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

Abstract

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.

Authors:
ORCiD logo [1];  [1]; ORCiD logo [1];  [1];  [1];  [2];  [1];  [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Northwestern Univ., Evanston, IL (United States)
  2. Koc Univ., Istanbul (Turkey)
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States); Northwestern Univ., Evanston, IL (United States)
Sponsoring Org.:
National Aeronautics and Space Administration (NASA); National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1436781
Alternate Identifier(s):
OSTI ID: 1775335
Grant/Contract Number:  
DMR-1708254; SC0014520
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 57; Journal Issue: 4; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
ENGLISH
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; thermal conductivity; phonons; crystal structure; chemical structure; electrical conductivity

Citation Formats

Khoury, Jason F., Hao, Shiqiang, Stoumpos, Constantinos C., Yao, Zhenpeng, Malliakas, Christos D., Aydemir, Umut, Slade, Tyler J., Snyder, G. Jeffrey, Wolverton, Chris, and Kanatzidis, Mercouri G. Quaternary Pavonites A1+xS2–xBi5+xS10 (A+ = Li+, Na+): Site Occupancy Disorder Defines Electronic Structure. United States: N. p., 2018. Web. doi:10.1021/acs.inorgchem.7b03091.
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. Quaternary Pavonites A1+xS2–xBi5+xS10 (A+ = Li+, Na+): Site Occupancy Disorder Defines Electronic Structure. United States. https://doi.org/10.1021/acs.inorgchem.7b03091
Khoury, Jason F., Hao, Shiqiang, Stoumpos, Constantinos C., Yao, Zhenpeng, Malliakas, Christos D., Aydemir, Umut, Slade, Tyler J., Snyder, G. Jeffrey, Wolverton, Chris, and Kanatzidis, Mercouri G. Wed . "Quaternary Pavonites A1+xS2–xBi5+xS10 (A+ = Li+, Na+): Site Occupancy Disorder Defines Electronic Structure". United States. https://doi.org/10.1021/acs.inorgchem.7b03091. https://www.osti.gov/servlets/purl/1436781.
@article{osti_1436781,
title = {Quaternary Pavonites A1+xS2–xBi5+xS10 (A+ = Li+, Na+): Site Occupancy Disorder Defines Electronic Structure},
author = {Khoury, Jason F. and Hao, Shiqiang and Stoumpos, Constantinos C. and Yao, Zhenpeng and Malliakas, Christos D. and Aydemir, Umut and Slade, Tyler J. and Snyder, G. Jeffrey and Wolverton, Chris and Kanatzidis, Mercouri G.},
abstractNote = {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.},
doi = {10.1021/acs.inorgchem.7b03091},
journal = {Inorganic Chemistry},
number = 4,
volume = 57,
place = {United States},
year = {Wed Feb 07 00:00:00 EST 2018},
month = {Wed Feb 07 00:00:00 EST 2018}
}

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