Phase stability and structural comparison of phases in the Cu-Zn-Sn-S system using solid-state NMR

• Published in: Solar energy materials and solar cells 2019-02, Vol.190, p.37-48
• Main Authors: Pogue, Elizabeth A., Sutrisno, Andre, Johnson, Nicole E., Goetter, Melissa B., Jiang, Zhelong, Shoemaker, Daniel P., Rockett, Angus A.
• Format: Article
• Language: English
• Subjects: Comparative analysis; Copper; Copper sulfides; Kesterite; Nanocrystals; NMR; Nuclear magnetic resonance; Phase diagram; Phase diagrams; Phase stability; Phase transitions; Phases; Raman; Raman spectroscopy; S phase; Solid state; Structural stability; Structure; Sulfide; Temperature; Ternary systems; Thermodynamics; Thin films; Tin; X ray spectra; X-ray diffraction; Zinc
• ISSN: 0927-0248; 1879-3398
• DOI: 10.1016/j.solmat.2018.10.007

Phases in the Cu-Zn-Sn-S system are of interest to the solar and thermoelectrics communities because all elements are earth-abundant and non-toxic. A better understanding of the structures of these phases and the equilibria between them is necessary to guide device manufacturers. This work reviews all the phases reported in this system and reports which phases form and are stable at 200 °C and 400 °C. In this work, the stable phases in the Cu-Zn-Sn-S system (Cu4Sn7S16, Cu4SnS4, Cu2ZnSnS4, and Cu2SnS3) are synthesized and their structures are investigated using solid-state NMR, X-ray diffraction, and Raman spectroscopy. The existing Cu-Sn-S and Cu-Zn-Sn-S phase diagrams are revised based on our synthesis results. Cu3SnS4 and Cu2ZnSn3S8 are removed from the quaternary and ternary phase diagrams because we did not observe either phase. Prior reports (in thin films and nanocrystals) of Cu3SnS4 may be related to trace amounts of In or large surface areas. Monoclinic Cu2SnS3 is not stable at 400 °C and, at this temperature, a disordered tetragonal phase is stable. At lower temperatures (room-temperature and 200 °C ), this same (disordered) tetragonal phase is stable at compositions that are Cu-rich and Sn-poor from Cu2SnS3. Cu4SnS6 was added to the phase diagram at 400 °C. Significant differences in reaction rate when forming Cu4SnS4 from either elemental or binary sulfide precursors are noted and explained. The NMR results are generalized to aid in distinguishing octahedral versus tetrahedral Sn4+ coordinations. [Display omitted] •Ss-NMR: useful for studying Sn4+ coordination and Cu-Zn-Sn-S system structures.•Cu-Zn-Sn-S and Cu-Sn-S phase diagrams at room-temperature, 200 °C, and 400 °C.•Cu3SnS4 reports may be due to indium contamination.•Kinetic barriers to Cu4SnS4 from elemental precursors but not binary precursors.•Order-disorder transitions between 200 °C and 400 °C in Cu2SnS3 and Cu2ZnSnS4.