Formamidinium (FA) based perovskites are considered as one of the most promising light-absorbing perovskite materials owing to their narrower band gap and better thermal stability compared to conventional methylammonium-based perovskites. Constant improvement by using various additives stimulates the potential application of these perovskites. Amine molecules with different structures have been widely used as typical additives in FA-based perovskite solar cells, and decent performances have been achieved. Thus, a systematic review focusing on structural regulation and functional construction of amines in FA-based perovskites is of significance. Herein, we analyze the construction mechanism of different structural amines on the functional perovskite crystals. The influence of amine molecules on specific perovskite properties including defect conditions, charge transfer, and moisture resistance are evaluated. Finally, we summarize the design rules of amine molecules for the application in high-performance FA-based perovskites and propose directions for the future development of additive molecules.

Organic–inorganic hybrid perovskite solar cells (PSCs) have attracted great attentions due to their rapid increase of power conversion efficiency (PCE). Although the highest PCE of PSCs (25.7%) has been achieved via using formamidinium lead iodide (FAPbI3) with a suitable bandgap, there is still a lack of systematic analysis on FAPbI3‐based PSCs toward high stability and high efficiency. Herein, the progress in FAPbI3 films and achievements in their high‐efficiency and long‐term stability PSCs are comprehensively reviewed. First, the progress from the aspects of morphology, defect, dimension, and strain for FAPbI3 film optimization is summarized and then the development of FAPbI3 PSCs in both efficiency and stability is discussed. Then, the methods to improve the FAPbI3 film quality by morphology control, defect passivation, dimensional regulation, and strain engineering, as well as strategies to optimize the device structure and interface layers, which are critical to promote device stability and efficiency, are evaluated. Finally, the outlook and strategies for realizing commercialized FAPbI3 PSCs with high efficiency and long lifetime are discussed.

Formamidinium (FA) based perovskites are considered as one of the most promising light‐absorbing perovskite materials owing to their narrower band gap and better thermal stability compared to conventional methylammonium‐based perovskites. Constant improvement by using various additives stimulates the potential application of these perovskites. Amine molecules with different structures have been widely used as typical additives in FA‐based perovskite solar cells, and decent performances have been achieved. Thus, a systematic review focusing on structural regulation and functional construction of amines in FA‐based perovskites is of significance. Herein, we analyze the construction mechanism of different structural amines on the functional perovskite crystals. The influence of amine molecules on specific perovskite properties including defect conditions, charge transfer, and moisture resistance are evaluated. Finally, we summarize the design rules of amine molecules for the application in high‐performance FA‐based perovskites and propose directions for the future development of additive molecules.