One‐Source Strategy Boosting Dopant‐Free Hole Transporting Layers for Highly Efficient and Stable CsPbI2Br Perovskite Solar Cells

All‐inorganic perovskites have emerged as promising photovoltaic materials due to their superior thermal stability compared to their organic–inorganic hybrid counterparts. However, the inferior film quality and doped hole transport layer (HTL) have a strong tendency to degrade the perovskite under high temperatures or harsh operating conditions. To solve these problems, a one‐source strategy using the same polymer donor material (PDM) to simultaneously dope CsPbI2Br perovskite films via antisolvent engineering and fabricating the HTL is proposed. The doping assists perovskite film growth and forms a top–down gradient distribution, generating CsPbI2Br with enlarged grain size and reduced defect density. The PDM as the HTL suppresses the energy barrier and forms favorable electrical contacts for hole extraction, and assemble into a fingerprint‐like morphology that improves the conductivity, facilitating the creation of a dopant‐free HTL. Based on this one‐source strategy using PBDB‐T as PDM, the CsPbI2Br perovskite solar cell with a dopant‐free HTL achieves a power conversion efficiency (PCE) of 16.40%, which is one of the highest PCEs reported among all‐inorganic CsPbI2Br pero‐SCs with a dopant‐free HTL. Importantly, the devices exhibit the highest thermal stability at 85 °C and operational stability under continuous illumination even with Ag as the top electrode and present good universality. A one‐source strategy using the same polymer donor material to simultaneously dope CsPbI2Br perovskite films by antisolvent engineering and fabricating the hole transport layer is proposed. The perovskite solar cell (pero‐SC) based on this one‐source strategy exhibits a remarkable power conversion efficiency of 16.40% and possesses excellent thermal stability and operational stability at the same time.