Fabrication of Cs_xFA_1–xPbI₃ Mixed-Cation Perovskites via Gas-Phase-Assisted Compositional Modulation for Efficient and Stable Photovoltaic Devices

Over the past few years, significant attention has been focused on HC(NH2)2PbI3 (FAPbI3) perovskite due to its reduced band gap and enhanced thermal stability compared with the most studied CH3NH3PbI3 (MAPbI3). However, FAPbI3 is sensitive to moisture and also encounters a serious structural phase-transition from photoactive α-phase to photoinactive δ-phase. Herein, we first develop a novel FAI gas-phase-assisted mixed-cation compositional modulation method to fabricate CsxFA1-xPbI3 perovskite solar cells (PSCs), and realize the structural stabilization of α-phase FAPbI3 with the incorporation of smaller inorganic Cs+ ions. Through the setting of different Cs+ contents (x = 0, 0.05, 0.10, 0.15, 0.20, 0.25, 0.30, 0.50) along with a moderate FAI vapor deposition process, a series of CsxFA1-xPbI3 films with consistent compositions are fabricated, which perfectly resolves the main blocking problems of the conventional solution approach, such as difficulty in compositional control and rough film morphology. Meanwhile, we find that the Cs+ amount is crucial for generating phase-pure CsxFA1-xPbI3 (0 < x < 0.30) while higher contents result in phase segregation. Consequently, the optimum amount of Cs+ (x = 0.15) is verified, and Cs0.15FA0.85PbI3 shows the smallest unit cell volume and good moisture-resistant feature. Correspondingly, the highest power conversion efficiency (PCE) of 14.45% based on Cs0.15FA0.85PbI3 PSCs is successfully achieved in this work.