Transition metal dichalcogenide monolayers
Transition-metal dichalcogenide (TMD or TMDC) monolayers are atomically thin semiconductors of the type MX, 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 MoS 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., WTe 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: 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: 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 HfO 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 10 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 MoS have been used as a phototransistor and ultrasensitive detectors. Phototransistors are important devices: the first with a MoS monolayer active  region shows a photoresponsivity of 7.5 mA W which is similar to graphene devices that reach 6.1 mA W. Multilayer MoS show higher photoresponsivities, about 100 mA W, 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 , 10 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. Mechanical properties. Interest in the use of TMD monolayers such as MoS WS, and WSe 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 MoS 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 MoS 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 MoS flakes is 330 GPa. The mechanical properties of other TMDs such as WS and WSe have also been determined. The Young's modulus of multilayer, 5-14 layers, mechanically exfoliated WSe is found to be 167 GPa with a maximum strain of 7%. For WS, 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 MoS is found to be 264 GPa. This is an interesting result as the Young's modulus of the exfoliated MoS flake is nearly the same as that of the CVD grown MoS 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 MoS, 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 N or Ar, flowing through the tube. Some materials require H gas as a catalyst for formation, so it may be flowed through the furnace in smaller quantities than the inert gas. Outside of traditional CVD, metal organic chemical vapor deposition (MOCVD) has been used to synthesize TMDs. Unlike traditional CVD described above, MOCVD uses gaseous precursors, as opposed to solid precursors and MOCVD is usually carried out at lower temperatures, anywhere  from 300 to 900 °C. MOCVD has been shown to provide more consistent wafer-scale growth than traditional CVD. CVD is often used over mechanical exfoliation despite its added complexity because it can produce monolayers ranging anywhere from 5 to 100 microns in size as opposed to the surface areas of roughly 5-10 microns produced using the mechanical exfoliation method. Not only do TMD monolayers produced by CVD have a larger surface area than those flakes produced by mechanical exfoliation, they are often more uniform. Monolayer TMD flakes with very little or no multilayer areas can be produced  by chemical vapor deposition, in contrast to samples produced by mechanical exfoliation, which often have many multilayered areas. Molecular-beam epitaxy. Molecular-beam epitaxy (MBE) is an established technique for growing semiconductor devices with atomic monolayer thickness control. As a promising demonstration, high-quality monolayer MoSe samples have been grown on graphene by MBE. Electronic band structure. Band gap. In the bulk form, TMD have an indirect gap in the center of the Brillouin zone, whereas in monolayer form the gap becomes direct and is located in the K points. Spin–orbit coupling. For TMDs, the atoms are heavy and  the outer layers electronic states are from d-orbitals that have a strong spin–orbit coupling. This spin orbit coupling removes the spins degeneracy in both the conduction and valence band i.e. introduces a strong energy splitting between spin up and down states. In the case of MoS, the spin splitting in conduction band is in the meV range, it is expected to be more pronounced in other material like WS. The spin orbit splitting in the valence band is several hundred meV. Spin-valley coupling and the electron valley degree of freedom. By controlling the charge or spin degree  of freedom of carriers, as proposed by spintronics, novel devices have already been made. If there are different conduction/valence band extrema in the electronic band structure in k-space, the carrier can be confined in one of these valleys. This degree of freedom opens up a new field of physics: the controlling of carriers k-valley index, also called valleytronics. For TMD monolayers crystals, the parity symmetry is broken, there is no more inversion center. K valleys of different directions in the 2D hexagonal Brillouin zone are no longer equivalent. So there are two kinds of K valley called  K+ and K-. Also there is a strong energy degeneracy of different spin states in valence band. The transformation of one valley to another is described by the time reversal operator. Moreover, crystal symmetry leads to valley dependent optical selection rules: a right circular polarized photon (σ+) initializes a carrier in the K+ valley and a left circular polarized photon (σ-) initializes a carrier in the K- valley. Thanks to these two properties (spin-valley coupling and optical selection rules), a laser of specific polarization and energy allows to initialize the electron valley states (K+ or K-) and spin states  (up or down). Emission and absorption of light: excitons. A single layer of TMD can absorb up to 20% of incident light, which is unprecedented for such a thin material. When a photon of suitable energy is absorbed by a TMD monolayer, an electron is created in the conduction band; the electron now missing in the valence band is assimilated by a positively charged quasi-particle called a hole. The negatively charged electron and the positively charged hole are attracted via the Coulomb interaction, forming a bound state called an exciton which can be thought as a hydrogen atom (with  some difference). This Bosonic-like quasi-particle is very well known and studied in traditional semiconductors, such as GaAs and ZnO but in TMD it provides exciting new opportunities for applications and for studying fundamental physics. Indeed, the reduced dielectric screening and the quantum size effect present in these ultrathin materials make the binding energy of excitons much stronger than those in traditional semiconductors. Binding energies of several hundreds of meV are observed for all the four principal members of the TMD family. As mentioned before, we can think about an exciton as if it were a hydrogen atom, with  an electron bound to a hole. The main difference is that this system is not stable and tends to relax to the vacuum state, which is here represented by an electron in the valence band. The energy difference between the exciton 'ground state' (n=1) and the 'vacuum state' is called optical gap and is the energy of the photon emitted when an exciton recombines. This is the energy of the photons emitted by TMD monolayers and observed as huge emission peaks in photoluminescence (PL) experiments, such as the one labelled X in the figure. In this picture the binding energy  E is defined as the difference between the free particle band gap and the optical band gap and represent, as usual, the energy needed to take the hole and the electron apart. The existence of this energy difference is called band gap renormalization. The analogy with hydrogen atom doesn't stop here as excitonic excited states were observed at higher energies and with different techniques. Because of the spin–orbit splitting of the valence band two different series of excitons exist in TMD, called A- and B-excitons. In the A series the hole is located in the upper branch  of the Valence band while for the B-exciton the hole is in the lower branch. As a consequence the optical gap for B-exciton is larger and the corresponding peak is found at higher energy in PL and reflectivity measurements. Another peak usually appears in the PL spectra of TMD monolayers, which is associated to different quasi-particles called trions. These are excitons bound to another free carrier which can be either an electron or a hole. As a consequence a trion is a negative or positively charged complex. The presence of a strong trion peak in a PL  spectrum, eventually stronger than the peak associated with exciton recombination, is a signature of a doped monolayer. It is believed now that this doping is extrinsic, which means that it arises from charged trap states present in the substrate (generally SiO). Positioning a TMD monolayer between two flakes of hBN removes this extrinsic doping and greatly increase the optical quality of the sample. At higher excitation powers biexcitons have also been observed in monolayer TMDs. These complexes are formed by two bound excitons. Theory predicts that even larger charge-carrier complexes, such as charged biexcitons (quintons) and ion-bound biexcitons , are stable and should be visible in the PL spectra. Additionally, quantum light has been observed to originate from point defects in these materials in a variety of configurations. Radiation effects of TMD monolayers. Common forms of radiation used to create defects in TMDs are particle and electromagnetic irradiation, impacting the structure and electronic performance of these materials. Scientist have been studying the radiation response of these materials to be used in high-radiation environments, such as space or nuclear reactors. Damage to this unique class of materials occurs mainly through sputtering and displacement for metals or radiolysis and charging  for insulators and semiconductors. To sputter away an atom, the electron must be able to transfer enough energy to overcome the threshold for knock-on damage. Yet, the exact quantifiable determination of this energy still needs to be determined for TMDs. Consider MoS as an example, TEM exposure via sputtering creates vacancies in the lattice, these vacancies are then observed to be collected together in spectroscopic lines. Additionally, when looking at the radiation response of these materials, the three parameters that are proven to matter most are the choice of substrate, the sample thickness, and the sample preparation process. Janus  TMD monolayers. A new type of asymmetric transitional metal dichalcogenide, the Janus TMDs monolayers, has been synthesized by breaking the out-of-plane structural symmetry via plasma assisted chemical vapor deposition. Janus TMDs monolayers show an asymmetric structure MXY (M = Mo or W, X/Y = S, Se or Te) exhibiting out-of-plane optical dipole and piezoelectricity due to the imbalance of the electronic wave-function between the dichalcogenides, which are absent in a non-polar TMDs monolayer, MX. In addition, the asymmetric structure of Janus MoSSe provides an enhanced Rashba spin–orbit interaction, which suggests asymmetrically Janus  TMDs monolayer can be a promising candidate for spintronic applications. In addition, Janus TMDs monolayer has been considered as an excellent material for electrocatalysis or photocatalysis. Janus MoSSe can be synthesized by inductively coupled plasma CVD (ICP-CVD). The top layer of sulfur atoms on MoS is stripped using hydrogen ions, forming an intermediate state, MoSH. Afterward, the intermediate state is selenized by thermal annealing at 250 °C in an environment of hydrogen and argon gases. Aspirational uses. Electronics. A field-effect transistor (FET) made of monolayer MoS showed an on/off ratio exceeding 10 at room temperature owing  to electrostatic control over the conduction in the 2D channel. FETs made from MoS, MoSe, WS, and WSe have been made. All show promise not just because of their electron mobility and band gap, but because their very thin structure makes them promising for use in thin, flexible electronics. Sensing. The band gap TMDs possess makes them attractive for sensors as a replacement for graphene. FET-based biosensors rely on receptors attached to the monolayer TMD. When target molecules attach to the receptors, it affects the current flowing through the transistor. However, it has been shown that one can detect  nitrogenous bases in DNA when they pass through nanopores made in MoS. Nanopore sensors are based upon measuring ionic current through a nanopore in a material. When a single strand of DNA passes through the pore, there is a marked decrease in ionic current for each base. By measuring the current flowing through the nanopore, the DNA can then be sequenced. To this date, most sensors have been created from MoS, although WS has been explored as well. Specific examples. Molybdenum disulfide. Molybdenum disulfide monolayers consist of a unit of one layer of molybdenum atoms covalently bonded to two layers  of sulfur atoms. While bulk molybdenum sulfide exists as 1T, 2H, or 3R polymorphs, molybdenum disulfide monolayers are found only in the 1T or 2H form. The 2H form adopts a trigonal prismatic geometry while the 1T form adopts an octahedral or trigonal antiprismatic geometry. Molybdenum monolayers can also be stacked due to Van der Waals interactions between each layer. Electrical. The electrical properties of molybdenum sulfide in electrical devices depends on factors such as the number of layers, the synthesis method, the nature of the substrate on which the monolayers are placed on, and mechanical strain . As the number of layers decrease, the band gap begins to increase from 1.2eV in the bulk material up to a value of 1.9eV for a monolayer. Odd number of molybdenum sulfide layers also produce different electrical properties than even numbers of molybdenum sulfide layers due to cyclic stretching and releasing present in the odd number of layers. Molybdenum sulfide is a p-type material, but it shows ambipolar behavior when molybdenum sulfide monolayers that were 15 nm thick were used in transistors. However, most electrical devices containing molybdenum sulfide monolayers tend to show n-type behavior. The band gap  of molybdenum disulfide monolayers can also be adjusted by applying mechanical strain or an electrical field. Increasing mechanical strain shifts the phonon modes of the molybdenum sulfide layers. This results in a decrease of the band gap and metal-to-insulator transition. Applying an electric field of 2-3Vnm also decreases the indirect bandgap of molybdenum sulfide bilayers to zero. Solution phase lithium intercalation and exfoliation of bulk molybdenum sulfide produces molybdenum sulfide layers with metallic and semiconducting character due to the distribution of 1T and 2H geometries within the material. This is due to the two forms of  molybdenum sulfide monolayers having different electrical properties. The 1T polymorph of molybdenum sulfide is metallic in character while the 2H form is more semiconducting. However, molybdenum disulfide layers produced by electrochemical lithium intercalation are predominantly 1T and thus metallic in character as there is no conversion to the 2H form from the 1T form. Thermal. The thermal conductivity of molybdenum disulfide monolayers at room temperature is 34.5W/mK while the thermal conductivity of few-layer molybdenum disulfide is 52W/mK. The thermal conductivity of graphene, on the other hand, is 5300W/mK. Due to the rather low  thermal conductivity of molybdenum disulfide nanomaterials, it is not as promising material for high thermal applications as some other 2D materials. Exfoliation. Exfoliation techniques for the isolating of molybdenum disulfide monolayers include mechanical exfoliation, solvent assisted exfoliation, and chemical exfoliation. Solvent assisted exfoliation is done by sonicating bulk molybdenum disulfide in an organic solvent such as isopropanol and N-methyl-2-pyrrolidone, which disperses the bulk material into nanosheets as the Van der Waals interactions between the layers in the bulk material are broken. The amount of nanosheets produced is controlled by the sonication time, the solvent-molybdenum disulfide interactions, and  the centrifuge speed. Compared to other exfoliation techniques, solvent assisted exfoliation is the simplest method for large scale production of molybdenum disulfide nanosheets. The micromechanical exfoliation of molybdenum disulfide was inspired by the same technique used in the isolation of graphene nanosheets. Micromechanical exfoliation allows for low defect molybdenum disulfide nanosheets but is not suitable for large scale production due to low yield. Chemical exfoliation involves functionalizing molybdenum difsulfide and then sonicating to disperse the nanosheets. The most notable chemical exfoliation technique is lithium intercalation in which lithium is intercalated into bulk molybdenum disulfide and then dispersed into nanosheets by  the addition of water. Chemical vapor deposition. Chemical vapor deposition of molybdenum disulfide nanosheets involves reacting molybdenum and sulfur precursors on a substrate at high temperatures. This technique is often used in the preparing electrical devices with molybdenum disulfide components because the nanosheets are applied directly on the substrate; unfavorable interactions between the substrate and the nanosheets that would have occurred had they been separately synthesized are decreased. In addition, since the thickness and area of the molybdenum disulfide nanosheets can be controlled by the selection of specific precursors, the electrical properties of the nanosheets can be tuned. Among the  techniques that have been used to deposit molybdenum disulfide is electroplating. Ultra-thin films consisting of few-layers have been produced via this technique over graphene electrodes. In addition, other electrode materials were also electroplated with MoS2, such as Titanium Nitride (TiN), glassy carbon and polytetrafluoroethylene. The advantage that this technique offers in producing 2D materials is its spatial growth selectivity and its ability to deposit over 3D surfaces. Controlling the thickness of electrodeposited materials can be achieved by adjusting the deposition time or current. Laser ablation. Pulsed laser deposition involves the thinning of bulk molybdenum disulfide by laser to  produce single or multi-layer molybdenum disulfide nanosheets. This allows for synthesis of molybdenum disulfide nanosheets with a defined shape and size. The quality of the nanosheets are determined by the energy of the laser and the irradation angle. Lasers can also be used to form molybdenum disulfide nanosheets from molybdenum disulfide fullerene-like molecules. Hafnium disulfide. Hafnium disulfide () has a layered structure with strong covalent bonding between the Hf and S atoms in a layer and weak van der Waals forces between layers. The compound has type structure and is an indirect band gap semiconducting material. The interlayer spacing  between the layers is 0.56 nm, which is small compared to group VIB TMDs like , making it difficult to cleave its atomic layers. However, recently its crystals with large interlayer spacing has grown using a chemical vapor transport route. These crystals exfoliate in solvents like N-Cyclohexyl-2-pyrrolidone (CHP) in a time of just some minutes resulting in a high-yield production of its few-layers resulting in increase of its indirect bandgap from 0.9 eV to 1.3 eV. As an application in electronics, its field-effect transistors has been realised using its few layers as a conducting channel material  offering a high current modulation ratio larger than 10000 at room temperature. Therefore, group IVB TMDs also holds potential applications in the field of opto-electronics. Tungsten diselenide. Tungsten diselenide is an inorganic compound with the formula . The compound adopts a hexagonal crystalline structure similar to molybdenum disulfide. Every tungsten atom is covalently bonded to six selenium ligands in a trigonal prismatic coordination sphere, while each selenium is bonded to three tungsten atoms in a pyramidal geometry. The tungsten – selenium bond has a bond distance of 2.526 Å and the distance between selenium atoms is 3.34 Å. Layers stack together  via van der Waals interactions. is a stable semiconductor in the group-VI transition-metal dichalcogenides. The electronic bandgap of can be tuned by mechanical strain which can also allow for conversion of the band type from indirect-to-direct in a bilayer.