Organic–inorganic halide perovskite solar cells (PSCs) have emerged as attractive alternatives to conventional solar cells. It is still a challenge to obtain PSCs with good thermal stability and high permanence, especially at extreme outdoor temperatures. This work systematically studies the effects of Bi3+ modification on structural, electrical, and optical properties of perovskite films (FA0.83MA0.17Pb(I0.83Br0.17)3) and the performance of corresponding PSCs. The results indicate that Bi3+ modified PSCs can achieve better thermal stability, photovoltaic response, and reproducibility compared with control cells due to the decreased grain boundaries, enhanced crystallization, and improved electron extraction from perovskite film. As a result, the modified PSC exhibits an optimized power conversion efficiency (PCE) of 19.4% compared with 18.3% for the optimized control device, accompanied by better thermoresistant ability under 100–180 °C and enhanced long‐term stability. The degradation rate of the modified device is reduced by an order of magnitude due to effective structural defect modification in perovskite photoactive layer. It could maintain more than two months at 60 °C. These results shed light on the origin of crystallization and thermal stability of perovskite films, and provide an approach to solve thermal stability issue of PSCs.

Growing attention has been paid to CsPbIBr2 perovskite solar cells (PSCs) after balancing the band gap and stability features of the interested full-inorganic perovskites. However, their power-conversion efficiency (PCE) still lags behind that of the PSCs using hybrid halide perovskite and how to increase the corresponding PCE is still a challenge. Herein, antisolvents and organic ion surface passivation strategies were systematically applied to precisely control the growth of CsPbIBr2 crystals for constructing a high-quality full-inorganic perovskite film. Through careful adjustments, a CsPbIBr2 film with a pure phase, full coverage, and high crystallinity with preferable (100) orientation was successfully obtained by introducing diethyl ether as the antisolvent followed by guanidinium surface passivation. The optimal CsPbIBr2 film was composed by a large grain with an average size of 950 nm, few grain boundaries, and higher hydrophobic property. Planer PSC using the optimal CsPbIBr2 film and electron-beam-deposited TiO2 compact layer exhibits a PCE of 9.17%, which ranks among the highest PCE range of the reported CsPbIBr2 PSCs. Besides, the designed CsPbIBr2 PSC exhibited good long-term stability, which could maintain 90% of the initial PCE in 40% humidity ambient, which remained constant after heat treatment at 100 °C for 100 h. Based on the optimal CsPbIBr2 film, the flexible and large-area (up to 225 mm2) PSCs were further fabricated. The adopted film improvement methods were further extended to other kinds of full-organic PSCs, which demonstrated the universality of this strategy.

Since Yan's work, incorporation of some lanthanide elements, such as Eu and Nd, into MAPbI3 layer has been proven to be a powerful strategy on improving the permanence of the perovskite solar cells (PSCs). However, a comprehensive configuration has not been given for different lanthanide elements doping while the mechanism has not been clarified. Herein, the incorporation of various lanthanides ions (Ln3+ = Ce3+, Eu3+, Nd3+, Sm3+, or Yb3+) into perovskite films to largely enhance the performance of PSCs is presented. Arising from the enlarged grain size and crystallinity of perovskite film upon Ln3+ ions doping, the efficiency and stability of PSCs are significantly improved. Extraordinarily, PSCs with Ce3+ doping achieve the best performance, with a champion power conversion efficiency (PCE) of 21.67% in contrast to 18.50% for pristine PSCs, and outstanding long‐term and UV irradiation stability. Such high performance of PSCs after Ce3+ doping originates from special Ce3+/Ce4+ redox pair and the unique 4f‐5d absorption in the UV region. Finally, the flexible PSCs with low‐temperature preparation are explored. Considering the richer deposition of cerium element in the earth and lower price, the findings may provide new opportunities for developing low‐cost, highly efficient, air/UV stable, and flexible PSCs.