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 + Theoretical energies of the A and B excitons A (eV) A (nm) B (eV) B (nm) MoS2 1.78 695 1.96 632 MoSe2 1.50 825 1.75 708 MoTe2 1.06 1170 1.36 912 WS2 1.84 673 2.28 544 WSe2 1.52 815 2.00 620
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.
Atomic layers of MoS2 have been used as a phototransistor and ultrasensitive detectors. Phototransistors are important devices: the first with a MoS2 monolayer active region shows a photoresponsivity of 7.5 mA W−1 which is similar to graphene devices that reach 6.1 mA W−1. Multilayer MoS2 show higher photoresponsivities, about 100 mA W−1, which is similar to silicon devices. Making a gold contact at the far edges of a monolayer allows an ultrasensitive detector to be fabricated. Such a detector has a photoresponsivity reaching , 106 greater than the first graphene photodetectors. This high degree of electrostatic control is due to the thin active region of the monolayer. Its simplicity and the fact that it has only one semiconductor region, whereas the current generation of photodetectors is typically a p–n junction, makes possible industrial applications such as high-sensitivity and flexible photodetectors. The only limitation for currently available devices is the slow photoresponse dynamics. Utilizing WSe2 the photoresponse was improved to a bandwidth of over 230 MHz by device symmetry optimization
Mechanical properties Interest in the use of TMD monolayers such as MoS2, WS2, and WSe2 for the use in flexible electronics due to a change from an indirect band gap in 3D to a direct band gap in 2D emphasizes the importance of the mechanical properties of these materials. Unlike in bulk samples it is much more difficult to uniformly deform 2D monolayers of material and as a result, taking mechanical measurements of 2D systems is more challenging. A method that was developed to overcome this challenge, called atomic force microscopy (AFM) nanoindentation, involves bending a 2D monolayer suspended over a holey substrate with an AFM cantilever and measuring the applied force and displacement. Through this method, defect free mechanically exfoliated monolayer flakes of MoS2 were found to have a Young's modulus of 270 GPa with a maximum experienced strain of 10% before breaking. In the same study, it was found that bilayer mechanically exfoliated MoS2 flakes have a lower Young's modulus of 200 GPa, which is attributed to interlayer sliding and defects in the monolayer. With increasing flake thickness the bending rigidity of the flake plays a dominant role and it is found that the Young's modulus of multilayer, 5- 25 layers, mechanically exfoliated MoS2 flakes is 330 GPa.
The mechanical properties of other TMDs such as WS2 and WSe2 have also been determined. The Young's modulus of multilayer, 5-14 layers, mechanically exfoliated WSe2 is found to be 167 GPa with a maximum strain of 7%. For WS2, the Young's modulus of chemical vapor deposited monolayer flakes is 272 GPa. From this same study the Young's modulus of CVD-grown monolayer flakes of MoS2 is found to be 264 GPa. This is an interesting result as the Young's modulus of the exfoliated MoS2 flake is nearly the same as that of the CVD grown MoS2 flake. It is generally accepted that chemically vapor deposited TMDs will include more defects when compared with the mechanically exfoliated films that are obtained from bulk single crystals, which implies that defects (points defects, etc.) that are included in the flake do not drastically affect the strength of the flake itself.
Under the application of strain, a decrease in the direct and indirect band gap is measured that is approximately linear with strain. Importantly, the indirect bandgap decreases faster with applied strain to the monolayer than the direct bandgap, resulting in a crossover from direct to indirect band gap at a strain level of around 1%. As a result, the emission efficiency of monolayers is expected to decrease for highly strained samples. This property allows mechanical tuning of the electronic structure and also the possibility of fabrication of devices on flexible substrates.
Fabrication of TMD monolayers
Exfoliation Exfoliation is a top down approach. In the bulk form, TMDs are crystals made of layers, which are coupled by Van-der-Waals forces. These interactions are weaker than the chemical bonds between the Mo and S in MoS2, for example. So TMD monolayers can be produced by micromechanical cleavage, just as graphene.
The crystal of TMD is rubbed against the surface of another material (any solid surface). In practice, adhesive tape is placed on the TMD bulk material and subsequently removed. The adhesive tape, with tiny TMD flakes coming off the bulk material, is brought down onto a substrate. On removing the adhesive tape from the substrate, TMD monolayer and multilayer flakes are deposited. This technique produces small samples of monolayer material, typically about 5–10 micrometers in diameter.
Large quantities of exfoliated material can also be produced using liquid-phase exfoliation by blending TMD materials with solvents and polymers.
Chemical vapor deposition Chemical vapor deposition (CVD) is another approach used to synthesize transition-metal dichalcogenides. It has been used broadly to synthesize many different TMDs because it can be easily adapted for different TMD materials. Generally, CVD growth of TMDs is achieved by putting precursors to the material, typically a transition-metal oxide and pure chalcogen, into a furnace with the substrate on which the material will form. The furnace is heated to high temperatures (anywhere from 650 to 1000 °C) with an inert gas, typically N2 or Ar, flowing through the tube. Some materials require H2 gas as a catalyst for formation, so it may be flowed through the furnace in smaller quantities than the inert gas.