Transition Metal Dichalcogenides

: 220px, Cadmium sulfide, a prototypical metal chalcogenide, is used as a yellow pigment.
A chalcogenide is a chemical compound consisting of at least one chalcogen anion and at least one more electropositive element. Although all group 16 elements of the periodic table are defined as chalcogens, the term chalcogenide is more commonly reserved for sulfides, selenides, tellurides, and polonides, rather than oxides. Many metal ores exist as chalcogenides. Photoconductive chalcogenide glasses are used in xerography. Some pigments and catalysts are also based on chalcogenides. The metal dichalcogenide MoS₂ is a common solid lubricant.

Alkali metal and alkaline earth chalcogenides

Alkali metal and alkaline earth monochalcogenides are salt-like, being colourless and often water-soluble. The sulfides tend to undergo hydrolysis to form derivatives containing bisulfide (SH⁻) anions. The alkali metal chalcogenides often crystallize with the antifluorite structure and the alkaline earth salts in the sodium chloride motif.
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Transition metal chalcogenides

Transition metal chalcogenides occur with many stoichiometries and many structures.Vaughan, D. J.; Craig, J. R. “Mineral Chemistry of Metal Sulfides" Cambridge University Press, Cambridge: 1978. . Most common and most important technologically, however, are the chalcogenides of simple stoichiometries, such as 1:1 and 1:2. Extreme cases include metal-rich phases (e.g. Ta₂S), which exhibit extensive metal-metal bonding, and chalcogenide-rich materials such as Re₂S₇, which features extensive chalcogen-chalcogen bonding.

For the purpose of classifying these materials, the chalcogenide is often viewed as a dianion, i.e., S²⁻, Se²⁻, Te²⁻, and Po²⁻. In fact, transition metal chalcogenides are highly covalent, not ionic, as indicated by their semiconducting properties.

Metal-rich chalcogenides

In most of their chalcogenides, transition metals adopt oxidation states of II or greater. Nonetheless, several examples exist where the metallic atoms far outnumber the chalcogens. Such compounds typically have extensive metal-metal bonding.

Monochalcogenides

Metal monochalcogenides have the formula ME, where M = a transition metal and E = S, Se, Te. They typically crystallize in one of two motifs, named after the corresponding forms of zinc sulfide. In the zinc blende structure, the sulfide atoms pack in a cubic symmetry and the Zn²⁺ ions occupy half of the tetrahedral holes. The result is a diamondoid framework. The main alternative structure for the monochalcogenides is the wurtzite structure wherein the atom connectivities are similar (tetrahedral), but the crystal symmetry is hexagonal. A third motif for metal monochalcogenide is the nickel arsenide lattice, where the metal and chalcogenide each have octahedral and trigonal prismatic coordination, respectively. This motif is commonly subject to nonstoichiometry.

Important monochalcogenides include some pigments, notably cadmium sulfide. Many minerals and ores are monosulfides.Greenwood, N. N.; & Earnshaw, A. (1997). Chemistry of the Elements (2nd Edn.), Oxford:Butterworth-Heinemann. .

Dichalcogenides

Metal dichalcogenides have the formula ME₂, where M = a transition metal and E = S, Se, Te.Wells, A.F. (1984) Structural Inorganic Chemistry, Oxford: Clarendon Press. . The most important members are the sulfides. They are always dark diamagnetic solids, insoluble in all solvents, and exhibit semiconducting properties. Some are supeconductors.
In terms of their electronic structures, these compounds are usually viewed as derivatives of M⁴⁺, where M⁴⁺ = Ti⁴⁺ (d⁰ configuration), V⁴⁺ (d¹ configuration), Mo⁴⁺ (d² configuration). Titanium disulfide was investigated in prototype cathodes for secondary batteries, exploiting its ability to reversibly undergo intercalation by lithium. Molybdenum disulfide is the subject of thousand articles and the main ore of molybdenum, termed molybdenite. It is used as a solid lubricant and catalyst for hydrodesulfurization. The corresponding diselenides and even ditellurides are known, e.g., TiSe₂, MoSe₂, and WSe₂.

Transition metals

Transition metal dichalcogenides typically adopt either cadmium diiodide or molybdenum disulfide structures. In the CdI₂ motif, the metals exhibit octahedral structures. In the MoS₂ motif, which is not observed for dihalides, the metals exhibit trigonal prismatic structures. The strong bonding between the metal and chalcogenide ligands, contrasts with the weak chalcogenide—chalcogenide bonding between the layers. Owing to these contrasting bond strengths, these materials engage in intercalation by alkali metals. The intercalation process is accompanied by charge transfer, reducing the M(IV) centers to M(III). The attraction between electrons and holes in 2D tungsten diselenide is 100s of times stronger than in a typical 3D semiconductor.

Pyrite and related disulfides

In contrast to classical metal dichalcogenides, iron pyrite, a common mineral, is usually described as consisting of Fe²⁺ and the persulfido anion S₂²⁻. The sulfur atoms within the disulfido dianion are bound together via a short S-S bond. "Late" transition metal disulfides (Mn, Fe, Co, Ni) almost always adopt the pyrite or the related marcasite motif, in contrast to early metals (V, Ti, Mo, W) which adopt 4+ oxidation state with two chalcogenide dianions.

Tri- and tetrachalcogenides

Several metals, mainly for the early metals (Ti, V, Cr, Mn groups) also form trichalcogenides. These materials are usually described as M⁴⁺(E₂²⁻)(E²⁻) (where E = S, Se, Te). A well known example is niobium triselenide. Amorphous MoS₃ is produced by treatment of tetrathiomolybdate with acid:
:MoS₄²⁻ + 2 H⁺ → MoS₃ + H₂S
The mineral patrónite, which has the formula VS₄, is an example of a metal tetrachalcogenide. Crystallographic analysis shows that the material can be considered a bis(persulfide), i.e. V⁴⁺,(S₂²⁻)₂.

Main group chalcogenides

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Chalcogen derivatives are known for all of the main group elements except the noble gases. Usually, their stoichiometries follow the classical valence trends, e.g. SiS₂, B₂S₃, Sb₂S₃. Many exceptions exist however, e.g. P₄S₃ and S₄N₄. The structures of many main group materials are dictated by directional covalent bonding, rather than by close packing.

The chalcogen is assigned positive oxidation states for the halides, nitrides, and oxides.

See also

*Phase-change memory
*Chalcogen
*Negative resistance
*Chalcogenide glass
*Hydrogen chalcogenide
*Carbon dichalcogenide

References

External links

Advanced Chalcogenide Technologies and Applications Lab
''ACTAlab'' Jun 14, 2016
Phase change memory-based 'moneta' system points to the future of computer storage
''ScienceBlog'' Jun 03, 2011
*{{cite journal , last1 = Kovalenko , first1 = Maksym V. , last2 = Scheele , first2 = Marcus , last3 = Talapin , first3 = Dmitri V. , title = Colloidal Nanocrystals with Molecular Metal Chalcogenide Surface Ligands , journal = Science , year = 2009 , volume = 324 , issue = 5933 , pages = 1417–1420 , doi=10.1126/science.1170524, pmid = 19520953 , bibcode = 2009Sci...324.1417K, s2cid = 21845356
Big Blue boffins hatch dirt-cheap solar cells
The Register, 12 February 2010