Physics and chemistry of MoS2 intercalation compounds

John A. Woollam, Robert B. Somoano

Research output: Contribution to journalArticle

42 Citations (Scopus)

Abstract

Molybdenum disulfide is a layered diamagnetic semiconductor. Trigonal prismatic coordination exists between the Mo and the S atoms, which are primarily covalently bonded. The layers can stack to form either a hexagonal (2H), or a rhombohedral (3R) polymorph. The reaction of MoS2 with alkali and alkaline-earth metals dissolved in liquid ammonia results in a series of metallic superconducting intercalation compounds. The alkali and alkalline-earth intercalates, AxMoS2 (A = Na, K, Rb, Cs, Ca, and Sr) can be separated into two groups according to their stoichiometry, structure and superconducting properties. The first group (I) consists of the Na, Ca, and Sr intercalates, which have nonhexagonal structures, less well-defined stoichiometries, small intercalate ion diameters, and superconduct at temperatures of 3.6, 4.0, and 5.6 K, respectively. The uncertainties in the stoichiometries in this group are NaxMoS2 (0.3 ≤ x ≤ 0.6), CaxMoS2 (0.05 ≤ x ≤ 0.07), and SrxMoS2 (0.06 ≤ x ≤ 0.1). The second group (II) consists of the K, Rb, and Cs intercalates which form compounds of definite stoichiometry (x {all equal to} 0.3), have a well-ordered hexagonal crystal structure, larger intercalate ion diameters, and superconduct at 6.9 K. The compound LixMoS2 differs from the above groups in that NH3 or NH2 intercalates along with Li, and the structure exibits considerable disorder. It superconducts at 3.7 K. The electronic energy band structure of MoS2 results from strong intralayer hybridization between metal dz2 and dxy, dx2-y2 bands resulting in at least a 1 eV gap within the d band manifold. The lowest d sub-band is filled in MoS2, and upon intercalation the Fermi level is raised into the upper d sub-band. The high density of states at the Fermi energy in the intercalates is believed to be the major reason for superconductivity up to 7 K. The superconducting critical magnetic fields are highly anisotropic, and are very large (greater than 20 Tesla for group II) for fields parallel to the layer planes. The critical field angular dependencies can be fitted to either a model for thin film superconductivity (group I), or to an anisotropic effective mass model (group II). An unusual positive curvature in the critical field vs. temperature plots is found in all compounds.

Original languageEnglish (US)
Pages (from-to)289-295
Number of pages7
JournalMaterials Science and Engineering
Volume31
Issue numberC
DOIs
StatePublished - Dec 1977

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Intercalation compounds
Stoichiometry
Physics
Superconductivity
Fermi level
Band structure
Alkaline earth metals
Intercalation
Polymorphism
Heavy ions
Molybdenum
Ammonia
Crystal structure
Earth (planet)
Semiconductor materials
Magnetic fields
Thin films
Atoms
Temperature
Ions

ASJC Scopus subject areas

  • Engineering(all)

Cite this

Physics and chemistry of MoS2 intercalation compounds. / Woollam, John A.; Somoano, Robert B.

In: Materials Science and Engineering, Vol. 31, No. C, 12.1977, p. 289-295.

Research output: Contribution to journalArticle

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abstract = "Molybdenum disulfide is a layered diamagnetic semiconductor. Trigonal prismatic coordination exists between the Mo and the S atoms, which are primarily covalently bonded. The layers can stack to form either a hexagonal (2H), or a rhombohedral (3R) polymorph. The reaction of MoS2 with alkali and alkaline-earth metals dissolved in liquid ammonia results in a series of metallic superconducting intercalation compounds. The alkali and alkalline-earth intercalates, AxMoS2 (A = Na, K, Rb, Cs, Ca, and Sr) can be separated into two groups according to their stoichiometry, structure and superconducting properties. The first group (I) consists of the Na, Ca, and Sr intercalates, which have nonhexagonal structures, less well-defined stoichiometries, small intercalate ion diameters, and superconduct at temperatures of 3.6, 4.0, and 5.6 K, respectively. The uncertainties in the stoichiometries in this group are NaxMoS2 (0.3 ≤ x ≤ 0.6), CaxMoS2 (0.05 ≤ x ≤ 0.07), and SrxMoS2 (0.06 ≤ x ≤ 0.1). The second group (II) consists of the K, Rb, and Cs intercalates which form compounds of definite stoichiometry (x {all equal to} 0.3), have a well-ordered hexagonal crystal structure, larger intercalate ion diameters, and superconduct at 6.9 K. The compound LixMoS2 differs from the above groups in that NH3 or NH2 intercalates along with Li, and the structure exibits considerable disorder. It superconducts at 3.7 K. The electronic energy band structure of MoS2 results from strong intralayer hybridization between metal dz2 and dxy, dx2-y2 bands resulting in at least a 1 eV gap within the d band manifold. The lowest d sub-band is filled in MoS2, and upon intercalation the Fermi level is raised into the upper d sub-band. The high density of states at the Fermi energy in the intercalates is believed to be the major reason for superconductivity up to 7 K. The superconducting critical magnetic fields are highly anisotropic, and are very large (greater than 20 Tesla for group II) for fields parallel to the layer planes. The critical field angular dependencies can be fitted to either a model for thin film superconductivity (group I), or to an anisotropic effective mass model (group II). An unusual positive curvature in the critical field vs. temperature plots is found in all compounds.",
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