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Title: New insights into the structure, chemistry, and properties of Cu 4SnS 4

The ambient temperature structure of Cu 4SnS 4 has been revisited and the recently reported low temperature structure has been confirmed from single-crystal X-ray diffraction data. A structural phase transition from a large monoclinic unit cell at low temperature to a smaller orthorhombic unit cell at high temperature has been observed. The room temperature phase exhibited disorder in the two copper sites, which is a different finding from earlier reports. The low temperature monoclinic form crystallizes in P2 1/c space group, which is isostructural with Cu 4GeS 4. The phase transition has also been studied with variable temperature powder X-ray diffraction and 119Sn Mössbauer spectroscopy. The Seebeck coefficients and electrical resistivity of polycrystalline Cu 4SnS 4 are reported from 16 to 400 K on hot pressed pellets. Thermal conductivity measurements at high temperatures, 350 – 750 K exhibited very low thermal conductivities in the range 0.28 – 0.35 W K –1 m –1. In all the transport measurements the phase transition has been observed at around 232 K. Resistivity decreases, while Seebeck coefficient increases after the phase transition during warming up from low to high temperatures. This change in resistivity has been correlated with the results of first-principles electronic bandmore » structure calculations using highly-accurate screened-exchange local density approximation. It was found that both the low hole effective mass of 0.63 me for the Γ→Y crystallographic direction and small band gap, 0.49 eV, are likely to contribute to the observed higher conductivity of the orthorhombic phase. Cu 4SnS 4 is also electrochemically active and shows reversible reaction with lithium between 1.7 and 3.5 volts.« less
Authors:
 [1] ;  [1] ;  [1] ;  [1] ;  [1] ;  [1] ;  [1] ;  [1] ;  [2] ;  [2] ;  [2] ;  [2] ;  [3] ;  [3] ;  [4] ;  [4] ;  [5] ;  [6]
  1. Missouri Univ. of Science and Technology, Rolla, MO (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  3. Univ. of Cincinnati, OH (United States)
  4. Duquesne Univ., Pittsburgh, PA (United States)
  5. Univ. Gottingen (Germany)
  6. Academy of Sciences of the Czech Republic (ASCR), Prague (Czech Republic). Inst. of Physics
Publication Date:
Grant/Contract Number:
AC05-00OR22725
Type:
Accepted Manuscript
Journal Name:
Journal of Solid State Chemistry
Additional Journal Information:
Journal Volume: 253; Journal ID: ISSN 0022-4596
Publisher:
Elsevier
Research Org:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1376545

Choudhury, Amitava, Mohapatra, Sudip, Yaghoobnejad Asl, Hooman, Lee, Seng Huat, Hor, Yew San, Medvedeva, Julia E., McClane, Devon L., Hilmas, Gregory E., McGuire, Michael A., May, Andrew F., Wang, Hsin, Dash, Shreeram, Welton, Aaron, Boolchand, Punit, Devlin, Kasey P., Aitken, Jennifer, Herbst-Irmer, Regine, and Petříček, Váčlav. New insights into the structure, chemistry, and properties of Cu4SnS4. United States: N. p., Web. doi:10.1016/j.jssc.2017.05.033.
Choudhury, Amitava, Mohapatra, Sudip, Yaghoobnejad Asl, Hooman, Lee, Seng Huat, Hor, Yew San, Medvedeva, Julia E., McClane, Devon L., Hilmas, Gregory E., McGuire, Michael A., May, Andrew F., Wang, Hsin, Dash, Shreeram, Welton, Aaron, Boolchand, Punit, Devlin, Kasey P., Aitken, Jennifer, Herbst-Irmer, Regine, & Petříček, Váčlav. New insights into the structure, chemistry, and properties of Cu4SnS4. United States. doi:10.1016/j.jssc.2017.05.033.
Choudhury, Amitava, Mohapatra, Sudip, Yaghoobnejad Asl, Hooman, Lee, Seng Huat, Hor, Yew San, Medvedeva, Julia E., McClane, Devon L., Hilmas, Gregory E., McGuire, Michael A., May, Andrew F., Wang, Hsin, Dash, Shreeram, Welton, Aaron, Boolchand, Punit, Devlin, Kasey P., Aitken, Jennifer, Herbst-Irmer, Regine, and Petříček, Váčlav. 2017. "New insights into the structure, chemistry, and properties of Cu4SnS4". United States. doi:10.1016/j.jssc.2017.05.033. https://www.osti.gov/servlets/purl/1376545.
@article{osti_1376545,
title = {New insights into the structure, chemistry, and properties of Cu4SnS4},
author = {Choudhury, Amitava and Mohapatra, Sudip and Yaghoobnejad Asl, Hooman and Lee, Seng Huat and Hor, Yew San and Medvedeva, Julia E. and McClane, Devon L. and Hilmas, Gregory E. and McGuire, Michael A. and May, Andrew F. and Wang, Hsin and Dash, Shreeram and Welton, Aaron and Boolchand, Punit and Devlin, Kasey P. and Aitken, Jennifer and Herbst-Irmer, Regine and Petříček, Váčlav},
abstractNote = {The ambient temperature structure of Cu4SnS4 has been revisited and the recently reported low temperature structure has been confirmed from single-crystal X-ray diffraction data. A structural phase transition from a large monoclinic unit cell at low temperature to a smaller orthorhombic unit cell at high temperature has been observed. The room temperature phase exhibited disorder in the two copper sites, which is a different finding from earlier reports. The low temperature monoclinic form crystallizes in P21/c space group, which is isostructural with Cu4GeS4. The phase transition has also been studied with variable temperature powder X-ray diffraction and 119Sn Mössbauer spectroscopy. The Seebeck coefficients and electrical resistivity of polycrystalline Cu4SnS4 are reported from 16 to 400 K on hot pressed pellets. Thermal conductivity measurements at high temperatures, 350 – 750 K exhibited very low thermal conductivities in the range 0.28 – 0.35 W K–1 m–1. In all the transport measurements the phase transition has been observed at around 232 K. Resistivity decreases, while Seebeck coefficient increases after the phase transition during warming up from low to high temperatures. This change in resistivity has been correlated with the results of first-principles electronic band structure calculations using highly-accurate screened-exchange local density approximation. It was found that both the low hole effective mass of 0.63 me for the Γ→Y crystallographic direction and small band gap, 0.49 eV, are likely to contribute to the observed higher conductivity of the orthorhombic phase. Cu4SnS4 is also electrochemically active and shows reversible reaction with lithium between 1.7 and 3.5 volts.},
doi = {10.1016/j.jssc.2017.05.033},
journal = {Journal of Solid State Chemistry},
number = ,
volume = 253,
place = {United States},
year = {2017},
month = {5}
}