Co‐Evaporated MAPbI3 with Graded Fermi Levels Enables Highly Performing, Scalable, and Flexible p‐i‐n Perovskite Solar Cells

Abstract Recent progress of vapor‐deposited perovskite solar cells (PSCs) has proved the feasibility of this deposition method in achieving promising photovoltaic devices. For the first time, it is probed the versatility of the co‐evaporation process in creating perovskite layers customizable for different device architectures. A gradient of composition is created within the perovskite films by tuning the background chamber pressure during the growth process. This method leads to co‐evaporated MAPbI 3 film with graded Fermi levels across the thickness. Here it is proved that this growth process is beneficial for p‐i‐n PSCs as it can guarantee a favorable energy alignment at the charge selective interfaces. Co‐evaporated p‐i‐n PSCs, with different hole transporting layers, consistently achieve power conversion efficiency (PCE) over 20% with a champion value of 20.6%, one of the highest reported to date. The scaled‐up p‐i‐n PSCs, with active areas of 1 and 1.96 cm 2 , achieved the record PCEs of 19.1% and 17.2%, respectively, while the flexible PSCs reached a PCE of 19.3%. Unencapsulated PSCs demonstrate remarkable long‐term stability, retaining ≈90% of their initial PCE when stored in ambient for 1000 h. These PSCs also preserve over 80% of their initial PCE after 500 h of thermal aging at 85 °C.