Investigations of two-dimensional transition-metal chalcogenides (TMCs) have recently revealed interesting physical phenomena, including the quantum spin Hall effect, valley polarization and two-dimensional superconductivity , suggesting potential applications for functional devices. However, of the numerous compounds available, only a handful, such as Mo- and W-based TMCs, have been synthesized, typically via sulfurization, selenization and tellurization of metals and metal compounds. Many TMCs are difficult to produce because of the high melting points of their metal and metal oxide precursors. Molten-salt-assisted methods have been used to produce ceramic powders at relatively low temperature and this approach was recently employed to facilitate the growth of monolayer WS and WSe. Here we demonstrate that molten-salt-assisted chemical vapour deposition can be broadly applied for the synthesis of a wide variety of two-dimensional (atomically thin) TMCs. We synthesized 47 compounds, including 32 binary compounds (based on the transition metals Ti, Zr, Hf, V, Nb, Ta, Mo, W, Re, Pt, Pd and Fe), 13 alloys (including 11 ternary, one quaternary and one quinary), and two heterostructured compounds. We elaborate how the salt decreases the melting point of the reactants and facilitates the formation of intermediate products, increasing the overall reaction rate. Most of the synthesized materials in our library are useful, as supported by evidence of superconductivity in our monolayer NbSe and MoTe samples and of high mobilities in MoS and ReS. Although the quality of some of the materials still requires development, our work opens up opportunities for studying the properties and potential application of a wide variety of two-dimensional TMCs.
Phase transitions can be used to alter the properties of a material without adding any additional atoms and are therefore of significant technological value. In a solid, phase transitions involve collective atomic displacements, but such atomic processes have so far only been investigated using macroscopic approaches. Here, we show that in situ scanning transmission electron microscopy can be used to follow the structural transformation between semiconducting (2H) and metallic (1T) phases in single-layered MoS2, with atomic resolution. The 2H/1T phase transition involves gliding atomic planes of sulphur and/or molybdenum and requires an intermediate phase (α-phase) as a precursor. The migration of two kinds of boundaries (β- and γ-boundaries) is also found to be responsible for the growth of the second phase. Furthermore, we show that areas of the 1T phase can be controllably grown in a layer of the 2H phase using an electron beam.
Atomic-scale defects in graphene layers alter the physical and chemical properties of carbon nanostructures. Theoretical predictions have recently shown that energetic particles such as electrons and ions can induce polymorphic atomic defects in graphene layers as a result of knock-on atom displacements. However, the number of experimental reports on these defects is limited. The graphite network in single-walled carbon nanotubes has been visualized by transmission electron microscopy (TEM) and their chiral indices have been determined. But the methods used require a long image acquisition time and intensive numerical treatments after observations to find an 'average' image, which prevents the accurate detection and investigation of defect structures. Here we report observations in situ of defect formation in single graphene layers by high-resolution TEM. The observed structures are expected to be of use when engineering the properties of carbon nanostructures for specific device applications.
Artificial van der Waals heterostructures with two-dimensional (2D) atomic crystals are promising as an active channel or as a buffer contact layer for next-generation devices. However, genuine 2D heterostructure devices remain limited because of impurity-involved transfer process and metastable and inhomogeneous heterostructure formation. We used laser-induced phase patterning, a polymorph engineering, to fabricate an ohmic heterophase homojunction between semiconducting hexagonal (2H) and metallic monoclinic (1T') molybdenum ditelluride (MoTe2) that is stable up to 300°C and increases the carrier mobility of the MoTe2 transistor by a factor of about 50, while retaining a high on/off current ratio of 10(6). In situ scanning transmission electron microscopy results combined with theoretical calculations reveal that the Te vacancy triggers the local phase transition in MoTe2, achieving a true 2D device with an ohmic contact.
Electronic junctions on edge Two-dimensional materials such as graphene are attractive materials for making smaller transistors because they are inherently nanoscale and can carry high currents. However, graphene has no band gap and the transistors are “leaky”; that is, they are hard to turn off. Related transition metal dichalcogenides (TMDCs) such as molybdenum sulfide have band gaps. Transistors based on these materials can have high ratios of “on” to “off” currents. However, it is often difficult to make a good voltage-biased (p-n) junction between different TMDC materials. Li et al. succeeded in making p-n heterojunctions between two of these materials, molybdenum sulfide and tungsten selenide. They did this not by stacking the layers, which make a weak junction, but by growing molybdenum sulfide on the edge of a triangle of tungsten selenide with an atomically sharp boundary Science , this issue p. 524
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