Role of iron in synthetic tetrahedrites revisited

Nasonova, Daria I.; Presniakov, Igor A.; Sobolev, A. V.; Verchenko, Valeriy Yu.; Tsirlin, Alexander A.; Wei, Zheng; Dikarev, Evgeny V.; Shevelkov, Аndrei V.

doi:10.1016/j.jssc.2015.12.015

Cited by 16 publications

(17 citation statements)

References 28 publications

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“…The crystal structure was refined by varying the atomic coordinates, lattice parameters, occupancies and isotropic displacement parameters. The transition metal (TM) element was substituted at the 12d tetrahedral site in accordance with various literature reports, ,,,, where it was proved that transition metal elements prefer substitution on the 12d site rather than the trigonally coordinated 12e site. Moreover, it was found from theoretical calculations that TM substitution is energetically more favorable at the 12d site as compared to the 12e site, which leads to the conclusion that TM substitutes at the 12d site.…”

Section: Results and Discussionsupporting

confidence: 67%

Electronic and Thermoelectric Properties of Transition Metal Substituted Tetrahedrites

et al. 2018

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A detailed theoretical and experimental study is carried out to understand the effect of transition metal atom (TM) substitution at the Cu tetrahedral site in synthetic tetrahedrite material Cu 12−x TM x Sb 4 S 13 (TM = Mn, Fe, Co, Ni, and Zn). The samples are prepared by solid state synthesis method with the desired compositions. The X-ray diffraction (XRD) pattern of all the samples reveal tetrahedrite as the main phase with traces of secondary phases, confirmed by Electron Probe Micro Analysis (EPMA). X-ray Photoelectron Spectroscopy (XPS) reveals that TM is in +2 oxidation state for all samples except for Fe which shows a + 3 oxidation state. Ultraviolet Photoelectron Spectroscopy (UPS) measurements show the highest work function for Cu 11.5 Co 0.5 Sb 4 S 13 , indicating high band degeneracy. Density Functional Theory (DFT) calculations reveal that TM substitution introduces spin polarized states within the band structure, thus, changing the band degeneracy and density of states (DOS) at the Fermi level (E F ). It is confirmed from DFT calculations that band degeneracy is highest for Cu 11.5 Co 0.5 Sb 4 S 13 among the TM substituted samples, with high DOS at E F , which is experimentally confirmed by magnetic susceptibility analysis. The electrical resistivity (ρ) and Seebeck coefficients (S) of the substituted samples are higher than the pristine compound due to compensation of holes caused by substitution of TM +2 or TM +3 on the Cu tetrahedral site. Because of the high band degeneracy and DOS at E F , a high power factor is achieved for the composition Cu 11.5 Co 0.5 Sb 4 S 13 , enabling it to attain the maximum figure of merit (zT) among the substituted tetrahedrite compositions. The paper presents a comprehensive study to understand the role of magnetic impurities (TM) in influencing the band structure and, hence, the transport properties in substituted tetrahedrite.

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Section: Results and Discussionsupporting

confidence: 67%

Electronic and Thermoelectric Properties of Transition Metal Substituted Tetrahedrites

et al. 2018

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“…Since then, several structural refinements, both on natural and synthetic samples, have been reported (e.g. Wuensch et al, 1966;Kalbskopf, 1972Kalbskopf, , 1974Makovicky & Skinner, 1979;Johnson & Burnham, 1985;Peterson & Miller, 1986;Dmitrieva et al, 1987;Rozhdestvenskaya et al, 1993;Pfitzner et al, 1997;Foit & Hughes, 2004;Makovicky et al, 2005;Andreasen et al, 2008;Pervukhina et al, 2010b;Nasonova et al, 2016;Š ká cha et al, 2016).…”

Section: The Tetrahedrite Isotypic Seriesmentioning

confidence: 99%

“…understand the role of certain components such as Fe (e.g. Makovicky et al, 1990Makovicky et al, , 2003Nasonova et al, 2016), Hg (e.g. Foit & Hughes, 2004), Te and Se (e.g.…”

Section: Figurementioning

confidence: 99%

A crystallographic excursion in the extraordinary world of minerals: the case of Cu- and Ag-rich sulfosalts

Bindi

Biagioni

2018

Acta Crystallogr Sect B

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Copper and silver are common constituents in natural sulfosalts and can be present as minor or major components. Owing to the different kinds of coordination they can assume, these elements give rise to a number of sulfosalts that are usually quite complex to describe from a structural point of view because of the presence of twinning, disorder, polytypism and sometimes incommensurate modulation. Moreover, it is common to find them in different, partially occupied split sites, favoring the presence of strong ionic conductivity that can be related to a number of interesting technological properties. In this regard, a series of Cu-and Ag-rich sulfosalts showing an excess of these cations with respect to As, Sb and Bi is particularly interesting. Their crystal structures as well as their potential interest for materials science and solid-state physics are outlined. Copper-and mixed (Cu, Ag)-sulfosalts belonging to the wittichenite, tetrahedrite, galkhaite, routhierite and nowackiite series are discussed, together with some related compounds. Whereas in the wittichenite series Cu has either a trigonal planar or tetrahedral coordination, in members of the other series this element forms three-dimensional tetrahedral frameworks giving rise to cavities hosting other cations and anions. More difficult is the description of Ag-rich sulfosalts owing to the highly variable coordination environments shown by this element. Structural features of selected Ag sulfosalts together with members of the argyrodite series are discussed, highlighting the particular properties derived from the behavior of Ag.

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“…The voluminous literature concerned with the chemistry of natural and synthetic tetrahedrite and tennantite and with selected synonyms (e.g., binnite and coppite) has recently been summarized and referenced by Biagioni et al [4]. The principal complication of the chemistry of this solid solution, the interplay of Fe 3+ and Fe 2+ in tetrahedrite and tennatite, has been studied by several authors (e.g., Makovicky et al [5,6]; Andreasen et al [7]; Nasonova et al [8]). It does not alter the crystal structure principles of these minerals.…”

Section: Introductionmentioning

confidence: 99%

Twinning of Tetrahedrite—OD Approach

Makovicky

2021

Minerals

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The common twinning of tetrahedrite and tennantite can be described as an order–disorder (OD) phenomenon. The unit OD layer is a one-tetrahedron-thick (111) layer composed of six-member rings of tetrahedra, with gaps between them filled with Sb(As) coordination pyramids and triangular-coordinated (Cu, Ag). The stacking sequence of six-member rings is ABCABC, which can also be expressed as a sequence of three consecutive tetrahedron configurations, named α, β, and γ. When the orientation of component tetrahedra is uniform, the α, β, γ, α sequence builds the familiar cage structure of tetrahedrite. However, when the tetrahedra of the β layer are rotated by 180° against those in the underlying α configurations and/or when a rotated α configuration follows after the β configuration (instead of γ), twinning is generated. If repeated, this could generate the ABAB sequence which would modify the structure considerably. If the rest of the structure grows as a regular cubic tetrahedrite structure, the single occurrence of the described defect sequences creates a twin.

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Role of iron in synthetic tetrahedrites revisited

Cited by 16 publications

References 28 publications

Electronic and Thermoelectric Properties of Transition Metal Substituted Tetrahedrites

Electronic and Thermoelectric Properties of Transition Metal Substituted Tetrahedrites

A crystallographic excursion in the extraordinary world of minerals: the case of Cu- and Ag-rich sulfosalts

Twinning of Tetrahedrite—OD Approach

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