Extended Occupational and Positional Disorder in Pavonite Homologous Copper Bismuth Chalcogenide Halogenides

Heerwig, Andreas; Thybaut, Cyril Louis Jaques; Ruck, Michael

doi:10.1002/zaac.201000177

Cited by 15 publications

(8 citation statements)

References 27 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…48 Halogen members of this series can be obtained by substituting some of the sulfur atoms with the univalent anions Cl, Br, or I. 48,49 This halogen substitution approach has also been demonstrated to be an effective means of designing new structures, as reported for the pavonite series with n = 1, 2, 3, 4, 5, and 7 compounds in the Ag−Bi−S−Cl (or −Br) system. 20,50 Notably, the n = 6 member is conspicuously rare, both among minerals and synthetic compounds, with only Ag 5 Bi 13 S 22 (n = 6) being structurally analyzed.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Six Quaternary Chalcogenides of the Pavonite Homologous Series with Ultralow Lattice Thermal Conductivity

Zhao

Hao²,

Islam

et al. 2019

Chem. Mater.

View full text Add to dashboard Cite

Six new quaternary chalcogenides belonging to the pavonite sulfosalt mineral family with the general formula M n+1 (Bi/ Sb) 2 Q n+5 (n = 2−7) were synthesized by direct reactions of the elements at high temperatures. The compounds include InPbBi 3 S 7 (n = 2), In 0.5 Mn 2 Bi 3.5 Se 8 (n = 3), CdPb 2 Bi 4 S 9 (n = 4), Ag 1.5 CdBi 5.5 Se 10 (n = 5), Ag 2 CdBi 6 Se 11 (n = 6), and Ag 2.5 CdSb 6.5 Se 12 (n = 7) and crystallized in the monoclinic space group C2/m. The pavonite structure consists of two alternating slabs, a thinner slab composed of pairs of monocapped trigonal prisms separated by octahedra and a thicker slab with a galenalike structure motif. In the general formula, n corresponds to the number of octahedra along the diagonal direction of the galena-like slab. The complex compositions, mixed occupancies of the cations, and quasi-two-dimensional structures endow compounds of this family with extremely low thermal conductivity. The charge and thermal transport properties of CdPb 2 Bi 4 S 9 and CdAg 2 Bi 6 Se 11 were characterized from 300 to 810 K, and both materials exhibited n-type semiconductor behaviors and ultralow lattice thermal conductivities of less than 0.35 W•m −1 •K −1 for CdAg 2 Bi 6 Se 11 and 0.73 W•m −1 •K −1 for CdPb 2 Bi 4 S 9 in the measured temperature range. Density functional theory calculations revealed the origins of this low lattice thermal conductivity to be a combination of the low Debye temperature, small phonon velocities, and large Gruneisen parameters. Thermoelectric properties were measured, and the highest ZT values of 0.53 and 0.95 for undoped CdPb 2 Bi 4 S 9 and CdAg 2 Bi 6 Se 11 , respectively, were attained at 775 K.

show abstract

Section: ■ Results and Discussionmentioning

confidence: 99%

Six Quaternary Chalcogenides of the Pavonite Homologous Series with Ultralow Lattice Thermal Conductivity

Zhao

Hao²,

Islam

et al. 2019

Chem. Mater.

View full text Add to dashboard Cite

show abstract

“…To a certain degree, the octahedrally coordinated Bi 3+ cations are substituted by Cu + cations, or more precisely, [BiSe 2 ] – is replaced by [Cu X 2 ] – . Mixed Cu/Bi occupancy in networksof octahedra was also found in the minerals hodrushite(Cu 8 Bi 12 S 22 )7 and cuprobismutite (Cu 10 Bi 12 S 23 ),8 as well as in synthetic compounds such as Cu 9 BiS 6 ,9 the pavonitehomologues Cu 1.77 Bi 4.57 S 8 10 and Cu 2.93 Bi 4.79 S 9 ,11 andCu 1.57 Bi 2.37 Se 2.68 Br 3.32 4g. On the other hand, there are numerous related compounds, predominantly chalcogenide halogenides, with various structure types, in which copper does not occupy the bismuth sites, such as CuBiSCl 2 ,4cCu 9 Bi 9 S 16 Cl 8 ,4e Cu 7.4 Bi 6 Se 12 Cl 7 ,4e Cu 7 Bi 6 S 10 Cl 5 ,4fCu 22 Bi 12 S 21 Cl 16 ,4h Cu 3 BiS 2 Br 2 ,4i and Cu 4 Bi 3 S 5 Br 1.81 Cl 1.19 4i…”

Section: Resultsmentioning

confidence: 78%

“…Secondly, the option for the inclusion of additional copper cations, found for example in Cu 1.57 Bi 2.37 Se 2.68 Br 3.32 ,4g is not used. Also in the case of Cu1, where a crystallographic center of inversion resides in the polyhedron, the structure refinement shows that only one of the faces of the octahedron is occupied.…”

Section: Resultsmentioning

confidence: 99%

Copper Bismuth Chalcogenide Halogenides with Extensively Disordered and Mobile Copper(I) Cations

Heerwig

Müller

Nitsche

et al. 2012

Zeitschrift anorg allge chemie

Self Cite

View full text Add to dashboard Cite

A new family of quaternary phases with the general sum formula Cu 3+δ Bi 5-δ Se 8-2δ X 2+2δ (X = Cl, Br) was discovered by slow cooling of high temperature melts. Cu 3.58(1) Bi 4.42(1) Se 6.84(2) Cl 3.16(2) (δ = 0.58) and Cu 4.52(1) Bi 3.48(1) Se 4.96(2) Br 5.04(2) (δ = 1.52) crystallize isostructural in the orthorhombic space group type Pnnm with a = 1332.3(1)/1340.2(3) pm, b = 1683.7(2)/1717.2(1) pm, and c = 406.2(1)/407.1(2) pm. The new structure type resembles in some aspects the hollandite as well as the pavonite type. A framework of faceand edge-sharing anion polyhedra around Bi 3+ cations hosts Cu + cations. The characteristic motif is an infinite band of polyhedra that has

show abstract

“…[3] Other copper bismuth chalcohalides have been reported with complex compositions and mixed valency elements. [57,58] Similarly, Cd-, [59,60] In-, [60] and Hg- [61] quaternary pnictogen chalcohalides have been investigated, but seem unlikely to be implemented today as alternative PV absorbers due to the scarcity and/or toxicity of these elements. Lead-based compounds, despite lead toxicity, have been employed.…”

Section: Mixed-metal Chalcohalidesmentioning

confidence: 99%

“…[ 3 ] Other copper bismuth chalcohalides have been reported with complex compositions and mixed valency elements. [ 57,58 ]…”

Section: Mixed‐metal Chalcohalidesmentioning

confidence: 99%

Metal Chalcohalides: Next Generation Photovoltaic Materials?

Palazón

2021

Solar RRL

View full text Add to dashboard Cite

Metal chalcohalides have recently been highlighted as so‐far overlooked semiconductors that could play an important role in the future of photovoltaics (PV). Indeed, the blooming field of emergent PV technologies is still in search for stable, efficient, and environmentally‐friendly light‐harvesting materials to be used either in single‐junction solar cells or multijunction devices in combination with silicon or another absorbers. Under the broad terms of metal chalcohalides, there exists a plethora of semiconductor materials with different chemical, structural, and optoelectronic characteristics. While some have already been implemented in solar cells with power conversion efficiencies up to 4–5%, others are only theoretically described. This perspective article offers a general overview of these materials as potential next‐generation absorbers in PV and also discusses possible limitations, not only related to intrinsic materials’ properties but also to processing conditions.

show abstract

Extended Occupational and Positional Disorder in Pavonite Homologous Copper Bismuth Chalcogenide Halogenides

Abstract: Abstract. Melting reactions of CuBr, BiBr 3 and Bi 2 Q 3 (Q = S or Se) resulted in black needles of quaternary chalcogenide bromides. Cu 1.5 Bi 2.64 S 3.42 Br 2.58 has a melting point of 708 (5)

Cited by 15 publications

References 27 publications

Six Quaternary Chalcogenides of the Pavonite Homologous Series with Ultralow Lattice Thermal Conductivity

Six Quaternary Chalcogenides of the Pavonite Homologous Series with Ultralow Lattice Thermal Conductivity

Copper Bismuth Chalcogenide Halogenides with Extensively Disordered and Mobile Copper(I) Cations

Metal Chalcohalides: Next Generation Photovoltaic Materials?

Contact Info

Product

Resources

About