Highly Efficient and Stable Perovskite Solar Cells: Competitive Crystallization Strategy and Synergistic Passivation

Defects of perovskite (PVK) films are one of the main obstacles to achieving high‐performance perovskite solar cells (PSCs). Here, the authors fabricated highly efficient and stable PSCs by introducing prolinamide (ProA) into the PbI2 precursor solution, which improves the performance of PSCs by the competitive crystallization and efficient defect passivation of perovskite. The theoretical and experimental results indicate that ProA forms an adduct with PbI2, competes with free I− to coordinate with Pb2+, leads to the increase of the energy barrier of crystallization, and slows down the crystallization rate. Furthermore, the dual‐site synergistic passivation of ProA is revealed by density functional theory (DFT) calculations and experimental results. ProA effectively reduces non‐radiative recombination in the resultant films to improve the photovoltaic performance of PSCs. Notably, ProA‐assisted PSCs achieve 24.61% power conversion efficiency (PCE) for the champion device and the stability of PSCs devices under ambient and thermal environments is improved. Prolinamide (ProA) is introduced into the PbI2 precursor solution, which improves the performance of perovskite solar cells (PSCs) by the competitive crystallization and efficient defect passivation of perovskite. The results indicate that ProA can lead to the increase of the energy barrier of crystallization and slows down the crystallization rate. Notably, ProA‐assisted PSCs achieve 24.61% power conversion efficiency and high stability.