Improved performance of kesterite Cu2ZnSn(S,Se)4 thin film solar cells by Ag/Ge co-doping

Cation doping is an important approach to improve the performance of kesterite Cu2ZnSn(S,Se)4 (CZTSSe) thin film solar cells. Since different cation dopant has different effects on the defects and crystallization of CZTSSe absorber, it is expected to achieve better device performance via the synergistic effects of double cation co-doping compared with the single cation doping. Herein, we investigated the effects of Ag/Ge co-doping on CZTSSe solar cells by doping Ge in an already optimized Ag-alloyed CZTSSe (ACZTSSe). It is found that incorporating a small amount of Ge can further improve the crystallinity and minority carrier lifetime of ACZTSSe. The low-temperature photoluminescence results reveal that the Ge doping primarily suppressed the SnZn defects in ACZTSSe, thereby further boosting the device performance. However, higher Ge doping concentration can lead to a discontinuous surface morphology, which is believed to be related with the relatively low melting temperature and double-layered structure of ACZTSSe absorber. The deteriorated surface morphology results in photocurrent loss in the near-infrared region and decreased fill factor. As the Ge doping ratio increases, there is a balance between the defects and morphology. A champion power conversion efficiency (PCE), 11.4%, was achieved for the Ag/Ge co-doped CZTSSe solar cells at Ge substitution rate of 3%. Compared with the single Ag doping, the average PCE was further promoted by 0.5% due to Ag/Ge co-doping.