Cd‐Free Pure Sulfide Kesterite Cu2ZnSnS4 Solar Cell with Over 800 mV Open‐Circuit Voltage Enabled by Phase Evolution Intervention

The Cd-free Cu2 ZnSnS4 (CZTS) solar cell is an ideal candidate for producing low-cost clean energy through green materials owing to its inherent environmental friendliness and earth abundance. Nevertheless, sulfide CZTS has long suffered from severe open-circuit voltage (VOC ) deficits, limiting the full exploitation of performance potential and further progress. Here, an effective strategy is proposed to alleviate the nonradiative VOC loss by manipulating the phase evolution during the critical kesterite phase formation stage. With a Ge cap layer on the precursor, premature CZTS grain formation is suppressed at low temperatures, leading to fewer nucleation centers at the initial crystallization stage. Consequently, the CZTS grain formation and crystallization are deferred to high temperatures, resulting in enhanced grain interior quality and less unfavorable grain boundaries in the final film. As a result, a champion efficiency of 10.7% for Cd-free CZTS solar cells with remarkably high VOC beyond 800 mV (63.2% Schockley-Queisser limit) is realized, indicating that nonradiative recombination is effectively inhibited. This strategy may advance other compound semiconductors seeking high-quality crystallization.