This review article gives an overview of progress in planar heterojunction perovskite solar cells and the roles of interfacial layers in the device, and suggests a practical strategy to fabricate highly efficient and flexible planar heterojunction perovskite solar cells.

Abstract The power conversion efficiency of perovskite solar cells continues to increase. However, defects in perovskite materials are detrimental to their carrier dynamics and structural stability, ultimately limiting the photovoltaic characteristics and stability of perovskite solar cells. Herein, we report that 6H polytype perovskite effectively engineers defects at the interface with cubic polytype FAPbI 3 , which facilitates radiative recombination and improves the stability of the polycrystalline film. We particularly show the detrimental effects of shallow-level defect that originates from the formation of the most dominant iodide vacancy (V I + ) in FAPbI 3 . Furthermore, additional surface passivation on top of the hetero-polytypic perovskite film results in an ultra-long carrier lifetime exceeding 18 μs, affords power conversion efficiencies of 24.13% for perovskite solar cells, 21.92% (certified power conversion efficiency: 21.44%) for a module, and long-term stability. The hetero-polytypic perovskite configuration may be considered as close to the ideal polycrystalline structure in terms of charge carrier dynamics and stability.