The role of iron in tetrahedrite and tennantite determined by Rietveld refinement of neutron powder diffraction data

Andreasen, Jens Wenzel; Makovicky, Emil; Lebech, B.; Möller, Sven

doi:10.1007/s00269-008-0239-1

Cited by 42 publications

(42 citation statements)

References 16 publications

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“…Indeed, for TM ¼ Fe, neutron powder diffraction 29 and M€ ossbauer spectroscopy 30 The spin-resolved DOS for U ¼ 0 of TM ¼ Mn, Fe, Co, and Zn is shown in Fig. 6 together with that of TM ¼ Ni.…”

Section: Resultsmentioning

confidence: 99%

Systematic study of electronic and magnetic properties for Cu12–xTMxSb4S13 (TM = Mn, Fe, Co, Ni, and Zn) tetrahedrite

Suekuni

Tomizawa

Ozaki

et al. 2014

Journal of Applied Physics

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Magnetism and superconductivity in Mn, Co, Ni, Cu, and Zn) single crystals J. Appl. Phys. 109, 07E113 (2011); 10.1063/1.3565424 Room-temperature spin glass and near band edge properties of highly disorder ( FeCo ) 0.03 Zn 0.97 O and ( FeCoNi ) 0.03 Zn 0.97 O nanorodsSubstitution effects of 3d transition metal (TM) impurities on electronic and magnetic properties for Cu 12 Sb 4 S 13 tetrahedrite are investigated by the combination of low-temperature experiments and first-principles electronic-structure calculations. The electrical resistivity for the cubic phase of Cu 12 Sb 4 S 13 exhibits metallic behavior due to an electron-deficient character of the compound. Whereas that for 0.5 x 2.0 of Cu 12Àx Ni x Sb 4 S 13 exhibits semiconducting behavior. The substituted Ni for Cu is in the divalent ionic state with a spin magnetic moment and creates impurity bands just above the Fermi level at the top of the valence band. Therefore, the semiconducting behavior of the electrical resistivity is attributed to the thermal excitation of electrons from the valence band to the impurity band. The substitution effect of TM on the electronic structure and the valency of TM for Cu 11.0 TM 1.0 Sb 4 S 13 are systematically studied by the calculation. The substituted Mn, Fe, and Co for Cu are found to be in the ionic states with the spin magnetic moments due to the large exchange splitting of the 3d bands between the minority-and majority-spin states. V C 2014 AIP Publishing LLC.

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Section: Resultsmentioning

confidence: 99%

Systematic study of electronic and magnetic properties for Cu12–xTMxSb4S13 (TM = Mn, Fe, Co, Ni, and Zn) tetrahedrite

Suekuni

Tomizawa

Ozaki

et al. 2014

Journal of Applied Physics

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“…17,18,53 Thus, the suppression of the transition does not appear to be directly related to the disorder induced by the substitutions since the Cu(2) position appears to dominate the transition. Also, the change in unit cell volume does not appear critical.…”

Section: 41mentioning

confidence: 99%

Structural phase transition and phonon instability inCu12Sb4S13

et al. 2016

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A structural phase transition has been discovered in the synthetic tetrahedrite Cu12Sb4S13 at approximately 88 K. Upon cooling, the material transforms from its known cubic symmetry to a tetragonal unit cell that is characterized by an in-plane ordering that leads to a doubling of the unit cell volume. Specific heat capacity measurements demonstrate a hysteresis of more than two degrees in the associated anomaly. Similar hysteresis was observed in powder x-ray diffraction measurements that also indicate a coexistence of the two phases, and together these results suggest a first order transition. This structural transition coincides with a recently-reported metal-insulator transition, and the structural instability is related to the very low thermal conductivity κ in these materials. Inelastic neutron scattering was used to measure the phonon density of states in Cu12Sb4S13 and Cu10Zn2Sb4S13, both of which possess a localized, low-energy phonon mode associated with strongly anharmonic copper displacements that suppress κ. In Cu12Sb4S13, signatures of the phase transition are observed in the temperature dependence of the localized mode, which disappears at the structural transition. In contrast, in the cubic Zn-doped material the mode is at slightly higher-energy but observable for all temperatures, though it softens upon cooling.

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“…The large ADP was interpreted as the dynamical occupation of Cu(2) at off-plane split sites 0.3-0.4 Å away from the 12e site. [15][16][17] This "rattling" of Cu(2) between two off-plane sites is reminiscent of the off-center rattling of guests in the type-I clathrates. In a previous work, the tetrahedrites Cu 10 Tr 2 Sb 4 S 13 were found to exhibit L ðTÞ with no crystalline peak as in disordered systems.…”

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“…The typical examples of such solids are the intermetallic type-I clathrates (Sr=Eu) 8 Ga 16 Ge 30 and Ba 8 Ga 16 Sn 30 . 4,5) The crystal structure consists of dodecahedral and tetrakaidecahedral cages in which the Sr, Ba, and Eu guests are encapsulated.…”

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Glasslike versus Crystalline Thermophysical Properties of the Cu–S based Minerals: Tetrahedrite and Colusite

et al. 2015

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We report the thermal conductivity and specific heat measurements at temperatures down to 0.3 and 0.4 K, respectively, for synthetic Cu-S based minerals, namely, tetrahedrite Cu 10 Zn 2 Sb 4 S 13 with rattling Cu atoms and colusite Cu 23 Zn 3 V 2 Sn 6 S 32 without the rattling mode. Because both are semiconducting and diamagnetic, thermal conductivity and specific heat are predominated by the lattice contribution. For the tetrahedrite, thermal conductivity exhibits a plateau at approximately 4 K and T 1.6 dependence at T < 0.7 K. The specific heat C divided by T 3 displays a broad peak at around 4 K, almost identical to the so-called boson peak generally observed in structural glasses. This peak indicates the presence of an optical mode with the characteristic temperature θ of 20 K, involving the out-of-plane motion of the threefold-coordinated Cu atom. For the colusite, in contrast, thermal conductivity shows a significant peak at 15 K and specific heat reveals an optical mode with a higher θ of 90 K. The contrasting behaviors of the two Cu-S based minerals indicate that the out-of-plane motion of Cu in the tetrahedrite is the source of the glasslike thermophysical properties.

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The role of iron in tetrahedrite and tennantite determined by Rietveld refinement of neutron powder diffraction data

Cited by 42 publications

References 16 publications

Systematic study of electronic and magnetic properties for Cu12–xTMxSb4S13 (TM = Mn, Fe, Co, Ni, and Zn) tetrahedrite

Systematic study of electronic and magnetic properties for Cu12–xTMxSb4S13 (TM = Mn, Fe, Co, Ni, and Zn) tetrahedrite

Structural phase transition and phonon instability inCu12Sb4S13

Glasslike versus Crystalline Thermophysical Properties of the Cu–S based Minerals: Tetrahedrite and Colusite

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