Daily temperature variations induce phase transitions and lattice strains in halide perovskites, challenging their stability in solar cells. We stabilized the perovskite black phase and improved solar cell performance using the ordered dipolar structure of β-poly(1,1-difluoroethylene) to control perovskite film crystallization and energy alignment. We demonstrated p-i-n perovskite solar cells with a record power conversion efficiency of 24.6% over 18 square millimeters and 23.1% over 1 square centimeter, which retained 96 and 88% of the efficiency after 1000 hours of 1-sun maximum power point tracking at 25° and 75°C, respectively. Devices under rapid thermal cycling between −60° and +80°C showed no sign of fatigue, demonstrating the impact of the ordered dipolar structure on the operational stability of perovskite solar cells.

Tin halide perovskites attract incremental attention to deliver lead‐free perovskite solar cells. Nevertheless, disordered crystal growth and low defect formation energy, related to Sn(II) oxidation to Sn(IV), limit the efficiency and stability of solar cells. Engineering the processing from perovskite precursor solution preparation to film crystallization is crucial to tackle these issues and enable the full photovoltaic potential of tin halide perovskites. Herein, the ionic liquid n‐butylammonium acetate (BAAc) is used to tune the tin coordination with specific O…Sn chelating bonds and NH…X hydrogen bonds. The coordination between BAAc and tin enables modulation of the crystallization of the perovskite in a thin film. The resulting BAAc‐containing perovskite films are more compact and have a preferential crystal orientation. Moreover, a lower amount of Sn(IV) and related chemical defects are found for the BAAc‐containing perovskites. Tin halide perovskite solar cells processed with BAAc show a power conversion efficiency of over 10%. This value is retained after storing the devices for over 1000 h in nitrogen. This work paves the way toward a more controlled tin‐based perovskite crystallization for stable and efficient lead‐free perovskite photovoltaics.

Tin is the frontrunner for substituting toxic lead in perovskite solar cells. However, tin suffers the detrimental oxidation of Sn^II to Sn^IV. Most of reported strategies employ SnF₂ in the perovskite precursor solution to prevent Sn^IV formation. Nevertheless, the working mechanism of this additive remains debated. To further elucidate it, we investigate the fluoride chemistry in tin halide perovskites by complementary analytical tools. NMR analysis of the precursor solution discloses a strong preferential affinity of fluoride anions for Sn^IV over Sn^II, selectively complexing it as SnF₄. Hard X‐ray photoelectron spectroscopy on films shows the lower tendency of SnF₄ than SnI₄ to get included in the perovskite structure, hence preventing the inclusion of Sn^IV in the film. Finally, small‐angle X‐ray scattering reveals the strong influence of fluoride on the colloidal chemistry of precursor dispersions, directly affecting perovskite crystallization.

Surface passivation in perovskite solar cells can enhance device efficiency, yet incomplete interfacial functionality poses challenges to long-term reliability. Here we present a strategic interfacial engineering approach using sodium heptafluorobutyrate to fully functionalize the perovskite surface. Sodium heptafluorobutyrate acts as an ion shield that tunes the perovskite surface work function and increases the defect formation energy, resulting in an improved interface with the electron transport layer that minimizes recombination and boosts electron extraction under operation. We find that a sodium-heptafluorobutyrate-functionalized perovskite surface promotes a uniform, compact C ₆₀ layer that effectively blocks ion diffusion and stabilizes the device stack. This approach allows p–i–n perovskite solar cells to achieve a record power conversion efficiency (PCE) of 27.02% (certified 26.96% with a maximum-power-point-tracking PCE of 26.61%). Devices with an active area of 1 cm ² deliver a PCE of 25.95%. Perovskite solar cells retain 100% of their initial efficiency following 1,200 h of continuous 1-sun illumination at the maximum power point. Devices also demonstrate exceptional thermal stability, retaining 92% of the initial PCE when ageing at 85 °C for 1,800 h and 94% after 200 thermal cycles between –40 °C and +85 °C.