Quaternary Pavonites A1+xS2–xBi5+xS10 (A+ = Li+, Na+): Site Occupancy Disorder Defines Electronic Structure

Khoury, Jason F.; Hao, Shiqiang; Stoumpos, Constantinos C.; Yao, Zhenpeng; Malliakas, Christos D.; Aydemir, Umut; Slade, Tyler J.; Snyder, G. Jeffrey; Wolverton, Chris; Kanatzidis, Mercouri G.

doi:10.1021/acs.inorgchem.7b03091

Title: Quaternary Pavonites A_1+xS_2–xBi_5+xS₁₀ (A⁺ = Li⁺, Na⁺): Site Occupancy Disorder Defines Electronic Structure

Journal Article · Wed Feb 07 00:00:00 EST 2018 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.7b03091· OSTI ID:1436781

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

^[1]; Yao, Zhenpeng ^[1]; Malliakas, Christos D. ^[1]; Aydemir, Umut ^[2]; Slade, Tyler J. ^[1]; Snyder, G. Jeffrey ^[1];

^[1];

^[1]

Northwestern Univ., Evanston, IL (United States)
Koc Univ., Istanbul (Turkey)

The field of mineralogy represents an area of untapped potential for the synthetic chemist, as there are numerous structure types that can be utilized to form analogues of mineral structures with useful optoelectronic properties. In this work, we describe the synthesis and characterization of two novel quaternary sulfides A1+xSn2-xBi5+xS10 (A = Li+, Na+). Though not natural minerals themselves, both compounds adopt the pavonite structure, which crystallizes in the C2/m space group and consists of two connected, alternating defect rock-salt slabs of varying thicknesses to create a three-dimensional lattice. Despite their commonalities in structure, their rystallography is noticeably different, as both structures have a heavy degree of site occupancy disorder that affects the actual positions of the atoms. The differences in site occupancy alter their electronic structures, with band gap values of 0.31(2) eV and 0.07(2) eV for the lithium and sodium analogues, respectively. LiSn2Bi5S10 exhibits ultralow thermal conductivity of 0.62 W m-1 K-1 at 723 K, and this result is corroborated by phonon dispersion calculations. This structure type is a promising host candidate for future thermoelectric materials investigation, as these materials have narrow band gaps and intrinsically low thermal conductivities.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States); Northwestern Univ., Evanston, IL (United States)

Sponsoring Organization:: National Aeronautics and Space Administration (NASA); National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: DMR-1708254; SC0014520

OSTI ID:: 1436781

Alternate ID(s):: OSTI ID: 1775335

Journal Information:: Inorganic Chemistry, Vol. 57, Issue 4; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: ENGLISH

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Cited by: 10 works

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Title: Quaternary Pavonites A1+xS2–xBi5+xS10 (A+ = Li+, Na+): Site Occupancy Disorder Defines Electronic Structure

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Title: Quaternary Pavonites A_1+xS_2–xBi_5+xS₁₀ (A⁺ = Li⁺, Na⁺): Site Occupancy Disorder Defines Electronic Structure