Tungsten(IV) sulfide

Tungsten disulfide is an inorganic chemical compound composed of tungsten and sulfur with the chemical formula WS₂. This compound is part of the group of materials called the transition metal dichalcogenides. It occurs naturally as the rare mineral tungstenite. This material is a component of certain catalysts used for hydrodesulfurization and hydrodenitrification.

WS₂ adopts a layered structure similar, or isotypic with MoS₂, instead with W atoms situated in trigonal prismatic coordination sphere (in place of Mo atoms). Owing to this layered structure, WS₂ forms non-carbon nanotubes, which were discovered after heating a thin sample of WS₂ in 1992.

Structure and physical properties

Bulk WS₂ forms dark gray hexagonal crystals with a layered structure. Like the closely related MoS₂, it exhibits properties of a dry lubricant.

Although it has long been thought that WS₂ is relatively stable in ambient air, recent reports on the ambient air oxidation of monolayer WS₂ have found this to not be the case. In the monolayer form, WS₂ is converted rather rapidly (over the course of days in ambient light and atmosphere) to tungsten oxide via a photo-oxidation reaction involving visible wavelengths of light readily absorbed by monolayer WS₂ (< ~660 nm; > ~1.88 eV). In addition to light of suitable wavelength, the reaction likely requires both oxygen and water to proceed, with the water thought to act as a catalyst for oxidation. The products of the reaction likely include various tungsten oxide species and sulfuric acid. The oxidation of other semiconductor transition metal dichalcogenides (S-TMDs) such as MoS₂, has similarly been observed to occur in ambient light and atmospheric conditions.

WS₂ is also attacked by a mixture of nitric and hydrofluoric acid. When heated in oxygen-containing atmosphere, WS₂ converts to tungsten trioxide. When heated in absence of oxygen, WS₂ does not melt but decomposes to tungsten and sulfur, but only at 1250 °C.

Historically monolayer WS₂ was isolated using chemical exfoliation via intercalation with lithium from n-butyl lithium (in hexane), followed by exfoliation of the Li intercalated compound by sonication in water. WS₂ also undergoes exfoliation by treatment with various reagents such as chlorosulfonic acid and the lithium halides.

Synthesis

WS₂ is produced by a number of methods. Many of these methods involve treating oxides with sources of sulfide or hydrosulfide, supplied as hydrogen sulfide or generated ''in situ''.

Thin films and monolayers

Widely used techniques for the growth of monolayer WS₂ include chemical vapor deposition (CVD), physical vapor deposition (PVD) or metal organic chemical vapor deposition (MOCVD), though most current methods produce sulfur vacancy defects in excess of 1×10¹³ cm⁻². Other routes entail thermolysis of tungsten(VI) sulfides (e.g., (R₄N)₂WS₄) or the equivalent (e.g., WS₃).

Freestanding WS₂ films can be produced as follows. WS₂ is deposited on a hydrophilic substrate, such as sapphire, and then coated with a polymer, such as polystyrene. After dipping the sample in water for a few minutes, the hydrophobic WS₂ film spontaneously peels off.

Applications

WS₂ is used, in conjunction with other materials, as catalyst for hydrotreating of crude oil. In recent years it has also found applications as a saturable for passively mode locked fibre lasers resulting in femtosecond pulses being produced.

Lamellar tungsten disulphide is used as a dry lubricant for fasteners, bearings, and molds, as well as having significant use in aerospace and military industries. WS₂ can be applied to a metal surface without binders or curing, via high-velocity air impingement. The most recent official standard for this process is laid out in the SAE International specification AMS2530A.

Research

Like MoS₂, nanostructured WS₂ is actively studied for potential applications, such as storage of hydrogen and lithium. WS₂ also catalyses hydrogenation of carbon dioxide:
: CO₂ + H₂ → CO + H₂O

Nanotubes

Tungsten disulfide is the first material which was found to form non-carbon nanotubes, in 1992. This ability is related to the layered structure of WS₂, and macroscopic amounts of WS₂ have been produced by the methods mentioned above. WS₂ nanotubes have been investigated as reinforcing agents to improve the mechanical properties of polymeric nanocomposites. In a study, WS₂ nanotubes reinforced biodegradable polymeric nanocomposites of polypropylene fumarate (PPF) showed significant increases in the Young's modulus, compression yield strength, flexural modulus and flexural yield strength, compared to single- and multi-walled carbon nanotubes reinforced PPF nanocomposites, suggesting that WS₂ nanotubes may be better reinforcing agents than carbon nanotubes. The addition of WS₂ nanotubes to epoxy resin improved adhesion, fracture toughness and strain energy release rate. The wear of the nanotubes-reinforced epoxy is lower than that of pure epoxy. WS₂ nanotubes were embedded into a poly(methyl methacrylate) (PMMA) nanofiber matrix via electrospinning. The nanotubes were well dispersed and aligned along fiber axis. The enhanced stiffness and toughness of PMMA fiber meshes by means of non-carbon nanotubes addition may have potential uses as impact-absorbing materials, e.g. for ballistic vests.

WS₂ nanotubes are hollow and can be filled with another material, to preserve or guide it to a desired location, or to generate new properties in the filler material which is confined within a nanometer-scale diameter. To this goal, non-carbon nanotube hybrids were made by filling WS₂ nanotubes with molten lead, antimony or bismuth iodide salt by a capillary wetting process, resulting in PbI₂@WS₂, SbI₃@WS₂ or BiI₃@WS₂ core–shell nanotubes.

Nanosheets

WS₂ can also exist in the form of atomically thin sheets. Such materials exhibit room-temperature photoluminescence in the monolayer limit.

Transistors

Taiwan Semiconductor Manufacturing Company (TSMC) is investigating use of as a channel material in field effect transistors. The approximately 6-layer thick material is created using chemical vapor deposition (CVD).

References

{{Sulfides

Tungsten compounds
Sulfides
Dry lubricants
Transition metal dichalcogenides
Monolayers