Structural and Electronic Properties of Cu2MnSnS4 from Experiment and First‐Principles Calculations.

Cu2MnSnS4 shares several promising properties with the widely investigated Cu2ZnSnS4 for photovoltaic applications such as containing only earth abundant and non‐toxic elements, and suitable absorption characteristics for absorber materials. Thin film Cu2MnSnS4 samples with various cation compositions are co‐sputtered reactively followed by a high temperature anneal. Formation of Cu2MnSnS4 and co‐existence of several secondary phases is verified by XRD and Raman. Our investigation of the crystal structure based on first‐principles DFT confirms that stannite crystal structure is preferred over kesterite, although, further verification considering cation disorder is needed. The direct band gap of Cu2MnSnS4 is calculated as 1.52 eV (1.62 eV) for stannite (kesterite), which coincides with the range of the measured band gaps from spectrophotometry of 1.42–1.59 eV. After further annealing treatments below 240 °C, the absorption shows reversible changes: the band gap blue‐shifts and the Urbach tail energy is reduced. It is concluded that, just like Cu2ZnSnS4, disorder also occurs in Cu2MnSnS4. The implications of our findings are discussed and related to the current understanding of cation disorder in Cu2ZnSnS4 and related compounds. Furthermore, for the first time first‐principles DFT investigations are presented for the thiospinel Cu2MnSn3S8 which is observed experimentally as a secondary phase in Sn‐rich Cu2MnSnS4 thin films. [ABSTRACT FROM AUTHOR]