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Role of the solvent medium in the wet-chemical synthesis of CuSbS2, Cu3SbS3, and bismuth substituted Cu3SbS3

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Abstract

Co-thermal decompositions of equimolar concentrations of thiourea complexes ([Cu(tu)3]Cl and [Sb(tu)2]Cl3) in ethylene glycol and ethanolamine were attempted. Based on the results from powder X-ray diffraction, Raman spectroscopy, and energy dispersive spectral analysis of the products, Cu3SbS3 in cubic symmetry emerged from ethylene glycol. In contrast, orthorhombic CuSbS2 resulted from the ethanolamine medium. The generation of copper-rich and copper-poor sulfides was found to be the major reason behind the formation of these stoichiometries of the Cu-Sb-S system as verified by reacting the preformed Cu-S and Sb-S species in ethanolamine and ethylene glycol. Attempts to include bismuth (up to 50 mol%) for antimony were successful only in ethylene glycol medium. The inclusion of bismuth stabilized the orthorhombic form of Cu3SbS3, possibly due to the non-bonded lone pairs present on Bi3+ and Sb3+-ions. The inclusion of bismuth confirmed from the successful refinement of powder X-ray diffraction pattern by the Rietveld method, Raman spectroscopy, and energy dispersive spectroscopy analysis. CuSbS2, Cu3SbS3 (cubic) and Cu3Sb0.50Bi0.50S3 showed broad absorption extending up to visible region in their UV-visible spectra. The bandgap values of 1.31, 1.40 and 0.94 eV were estimated by Tauc plots for Cu3SbS3, CuSbS2, and Cu3Sb0.50Bi0.50S3, respectively.

Graphic abstract

CuSbS2, Cu3SbS3 (cubic) and Cu3Sb0.50Bi0.50S3 showed broad absorption extending up to visible region in their UV-visible spectra. The bandgap values of 1.31, 1.40 and 0.94 eV were estimated by Tauc plots for Cu3SbS3, CuSbS2, and Cu3Sb0.50Bi0.50S3, respectively.

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Acknowledgments

Financial support from SERB (EMR/2016/006131 and EMR/2016/006762) Government of India for this work is gratefully acknowledged. Shalu thanks UGC, Govt. of India, for the research fellowship.

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Authors and Affiliations

  1. Materials Chemistry Group, Department of Chemistry, University of Delhi, Delhi, 110 007, India

    Shalu Atri, Meenakshi Gusain, Prashant Kumar, Sitharaman Uma & Rajamani Nagarajan

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  1. Shalu Atri
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  2. Meenakshi Gusain
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  3. Prashant Kumar
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  4. Sitharaman Uma
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  5. Rajamani Nagarajan
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Correspondence to Rajamani Nagarajan.

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Atri, S., Gusain, M., Kumar, P. et al. Role of the solvent medium in the wet-chemical synthesis of CuSbS2, Cu3SbS3, and bismuth substituted Cu3SbS3. J Chem Sci 132, 132 (2020). https://doi.org/10.1007/s12039-020-01831-z

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