The argyrodites — A new family of tetrahedrally close-packed structures

Kuhs, Werner F.; Nitsche, R.; Scheunemann, K.

doi:10.1016/0025-5408(79)90125-9

Cited by 280 publications

(186 citation statements)

References 16 publications

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“…All materials were investigated by X-ray powder diffraction in order to determine the resulting phases and to compare the results with those reported by Kuhs et al (1979). The compositions calculated from single crystal X-ray data were taken to prepare phase pure samples of the respective materials.…”

Section: X-ray Powder Diffractionmentioning

confidence: 99%

“…The argyrodites were declared as a structure family by Hahn, Schulze and Sechser (1965), and Kuhs, Nitsche and Scheunemann (1978a;1979), and can be derived from the mineral Ag 8 GeS 6 called Argyrodite (Goldschmidt, 1909;Palache, Berman and Fondel, 1944 (Krebs and Mandt, 1972;Susa and Steinfink, 1971) and Hg 2þ (Gulay, Olekseyuk and Parasyuk, 2002) but the B-cation can be substituted by tetravalent Ti and pentavalent Nb or Ta (e.g. in Ag (12Àn) B nþ Q 6 , Q ¼ S, Se) (Onoda, Wada, Hiroaki and Tansho, 1998;Wada, 1992;Wada, Sato, Onoda, Adams, Tansho and Ishii, 2002) and most of the group 13 to group 15 elements of the periodic table (trivalent Al and Ga (Gaudin, Deiseroth and Zaiss, 2001;Tansho, Wada, Ishii and Onoda, 1996) tetravalent Si, Ge and Sn (Matje and Schön, 1980) and pentavalent P and As.…”

Section: Introductionmentioning

confidence: 99%

“…Cu 6 PS 5 I is the best studied quaternary copper argyrodite. Besides high ionic conductivity this material exhibits ferroelastic and nonlinear optical properties (Kuhs et al, 1979;Studenyak, Stefanovich, Kranjcec, Desnica, Azhniuk, Kovacs and Panko, 1997). The determination of the electrical properties of Cu 7 GeS 5 I and the comparison of them with other quaternary silver and copper argyrodites like Cu 6 PS 5 I and Ag 7 GeS 5 I by Studenyak, Kranjcec, Kovac, Desnica-Frankovic, Molnar, Panko and Slivka (2002), proved an enhancement of conductivity after heterovalent substitution of P with Ge and the corresponding change in the content of monovalent cations.…”

Section: Introductionmentioning

confidence: 99%

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A structural differentiation of quaternary copper argyrodites: Structure — property relations of high temperature ion conductors

Nilges¹,

Pfitzner²

2005

Zeitschrift Für Kristallographie - Crystalline Materials

115

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Section: X-ray Powder Diffractionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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A structural differentiation of quaternary copper argyrodites: Structure — property relations of high temperature ion conductors

Nilges¹,

Pfitzner²

2005

Zeitschrift Für Kristallographie - Crystalline Materials

115

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“…Kuhs et al generalized the formula of argyrodites and found several substituted representatives with mixed anion substructure. 7 Today argyrodites consisting of mono-or divalent cations A (Cu + , Ag + , Li + , Cd 2+ , Hg 2+ ), and a tri-, tetra-, or pentavalent cation B forming a complex anion with a chalcogenide ion Q (O 2− , S 2− , Se 2− , Te 2− ) are known. The general formula is A m+ ((12−n−y)/m) B n+ Q 2− 6−y X − y .…”

Section: ■ Introductionmentioning

confidence: 99%

Synthesis and Crystal Structure Determination of Ag₉FeS_4.1Te_1.9, the First Example of an Iron Containing Argyrodite

et al. 2013

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Ag 9 FeS 4.1 Te 1.9 was prepared by solid state synthesis from stoichiometric amounts of the elements at 873 K. The compound forms gray crystals which are stable against air and moisture. The crystal structure was determined by X-ray diffraction from selected single crystals. Ag 9 FeS 4.1 Te 1.9 crystallizes in the space group F4̅ 3m, a = 11.0415(7) Å, V = 1346.1(1) Å 3 , and Z = 4 (powder data at 293 K). The compound shows a reversible phase transition upon cooling to the space group P2 1 3, a = 11.0213(1) Å, V = 1338.75(2) Å 3 , and Z = 4 (single crystal data at 200 K). The title compound is the first example of an iron containing argyroditetype material with Fe 3+ located in tetrahedral sites. Silver atoms are disordered at room temperature which was taken into account by nonharmonic refinement of the silver positions. The refinement converged to R 1 = 3.51% and wR 2 = 10.66% for the room temperature measurement and to R 1 = 1.55% and wR 2 = 5.23% for the 200 K data set (all data). Impedance measurements were performed in the temperature range from 323 to 473 K. Ionic conductivity values are 1.81 × 10 −2 S cm −1 at 323 K and 1.41 × 10 −1 S cm −1 at 468 K. The activation energy is 0.19 eV from 323 to 423 K and 0.06 eV from 393 to 473 K. DTA measurements reveal congruent melting at 907 K. A phase transition temperature of 232 K with an enthalpy of 7.9 kJ/mol was determined by DSC measurements. 57 Fe Mossbauer spectra show one signal at 298 K and a doublet at 78 K, indicating Fe 3+ and structural distortions upon cooling the samples. Hyperfine field splitting of iron is observed at 5 K. Measurements of the molar susceptibility revealed that the compound is paramagnetic down to a Neél temperature of T N = 22.1(5) K. Antiferromagnetic ordering is observed at lower temperatures. KEYWORDS: argyrodite, ion conductor, nonharmonic refinement, Mossbauer spectroscopy, magnetism ■ INTRODUCTIONThe mineral Argyrodite Ag 8 GeS 6 was the first representative of a large family of compounds which is nowadays called argyrodites. They have been investigated for a long time because of their interesting physical and chemical properties. Among these, ionic conductivity is the most prominent one. It is associated with argyrodites of Li, 1,2 Ag, 3,4 and Cu. 5,6 A huge number of argyrodites is known to date due to a manifold of substitution possibilities on the different sites. Kuhs et al. generalized the formula of argyrodites and found several substituted representatives with mixed anion substructure. 7 Today argyrodites consisting of mono-or divalent cations A (Cu + , Ag + , Li + , Cd 2+ , Hg 2+ ), and a tri-, tetra-, or pentavalent cation B forming a complex anion with a chalcogenide ion Q (O 2− , S 2− , Se 2− , Te 2− ) are known. The general formula is A m+ ((12−n−y)/m) B n+ Q 2− 6−y X − y . The multivalent cation B must have an appropriate size and must be capable of forming tetrahedra. Typical multivalent cations are the main group elements Al 3+ , Ga 3+ , Si 4+ , Ge 4+ , Sn 4+ , P 5+ , As 5+ , and Sb 5+ . A limited n...

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“…Rysanek, Laruelle & Katty (1976) ont d&ermin~ la structure de Ag8GeTe 6, Krebs & Mandt (1977), celle de AgsSiS 6 isotype de Ag8GeS 6 (Eulenberger, 1977). Kuhs, Nitsche & Scheunemann (1978) Cu8SiS 6 a +t6 isol+ par Thomas (1966) au cours de l'6tude du syst+me Cu-Si-S et les diagrammes de poudre avaient &6 interpr+t6s par une maille cubique (a = 9,81/k). A l'occasion d'exp~riences de fabrication de cristaux semi-conducteurs t+tra~driques, des cristaux de forme cubique et de composition CusSiS 6 sont apparus.…”

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Structure du sulfure de cuivre et de silicium Cu8SiS6

Levalois¹,

Allais²

1981

Acta Crystallogr B Struct Crystallogr Cryst Chem

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The argyrodites — A new family of tetrahedrally close-packed structures

Cited by 280 publications

References 16 publications

A structural differentiation of quaternary copper argyrodites: Structure — property relations of high temperature ion conductors

A structural differentiation of quaternary copper argyrodites: Structure — property relations of high temperature ion conductors

Synthesis and Crystal Structure Determination of Ag₉FeS_4.1Te_1.9, the First Example of an Iron Containing Argyrodite

Structure du sulfure de cuivre et de silicium Cu8SiS6

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The argyrodites — A new family of tetrahedrally close-packed structures

Cited by 280 publications

References 16 publications

A structural differentiation of quaternary copper argyrodites: Structure — property relations of high temperature ion conductors

A structural differentiation of quaternary copper argyrodites: Structure — property relations of high temperature ion conductors

Synthesis and Crystal Structure Determination of Ag9FeS4.1Te1.9, the First Example of an Iron Containing Argyrodite

Structure du sulfure de cuivre et de silicium Cu8SiS6

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Synthesis and Crystal Structure Determination of Ag₉FeS_4.1Te_1.9, the First Example of an Iron Containing Argyrodite