A Facile Process for Partial Ag Substitution in Kesterite CuZnSn(S,Se) Solar Cells Enabling a Device Efficiency of over 12.

A cation substitution in CuZnSn(S,Se) (CZTSSe) offers a viable strategy to reduce the open-circuit voltage ()-deficit by altering the characteristics of band-tail states, antisite defects, and related defect clusters. Herein, we report a facile single process, i.e., simply introducing a thin Ag layer on a metallic precursor, to effectively improve the device characteristics and performances in kesterite (Ag,Cu)ZnSn(S,Se) (ACZTSSe) solar cells. Probing into the relationship between the external quantum efficiency derivative (dEQE/dλ) and device performances revealed the -deficit characteristics in the ACZTSSe solar cells as a function of Cu and Ag contents. The fabricated champion ACZTSSe solar cell device showed an efficiency of 12.07% and a record low -deficit of 561 mV. Thorough investigations into the mechanism underpinning the improved performance in the ACZTSSe device further revealed the improved band-tailing characteristic, effective minority carrier lifetime, and diode factors as well as reduced antisite defects and related defect clusters as compared to the CZTSSe device. This study demonstrates the feasibility of effectively suppressing antisite defects, related defect clusters, and band-tailing characteristics by simply introducing a thin Ag layer on a metallic precursor in the kesterite solar cells, which in turn effectively reduces the -deficit.