A Thermally Induced Perovskite Crystal Control Strategy for Efficient and Photostable Wide‐Bandgap Perovskite Solar Cells

Wide‐bandgap perovskite solar cells (WBG PSCs) have gained attention as promising tandem partners for silicon solar cells due to their complementary absorption, superb open‐circuit voltage, and an easy solution process. Recently, both their performance and stability have been improved by compositional engineering or defect passivation strategies, due to the modulation of perovskite crystal size and reduction of crystal defects. Herein, a report on the thermally induced phase control (TIPC) strategy is provided, which enables efficient and photostable WBG PSCs without compositional engineering by exploring a thermal annealing process window (100–175 °C and 3–60 min) of the WBG perovskite films. Within this window, a key annealing regime is found that produces preferred crystal orientations of lead iodide and the WBG perovskite, suppressing phase segregation and reducing charge recombination in the perovskites. The WBG PSCs (composition of FA 0.75 MA 0.15 Cs 0.1 PbI 2 Br and E g of 1.73 eV) optimized by TIPC exhibit an excellent power conversion efficiency (PCE) of 18.60% and improved operational stability, maintaining >90% of the maximum PCE (during maximum power point tracking) without encapsulation after 12 h of operation (air mass 1.5 global irradiation in ambient air conditions) or after 500 h of operation (white light‐emitting diode irradiation (100 mW cm −2 ) in N 2 conditions).