Reducing the interfacial defect density of CZTSSe solar cells by Mn substitution

Cation disorder which arises from the size and chemical environment similarity of Cu and Zn is the limiting factor in Cu₂ZnSnS_xSe_4-x (CZTSSe) performance. Cation substitution is one effective way to solve this issue, however, the most commonly reported substitutes, Ag and Cd, are not ideal as they detract from the earth-abundant and non-toxic motivation of CZTSSe. Mn is a promising candidate in comparison with other candidates (e.g. Fe, Ni or Co), because of its oxidation state stability and larger ionic size mismatch with Cu. In this study, Cu₂Mn_xZn_1-xSn(S,Se)₄ (CMZTSSe) thin film solar cells were prepared by chemical spray pyrolysis and a subsequent selenization process. We study the influence of Mn substitution on the morphological, structural, optical, electrical and device properties. A distinct phase transformation from CZTSSe kesterite to C(M,Z)TSSe stannite is observed at 20% Mn substitution. A high amount of Mn substitution (x ≥ 0.6) is shown to increase the carrier density significantly which introduces more defects and non-radiative carrier recombination as shown by quenched photoluminescence intensity. Consequently, reduction in device performance is observed for these samples. The highest power conversion efficiency is achieved at x ≈ 0.05 with η = 7.59%, V_oc = 0.43 V, J_sc = 28.9 mA cm^-2 and FF = 61.03%. The improved open circuit voltage (V_oc) and fill factor (FF) are attributed to the improved shunt resistance and carrier transport due to low defect density especially at the CdS/CMZTSSe interface. Finally, based on our electrical characterization, a few suggestions to improve the efficiency are proposed.