Publication date: 15th December 2025
Tin halide perovskites (THPs) are promising non-toxic semiconductors for photovoltaics and optoelectronics, yet their practical application is hindered by the rapid oxidation of Sn²⁺. We established design principles that simultaneously enhance the air stability and optoelectronic performance of two-dimensional (2D) Ruddlesden–Popper (RP) THPs through targeted crystal structure control with tightly-packed hydrophobic spacer cations. Building on these insights, we synthesized new quasi-2D THPs using 4-fluorophenethylammonium (4FPEA) and demonstrated minimized octahedral distortion, ideal 180° Sn–I–Sn bond angles, and amplified spontaneous emission in microflakes, indicating excellent photophysical quality. A structural survey of over 60 reported quasi-2D RP perovskites revealed three perovskite cage types with distinct distortion parameters – “tilted,” “balanced,” and “buckled” – that reflect the interplay of spacer cations and A-cations in influencing structural distortion and photophysical properties. Finally, by further tuning spacer cation functionality and organic supramolecular interactions, we found new ultrastable 2D THPs that enable high power conversion efficiency in 2D/3D tin perovskite solar cells while significantly improving air stability and device durability. These findings establish rational design principles for developing stable, high-performance lead-free tin perovskites and enabling their practical optoelectronic applications.
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