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Title: High-temperature decomposition of Cu 2 BaSnS 4 with Sn loss reveals newly identified compound Cu 2 Ba 3 Sn 2 S 8

Abstract

The earth-abundant quaternary compound Cu2BaSnS4 is being currently studied as a candidate for photovoltaics and as a photocathode for water splitting. However, the chemical stability of this phase during synthesis is unclear. The synthesis of other quaternary tin–sulphur-based absorbers (e.g., Cu2ZnSnS4) involves an annealing step at high temperature under sulphur gas atmosphere, which can lead to decomposition into secondary phases involving Sn loss from the sample. As the presence of secondary phases can be detrimental for device performance, it is crucial to identify secondary phase chemical, structural and optoelectronic properties. Here we used a combination of in situ EDXRD/XRF and TEM to identify a decomposition pathway for Cu2BaSnS4. Our study reveals that, while Cu2BaSnS4 remains stable at high sulphur partial pressure, the material decomposes at high temperatures into Cu4BaS3 and the hitherto unknown compound Cu2Ba3Sn2S8 if the synthesis is performed under low partial pressure of sulphur. The presence of Cu4BaS3 in devices could be harmful due to its high conductivity and relatively lower band gap compared to Cu2BaSnS4. The analysis of powder diffraction data reveals that the newly identified compound Cu2Ba3Sn2S8 crystallizes in the cubic system (space group $$I\bar{4}3d$$) with a lattice parameter of a = 14.53(1) Å. A yellow powder of Cu2Ba3Sn2S8 has been synthesized, exhibiting an absorption onset at 2.19 eV.

Authors:
ORCiD logo [1];  [2];  [1];  [3];  [1];  [1];  [4]; ORCiD logo [3]; ORCiD logo [1]; ORCiD logo [5]; ORCiD logo [1]
  1. Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, 14109 Berlin, Germany
  2. Department of Mechanical Engineering and Materials Science, Duke University, Durham, USA
  3. Division of Applied Materials Sciences, Department of Engineering Sciences, Angstrom Laboratory, Uppsala University, SE 752 37 Uppsala
  4. Helmholtz-Zentrum Berlin für Materialien und Energie GmbH, 14109 Berlin, Germany, University of Florida, Department of Chemical Engineering
  5. Department of Mechanical Engineering and Materials Science, Duke University, Durham, USA, Department of Chemistry
Publication Date:
Research Org.:
Duke Univ., Durham, NC (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); European Research Council (ERC)
OSTI Identifier:
1632970
Alternate Identifier(s):
OSTI ID: 1783204
Grant/Contract Number:  
SC0020061; H2020-NMBP-03-2016-720907
Resource Type:
Published Article
Journal Name:
Journal of Materials Chemistry. A
Additional Journal Information:
Journal Name: Journal of Materials Chemistry. A Journal Volume: 8 Journal Issue: 22; Journal ID: ISSN 2050-7488
Publisher:
Royal Society of Chemistry (RSC)
Country of Publication:
United Kingdom
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Márquez, José A., Sun, Jon-Paul, Stange, Helena, Ali, Hasan, Choubrac, Leo, Schäfer, Stefan, Hages, Charles J., Leifer, Klaus, Unold, Thomas, Mitzi, David B., and Mainz, Roland. High-temperature decomposition of Cu 2 BaSnS 4 with Sn loss reveals newly identified compound Cu 2 Ba 3 Sn 2 S 8. United Kingdom: N. p., 2020. Web. https://doi.org/10.1039/D0TA02348E.
Márquez, José A., Sun, Jon-Paul, Stange, Helena, Ali, Hasan, Choubrac, Leo, Schäfer, Stefan, Hages, Charles J., Leifer, Klaus, Unold, Thomas, Mitzi, David B., & Mainz, Roland. High-temperature decomposition of Cu 2 BaSnS 4 with Sn loss reveals newly identified compound Cu 2 Ba 3 Sn 2 S 8. United Kingdom. https://doi.org/10.1039/D0TA02348E
Márquez, José A., Sun, Jon-Paul, Stange, Helena, Ali, Hasan, Choubrac, Leo, Schäfer, Stefan, Hages, Charles J., Leifer, Klaus, Unold, Thomas, Mitzi, David B., and Mainz, Roland. Wed . "High-temperature decomposition of Cu 2 BaSnS 4 with Sn loss reveals newly identified compound Cu 2 Ba 3 Sn 2 S 8". United Kingdom. https://doi.org/10.1039/D0TA02348E.
@article{osti_1632970,
title = {High-temperature decomposition of Cu 2 BaSnS 4 with Sn loss reveals newly identified compound Cu 2 Ba 3 Sn 2 S 8},
author = {Márquez, José A. and Sun, Jon-Paul and Stange, Helena and Ali, Hasan and Choubrac, Leo and Schäfer, Stefan and Hages, Charles J. and Leifer, Klaus and Unold, Thomas and Mitzi, David B. and Mainz, Roland},
abstractNote = {The earth-abundant quaternary compound Cu2BaSnS4 is being currently studied as a candidate for photovoltaics and as a photocathode for water splitting. However, the chemical stability of this phase during synthesis is unclear. The synthesis of other quaternary tin–sulphur-based absorbers (e.g., Cu2ZnSnS4) involves an annealing step at high temperature under sulphur gas atmosphere, which can lead to decomposition into secondary phases involving Sn loss from the sample. As the presence of secondary phases can be detrimental for device performance, it is crucial to identify secondary phase chemical, structural and optoelectronic properties. Here we used a combination of in situ EDXRD/XRF and TEM to identify a decomposition pathway for Cu2BaSnS4. Our study reveals that, while Cu2BaSnS4 remains stable at high sulphur partial pressure, the material decomposes at high temperatures into Cu4BaS3 and the hitherto unknown compound Cu2Ba3Sn2S8 if the synthesis is performed under low partial pressure of sulphur. The presence of Cu4BaS3 in devices could be harmful due to its high conductivity and relatively lower band gap compared to Cu2BaSnS4. The analysis of powder diffraction data reveals that the newly identified compound Cu2Ba3Sn2S8 crystallizes in the cubic system (space group $I\bar{4}3d$) with a lattice parameter of a = 14.53(1) Å. A yellow powder of Cu2Ba3Sn2S8 has been synthesized, exhibiting an absorption onset at 2.19 eV.},
doi = {10.1039/D0TA02348E},
journal = {Journal of Materials Chemistry. A},
number = 22,
volume = 8,
place = {United Kingdom},
year = {2020},
month = {6}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1039/D0TA02348E

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