New insights into the structure, chemistry, and properties of Cu4SnS4

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

doi:10.1016/j.jssc.2017.05.033

Title: New insights into the structure, chemistry, and properties of Cu₄SnS₄

Journal Article · Thu May 25 00:00:00 EDT 2017 · Journal of Solid State Chemistry

DOI:https://doi.org/10.1016/j.jssc.2017.05.033· OSTI ID:1376545

Choudhury, Amitava ^[1]; Mohapatra, Sudip ^[1]; Yaghoobnejad Asl, Hooman ^[1]; Lee, Seng Huat ^[1]; Hor, Yew San ^[1]; Medvedeva, Julia E. ^[1]; McClane, Devon L. ^[1]; Hilmas, Gregory E. ^[1]; McGuire, Michael A. ^[2]; May, Andrew F. ^[2]; Wang, Hsin ^[2]; Dash, Shreeram ^[2]; Welton, Aaron ^[3]; Boolchand, Punit ^[3]; Devlin, Kasey P. ^[4]; Aitken, Jennifer ^[4]; Herbst-Irmer, Regine ^[5]; Petříček, Váčlav ^[6]

Missouri Univ. of Science and Technology, Rolla, MO (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Univ. of Cincinnati, OH (United States)
Duquesne Univ., Pittsburgh, PA (United States)
Univ. Gottingen (Germany)
Academy of Sciences of the Czech Republic (ASCR), Prague (Czech Republic). Inst. of Physics

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.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1376545

Alternate ID(s):: OSTI ID: 1495583

Journal Information:: Journal of Solid State Chemistry, Vol. 253; ISSN 0022-4596

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 20 works

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Title: New insights into the structure, chemistry, and properties of Cu4SnS4

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