction is externally tuned from noncoupling to strong coupling. Following this trend, the luminescence spectrum of the heterostructures evolves from an additive line profile where each layer contributes independently to a new profile that is dictated by charge transfer and band normalization between the WS2 and MoS2 layers. These results and findings open up venues to creating new material systems with rich functionalities and novel physical effects.

Using first-principles calculations, we investigate the adsorption of various gas molecules (H2, O2, H2O, NH3, NO, NO2, and CO) on monolayer MoS2. The most stable adsorption configuration, adsorption energy, and charge transfer are obtained. It is shown that all the molecules are weakly adsorbed on the monolayer MoS2 surface and act as charge acceptors for the monolayer, except NH3 which is found to be a charge donor. Furthermore, we show that charge transfer between the adsorbed molecule and MoS2 can be significantly modulated by a perpendicular electric field. Our theoretical results are consistent with the recent experiments and suggest MoS2 as a potential material for gas sensing application.