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Title: Two-Dimensional CsAg5Te3–xSx Semiconductors: Multi-anion Chalcogenides with Dynamic Disorder and Ultralow Thermal Conductivity

Abstract

Metal chalcogenides underpin a wide variety of energyrelated applications and are ideal systems for probing lattice dynamics and fundamental transport phenomena. Here we describe the synthesis and transport properties of CsAg5TeS2 and its solid solution CsAg5Te3-xSx (x = 1-2), new semiconductors with tunable band gaps ranging from 0.17 to 0.30 eV. CsAg5TeS2 has a fully ordered two-dimensional structure that includes a group of Ag atoms in a heteroleptic tetrahedral coordination geometry (AgTe2S2). Single-crystal X-ray diffraction indicates that the compounds crystallize in the tetragonal space group P4/mmm, while pair distribution function (PDF) analysis reveals off-centering at the heteroleptic Ag sites, signifying the lower-symmetry I4/mcm space group. The underlying disorder as a phonon-blocking mechanism that helps facilitate an ultralow lattice thermal conductivity below 0.40 Wm-1 • K-1 at , ~ 300 K , highlighting the importance of local disorder in thermal transport. In conclusion, density functional theory provides additional insight into the electronic and thermal properties of the materials, which are good candidates for p-type thermoelectrics.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]
  1. Northwestern Univ., Evanston, IL (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
  3. Northwestern Univ., Evanston, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1487454
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 30; Journal Issue: 20; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Hodges, James M., Xia, Yi, Malliakas, Christos D., Alexander, Grant C. B., Chan, Maria K. Y., and Kanatzidis, Mercouri G.. Two-Dimensional CsAg5Te3–xSx Semiconductors: Multi-anion Chalcogenides with Dynamic Disorder and Ultralow Thermal Conductivity. United States: N. p., 2018. Web. https://doi.org/10.1021/acs.chemmater.8b03306.
Hodges, James M., Xia, Yi, Malliakas, Christos D., Alexander, Grant C. B., Chan, Maria K. Y., & Kanatzidis, Mercouri G.. Two-Dimensional CsAg5Te3–xSx Semiconductors: Multi-anion Chalcogenides with Dynamic Disorder and Ultralow Thermal Conductivity. United States. https://doi.org/10.1021/acs.chemmater.8b03306
Hodges, James M., Xia, Yi, Malliakas, Christos D., Alexander, Grant C. B., Chan, Maria K. Y., and Kanatzidis, Mercouri G.. Wed . "Two-Dimensional CsAg5Te3–xSx Semiconductors: Multi-anion Chalcogenides with Dynamic Disorder and Ultralow Thermal Conductivity". United States. https://doi.org/10.1021/acs.chemmater.8b03306. https://www.osti.gov/servlets/purl/1487454.
@article{osti_1487454,
title = {Two-Dimensional CsAg5Te3–xSx Semiconductors: Multi-anion Chalcogenides with Dynamic Disorder and Ultralow Thermal Conductivity},
author = {Hodges, James M. and Xia, Yi and Malliakas, Christos D. and Alexander, Grant C. B. and Chan, Maria K. Y. and Kanatzidis, Mercouri G.},
abstractNote = {Metal chalcogenides underpin a wide variety of energyrelated applications and are ideal systems for probing lattice dynamics and fundamental transport phenomena. Here we describe the synthesis and transport properties of CsAg5TeS2 and its solid solution CsAg5Te3-xSx (x = 1-2), new semiconductors with tunable band gaps ranging from 0.17 to 0.30 eV. CsAg5TeS2 has a fully ordered two-dimensional structure that includes a group of Ag atoms in a heteroleptic tetrahedral coordination geometry (AgTe2S2). Single-crystal X-ray diffraction indicates that the compounds crystallize in the tetragonal space group P4/mmm, while pair distribution function (PDF) analysis reveals off-centering at the heteroleptic Ag sites, signifying the lower-symmetry I4/mcm space group. The underlying disorder as a phonon-blocking mechanism that helps facilitate an ultralow lattice thermal conductivity below 0.40 Wm-1 • K-1 at , ~ 300 K , highlighting the importance of local disorder in thermal transport. In conclusion, density functional theory provides additional insight into the electronic and thermal properties of the materials, which are good candidates for p-type thermoelectrics.},
doi = {10.1021/acs.chemmater.8b03306},
journal = {Chemistry of Materials},
number = 20,
volume = 30,
place = {United States},
year = {2018},
month = {9}
}

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