LAUSR

High-quality perovskite films are beneficial for fabricating perovskite solar cells (PSCs) with excellent photoelectric performance. The substrate on which the perovskite film grows plays a profound role in improving the crystallization quality of the perovskite film. Here, we proposed a novel method for optimizing CsPbI3 perovskite films, that is, two-dimensional (2D) perovskite substrate-assisted growth (2D-PSAG) method. The prepared PEA2PbI4 2D perovskite with proper wettability and roughness is used as a substrate to fabricate the high-quality CsPbI3 film. Moreover, it is found that PEA cations show a vertical gradient distribution within the whole CsPbI3 film because of their bottom-up self-diffusion. Also, PEA cations induce the moderate distortion of [PbI6]4- octahedron and slight lattice contraction of CsPbI3 by chemically bonding between Pb and N atoms. Surprisingly, the trace amounts of PEA cations lead to a bottom-up gradient phase transition from γ-CsPbI3 to β-CsPbI3. Therefore, the energy-level alignment becomes more matched at the interface of the perovskite layer/hole transport layer (poly3-hexylthiophene, P3HT), which denotes a large improvement of hole transport and extraction in PSCs made with the 2D-PSAG method. As a result, the CsPbI3-based PSCs with P3HT as a hole transport layer exhibit a champion efficiency of 17.13%, while the control device exhibits a PCE of only 14.16%. The PSCs made by the 2D-PSAG method retain above 70% of the initial PCE value after storage of 9 days in air (RH 10-20%), while the control device decomposes completely after 9 days. The improved stability could originate from the steric effects of PEA cations and the high crystallization quality of the mixed-phase CsPbI3 film. Therefore, 2D-PSAG is a novel and promising strategy to develop all-inorganic PSCs with high performance and stability.