Room Temperature Crystallized Phase‐Pure α‐FAPbI₃ Perovskite with In‐Situ Grain‐Boundary Passivation

Abstract Energy loss in perovskite grain boundaries (GBs) is a primary limitation toward high‐efficiency perovskite solar cells (PSCs). Two critical strategies to address this issue are high‐quality crystallization and passivation of GBs. However, the established methods are generally carried out discretely due to the complicated mechanisms of grain growth and defect formation. In this study, a combined method is proposed by introducing 3,4,5‐Trifluoroaniline iodide (TFAI) into the perovskite precursor. The TFAI triggers the union of nano‐sized colloids into microclusters and facilitates the complete phase transition of α‐FAPbI₃ at room temperature. The controlled chemical reactivity and strong steric hindrance effect enable the fixed location of TFAI and suppress defects at GBs. This combination of well‐crystallized perovskite grains and effectively passivated GBs leads to an improvement in the open circuit voltage (V_oc) of PSCs from 1.08 V to 1.17 V, which is one of the highest recorded V_oc without interface modification. The TFAI‐incorporated device achieved a champion PCE of 24.81%. The device maintained a steady power output near its maximum power output point, showing almost no decay over 280 h testing without pre‐processing.