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.

ASnX₃ perovskite solar cells (Sn‐PSC) have the potential to deliver the most efficient solar cell technology with safe materials. In this review, a comprehensive introduction of the field is given, that is suitable for nonexperts, gradually leading the reader to a narrower and detailed analysis of the most recent and significant advances. A brief description is given of the leading alternatives for lead‐free PSC and the reasons for ASnX₃ compounds' status as one of the most promising candidates are presented. The last part of the review focuses on the stabilization of ASnX₃, which is the most compelling challenge to achieve the highest efficiency PSCs. The most promising approaches toward stable and efficient ASnX₃ PSCs are identified and discussed.

Due to their outstanding optoelectronic properties, lead-based halide perovskite materials have been applied as efficient photoactive materials in solution-processed solar cells. Current record efficiencies offer the promise to surpass those of silicon solar cells. However, uncertainty about the potential toxicity of lead-based halide perovskite materials and their facile dissolution in water requires a search for new alternative perovskite-like materials. Thanks to the foresight of scientists and their experience in lead-based halide perovskite preparation, remarkable results have been obtained in a short period of time using lead-free perovskite compositions. However, the lower solar-to-energy conversion efficiency and long-term stability issues are serious drawbacks that hinder the potential progression of these materials. Here, we review and analyse strategies in the literature and the most promising solutions to identify the factors that limit the power conversion efficiency and long-term stability of lead-free tin-based perovskite solar cells. In the light of the current state-of-the-art, we offer perspectives for further developing these promising materials.

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.

Controlling the crystallization of perovskite in a thin film is essential in making solar cells. Processing tin-based perovskite films from solution is challenging because of the uncontrollable faster crystallization of tin than the most used lead perovskite. The best performing devices are prepared by depositing perovskite from dimethyl sulfoxide because it slows down the assembly of the tin-iodine network that forms perovskite. However, while dimethyl sulfoxide seems the best solution to control the crystallization, it oxidizes tin during processing. This work demonstrates that 4-(tert-butyl) pyridine can replace dimethyl sulfoxide to control the crystallization without oxidizing tin. We show that tin perovskite films deposited from pyridine have a 1 order of magnitude lower defect density, which promotes charge mobility and photovoltaic performance.