Ruddlesden–Popper 2D Component to Stabilize γ‐CsPbI3 Perovskite Phase for Stable and Efficient Photovoltaics

The highest certified power conversion efficiency (PCE) of black phase based CsPbI₃ perovskite solar cells has exceeded 18%, and become a hotspot in recent progress. However, the black phase of CsPbI₃ rapidly transforms to yellow phase in ambient conditions due to its thermodynamic instability. Here, a Ruddlesden–Popper 2D structure is introduced into γ‐CsPbI₃ film to stabilize the black phase via reducing dimensionality. It is found that a judicious amount of phenylethylammonium iodide can adjust the dimensionality of γ‐CsPbI₃ film from 2D to quasi‐2D and 3D phase. Comprehensive consideration to obtain both the stability and high PCE, quasi‐2D (n = 40) γ‐CsPbI₃ delivers a reproducible PCE of 13.65% with negligible hysteresis. By utilizing femtosecond transient absorption and time‐resolved PL decay, similar carrier kinetics in n = 40 and ∞ samples are observed, meaning an efficient charge extraction. More importantly, when the device is placed at 80 °C in N₂ condition or in air with RH of 25–30%, its PCE keeps ≈88% and ≈89% of its initial PCE after 12 days, respectively. Such results are better than the 3D one (≈69% and ≈16%, respectively).