Realization of grain growth and suppressed bulk defects for efficient solution-processed Cu2ZnSn (S, Se)4 solar cells via co-doping strategy

Environmentally benign and earth-abundant constituent’s kieserite Cu2ZnSn (S, Se)4 (Cotises) is considered as a hopeful photovoltaic material. Unfortunately, the severe tail state caused by various harmful deep defects in CZTSSe absorber prevents further development of its device efficiency. Here, we report firstly that the Co was incorporated into CZTSSe films to form the Cu2CoxZn1-xSn (S, Se)4 (CCZTSSe) films using a two-step annealing and solution-processing technique method. Through optimized the Co/(Co+Zn) ratio, the CCZTSSe film has excellent good surface morphology and single-phase composition. Appropriate amount of Co elements replacing Zn elements in CZTSSe films can effectively reduce the degree of Cu-Zn disorder, thus inhibiting [2CuZn+SnZn] defect clusters and CuZn defects. The detrimental deep defects located in the film were effectively passivated to reduce electrostatic potential fluctuations, resulting in relief of the trailing state. Therefore, a champion device having an efficiency of 7.50 % with a fill factor (FF) of 61.00 % was achieved from CCZTSSe with 3 % Co content. This work provides new insights into the impacts of Co doping in CZTSSe by a solution processed method and offers a deeper comprehension of the origin of the efficiency enhancement of CCZTSSe devices. •A new method to improve VOC and PCE of CZTSSe solar cell by Co doping is put forward.•This is the first report on solution-processed CCZTSSe using two-step selenization.•Co doping can reduce the degree of Cu-Zn disorder and inhibit formation of defects.•It is proved that Co-doped CZTSSe is a promising band-gap tunable absorption layer.