Solution-processed copper zinc tin sulfide thin films from metal xanthate precursors

Monatshefte für Chemie - Chemical Monthly volume 144, pages273–283(2013)Cite this article

Abstract

The quaternary semiconductor copper zinc tin sulfide (Cu2ZnSnS4, CZTS) is one of the most promising alternatives to Ga and In based semiconductors for thin film solar cells. It consists of non-toxic, cheap, and abundant elements and displays highly beneficial optical as well as electronic properties for photovoltaic applications. In this work we present a solution-based preparation method for CZTS thin films using exclusively metal xanthates as precursor materials. The introduction of branched alkyl side chains (3,3-dimethyl-2-butyl) into the metal xanthates leads to highly soluble precursors with low decomposition temperatures. In addition, these precursors already contain the sulfur needed for the formation of the metal sulfide. Therefore, no external sulfur source such as thiourea, thioacetamide, or elemental sulfur is necessary. For the preparation of CZTS thin films, solutions containing these metal xanthates were used to coat precursor layers, which were subsequently annealed at temperatures between 180 and 350 °C. Depending on the temperature, nanocrystalline films with primary crystallite sizes ranging from 3 nm (180 °C) up to approximately 43 nm (350 °C) were obtained. A combined X-ray diffraction, Raman spectroscopy, and TEM-EDX study showed that a precursor solution with a Cu/(Zn + Sn) ratio of 0.6 has to be used to obtain CZTS films, which show high optical absorption (>2 × 105 cm−1) and an optical band gap of approximately 1.31 eV. First experiments concerning photovoltaic activity of the solution processed CZTS layers were carried out.

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Acknowledgments

The authors thank the Christian Doppler Research Association (CDG), the Federal Ministry of Economy, Family and Youth of Austria, and Isovoltaic AG for financial support. Part of the research work was performed in project IV-1.02 of the Polymer Competence Center Leoben GmbH (PCCL, Austria) within the framework of the COMET program of the Austrian Federal Ministry of Transport, Innovation and Technology and the Federal Ministry of Economy, Family and Youth with contributions by academic and commercial partners. The PCCL is funded by the Austrian Government and the State Governments of Styria and Upper Austria. Additional support by NAWI Graz is gratefully acknowledged.

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Affiliations

  1. Institute for Chemistry and Technology of Materials, Graz University of Technology, Graz, Austria

    Achim Fischereder, Alexander Schenk, Thomas Rath, Angelika Pateter, Robert Saf, Dorith Schenk, Michael Edler, Kathrin Bohnemann & Gregor Trimmel

  2. Christian Doppler Laboratory for Nanocomposite Solar Cells, Graz University of Technology and NanoTecCenter Weiz Forschungsgesellschaft mbH, Graz, Austria

    Achim Fischereder, Alexander Schenk, Thomas Rath, Wernfried Haas, Angelika Pateter, Michael Edler & Gregor Trimmel

  3. Polymer Competence Center Leoben GmbH, Leoben, Austria

    Alexander Schenk & Kathrin Bohnemann

  4. Institute for Electron Microscopy and Fine Structure Research, Graz University of Technology and Graz Centre for Electron Microscopy, Graz, Austria

    Wernfried Haas, Angelika Reichmann, Boril Chernev & Ferdinand Hofer

  5. EDF R&D, Institut de Recherche et Développement sur l’Energie Photovoltaïque (IRDEP), Chatou, France

    Sébastien Delbos, Corentin Gougaud & Negar Naghavi

  6. CNRS, Chatou, France

    Sébastien Delbos, Corentin Gougaud & Negar Naghavi

  7. Chimie ParisTech, Paris, France

    Sébastien Delbos, Corentin Gougaud & Negar Naghavi

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  1. Achim Fischereder
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  2. Alexander Schenk
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  3. Thomas Rath
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Correspondence to Thomas Rath or Gregor Trimmel.

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Fischereder, A., Schenk, A., Rath, T. et al. Solution-processed copper zinc tin sulfide thin films from metal xanthate precursors. Monatsh Chem 144, 273–283 (2013). https://doi.org/10.1007/s00706-012-0882-6

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Keywords

  • Material science
  • Chalcogenides
  • Raman spectroscopy
  • Electron microscopy
  • Mass spectroscopy
  • Thin film solar cells