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

Zhao, Jing; Hao, Shiqiang; Islam, Saiful M.; Chen, Haijie; Tan, Gangjian; Ma, Shulan; Wolverton, Christopher; Kanatzidis, Mercouri G.

doi:10.1021/acs.chemmater.9b00585

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

Journal Article · Tue Apr 09 00:00:00 EDT 2019 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.9b00585· OSTI ID:1777385

^[1]; Hao, Shiqiang ^[2];

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^[2]; Tan, Gangjian ^[4];

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Univ. of Science and Technology Beijing (China)
Northwestern Univ., Evanston, IL (United States)
Northwestern Univ., Evanston, IL (United States); Jackson State Univ., Jackson, MS (United States)
Wuhan Univ. of Technology (China)

Six new quaternary chalcogenides belonging to the pavonite sulfosalt mineral family with the general formula M_n+1(Bi/ Sb)₂Q_n+5 (n = 2-7) were synthesized by direct reactions of the elements at high temperatures. The compounds include InPbBi₃S₇ (n = 2), In_0.5Mn₂Bi_3.5Se₈ (n = 3), CdPb₂Bi₄S₉ (n = 4), Ag_1.5CdBi_5.5Se₁₀ (n = 5), Ag₂CdBi₆Se₁₁ (n = 6), and Ag_2.5CdSb_6.5Se₁₂ (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 galena-like 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. Here, the charge and thermal transport properties of CdPb₂Bi₄S₉ and CdAg₂Bi₆Se₁₁ 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 CdAg₂Bi₆Se₁₁ and 0.73 W·m^–1·K^–1 for CdPb₂Bi₄S₉ 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 Grüneisen parameters. Thermoelectric properties were measured, and the highest ZT values of 0.53 and 0.95 for undoped CdPb₂Bi₄S₉ and CdAg₂Bi₆Se₁₁, respectively, were attained at 775 K.

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Research Organization:: Northwestern Univ., Evanston, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: SC0014520; DMR-1708254; DMR-1720139

OSTI ID:: 1777385

Journal Information:: Chemistry of Materials, Vol. 31, Issue 9; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 15 works

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

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