Incorporating mixed ion is a frequently used strategy to stabilize black-phase formamidinum lead iodide perovskite for high-efficiency solar cells. However, these devices commonly suffer from photoinduced phase segregation and humidity instability. Herein, we find that the underlying reason is that the mixed halide perovskites generally fail to grow into homogenous and high-crystalline film, due to the multiple pathways of crystal nucleation originating from various intermediate phases in the film-forming process. Therefore, we design a multifunctional fluorinated additive, which restrains the complicated intermediate phases and promotes orientated crystallization of α-phase of perovskite. Furthermore, the additives in-situ polymerize during the perovskite film formation and form a hydrogen-bonded network to stabilize α-phase. Remarkably, the polymerized additives endow a strongly hydrophobic effect to the bare perovskite film against liquid water for 5 min. The unencapsulated devices achieve 24.10% efficiency and maintain >95% of the initial efficiency for 1000 h under continuous sunlight soaking and for 2000 h at air ambient of ~50% humid, respectively.

Although the power conversion efficiency values of perovskite solar cells continue to be refreshed, it is still far from the theoretical Shockley-Queisser limit. Two major issues need to be addressed, including disorder crystallization of perovskite and unbalanced interface charge extraction, which limit further improvements in device efficiency. Herein, we develop a thermally polymerized additive as the polymer template in the perovskite film, which can form monolithic perovskite grain and a unique “Mortise-Tenon” structure after spin-coating hole-transport layer. Importantly, the suppressed non-radiative recombination and balanced interface charge extraction benefit from high-quality perovskite crystals and Mortise-Tenon structure, resulting in enhanced open-circuit voltage and fill-factor of the device. The PSCs achieve certified efficiency of 24.55% and maintain >95% initial efficiency over 1100 h in accordance with the ISOS-L-2 protocol, as well as excellent endurance according to the ISOS-D-3 accelerated aging test.

Flexible perovskite solar cells (PSCs) have drawn increasing attention due to their promising applications for wearable electronics and aerospace applications. However, the efficiency and stability of flexible PSCs still lag behind their rigid counterparts. Here, we use N,N-dimethyl acrylamide (DMAA) to in situ synthesize cross-linking polymer for flexible Sn–Pb mixed PSCs. DMAA can gather at grain boundary as a scaffold to regulate the crystallization of perovskite and reduce defects. The rigid and flexible Sn–Pb mixed PSCs showed efficiencies of 16.44% and 15.44%, respectively. In addition, the flexible Sn–Pb mixed PSCs demonstrated excellent bending durability, which retained over 80% of the original efficiency after 5000 bending cycles at a radius of 5 mm.