Transition metal dichalcogenide monolayers

Transition-metal dichalcogenide (TMD or TMDC) monolayers are atomically thin semiconductors of the type MX2, with M a transition-metal atom (Mo, W, etc.) and X a chalcogen atom (S, Se, or Te). One layer of M atoms is sandwiched between two layers of X atoms. They are part of the large family of so-called 2D materials, named so to emphasize their extraordinary thinness. For example, a MoS2 monolayer is only 6.5 Å thick. The key feature of these materials is the interaction of large atoms in the 2D structure as compared with first-row transition-metal dichalcogenides, e.g., WTe2 exhibits anomalous giant magnetoresistance and superconductivity. The discovery of graphene shows how new physical properties emerge when a bulk crystal of macroscopic dimensions is thinned down to one atomic layer. Like graphite, TMD bulk crystals are formed of monolayers bound to each other by van-der-Waals attraction. TMD monolayers have properties that are distinctly different from those of the semimetal graphene:

TMD monolayers MoS2, WS2, MoSe2, WSe2, MoTe2 have a direct band gap, and can be used in electronics as transistors and in optics as emitters and detectors. The TMD monolayer crystal structure has no inversion center, which allows to access a new degree of freedom of charge carriers, namely the k-valley index, and to open up a new field of physics: valleytronics The strong spin–orbit coupling in TMD monolayers leads to a spin–orbit splitting of hundreds meV in the valence band and a few meV in the conduction band, which allows control of the electron spin by tuning the excitation laser photon energy and handedness. 2D nature and high spin–orbit coupling in TMD layers can be used as promising materials for spintronic applications. The work on TMD monolayers is an emerging research and development field since the discovery of the direct bandgap and the potential applications in electronics and valley physics. TMDs are often combined with other 2D materials like graphene and hexagonal boron nitride to make van der Waals heterostructures. These heterostructures need to be optimized to be possibly used as building blocks for many different devices such as transistors, solar cells, LEDs, photodetectors, fuel cells, photocatalytic and sensing devices. Some of these devices are already used in everyday life and can become smaller, cheaper and more efficient by using TMD monolayers.

Crystal structure

Transition-metal dichalcogenides (TMDs) are composed of three atomic planes and often two atomic species: a metal and two chalcogens. The honeycomb, hexagonal lattice has threefold symmetry and can permit mirror plane symmetry and/or inversion symmetry. In the macroscopic bulk crystal, or more precisely, for an even number of monolayers, the crystal structure has an inversion center. In the case of a monolayer (or any odd number of layers), the crystal may or may not have an inversion center.

Broken inversion symmetry Two important consequences of that are:

nonlinear optical phenomena, such as second-harmonic generation. When the crystal is excited by a laser, the output frequency can be doubled. an electronic band structure with direct energy gaps, where both conduction and valence band edges are located at the non-equivalent K points (K+ and K−) of the 2D hexagonal Brillouin zone. The interband transitions in the vicinity of the K+ (or K−) point are coupled to right (or left) circular photon polarization states. These so-called valley dependent optical selection rules arise from inversion symmetry breaking. This provides a convenient method to address specific valley states (K+ or K−) by circularly polarized (right or left) optical excitation. In combination with strong spin-splitting, the spin and valley degree of freedom are coupled, enabling stable valley polarization. These properties indicate that TMD monolayers represent a promising platform to explore spin and valley physics with the corresponding possible applications.

Properties

Transport properties

At submicron scales, 3D materials no longer have the same behavior as their 2D form, which can be an advantage. For example, graphene has a very high carrier mobility, and accompanying lower losses through the Joule effect. But graphene has zero bandgap, which results in a disqualifyingly low on/off ratio in transistor applications. TMD monolayers might be an alternative: they are structurally stable, display a band gap, and show electron mobilities comparable to those of silicon, so they can be used to fabricate transistors. Although thin-layer TMDs have been found to have a lower electron mobility than bulk TMDs, most likely because their thinness makes them more susceptible to damage, it has been found that coating the TMDs with HfO2 or hexagonal boron nitride (hBN) increases their effective carrier mobility.

Optical properties

A semiconductor can absorb photons with energy larger than or equal to its bandgap. This means that light with a shorter wavelength is absorbed. Semiconductors are typically efficient emitters if the minimum of the conduction band energy is at the same position in k-space as the maximum of the valence band, i.e., the band gap is direct. The band gap of bulk TMD material down to a thickness of two monolayers is still indirect, so the emission efficiency is lower compared to monolayered materials. The emission efficiency is about 104 greater for TMD monolayer than for bulk material. The band gaps of TMD monolayers are in the visible range (between 400 nm and 700 nm). The direct emission shows two excitonic transitions called A and B, separated by the spin–orbit coupling energy. The lowest energy and therefore most important in intensity is the A emission. Owing to their direct band gap, TMD monolayers are promising materials for optoelectronics applications.

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