LAUSR

The performance of perovskite solar cells is highly dependent on the fabrication method; thus, controlling the growth mechanism of perovskite crystals is a promising way towards increasing their efficiency and stability. Herein, a multi‐cation halide composition of perovskite solar cells is engineered via the two‐step sequential deposition method. Strikingly, it is found that adding mixtures of 1D polymorphs of orthorhombic δ‐RbPbI3 and δ‐CsPbI3 to the PbI2 precursor solution induces the formation of porous mesostructured hexagonal films. This porosity greatly facilitates the heterogeneous nucleation and the penetration of FA (formamidinium)/MA (methylammonium) cations within the PbI2 film. Thus, the subsequent conversion of PbI2 into the desired multication cubic α‐structure by exposing it to a solution of formamidinium methylammonium halides is greatly enhanced. During the conversion step, the δ‐CsPbI3 also is fully integrated into the 3D mixed cation perovskite lattice, which exhibits high crystallinity and superior optoelectronic properties. The champion device shows a power conversion efficiency (PCE) over 22%. Furthermore, these devices exhibit enhanced operational stability, with the best device retaining more than 90% of its initial value of PCE under 1 Sun illumination with maximum power point tracking for 400 h.