Investigation of Combinatorial Coevaporated Thin Film Cu2ZnSnS4 (II): Beneficial Cation Arrangement in Cu-Rich Growth

Cu₂ZnSn(S,Se)₄ (CZTSSe) is an earth-abundant semiconductor with potential for economical photovoltaic power generation at terawatt scales. In this work, we use Raman scattering to investigate phase coexistence in combinatorial CZTS thin films grown at 325 or 470°C. The surface of the samples grown at 325°C is rough except for a prominent specularly reflective band near and along the ZnS-Cu₂SnS₃ (CTS) tie line in the Cu-Zn-Sn-S quaternary phase diagram. All structurally incoherent secondary phases (SnS₂, CuS) exist only as surface phases or are embedded as separate grains, whereas the structurally coherent secondary phase CTS coexists with CZTS in the dense underlying film. In films grown at 325°C, which are kinetically trapped by the low growth temperature, a change is observed in Cu and Sn site occupancy, evidenced by the shift from cubic-CTS in the Cu-rich region (Cu/Sn>2) to more tetragonal-CTS in the Sn-rich region (Cu/Sn<2). For CZTS samples grown at 470°C, CTS is not observed and regions grown under excess Sn flux are more disordered than Cu-rich regions evidenced by broader CZTS A mode peaks. Therefore, increasing Sn chemical potential results in more CZTS lattice disorder, suggesting, with other evidence, the formation of Sn antisite defects. In contrast, the CZTS A mode breadth is insensitive to Zn richness suggesting that excess Zn does not induce significant disorder within the CZTS lattice. We postulate that initially growing CZTS films Cu-rich (Cu/Sn>2) results in higher cation ordering meaning fewer antisite defects.