Over-18%-Efficiency Quasi-2D Ruddlesden–Popper Pb–Sn Mixed Perovskite Solar Cells by Compositional Engineering

[Image: see text] Quasi-two-dimensional (2D) Pb–Sn mixed perovskites show great potential in applications of single and tandem photovoltaic devices, but they suffer from low efficiencies due to the existence of horizontal 2D phases. Here, we obtain a record high efficiency of 18.06% based on 2D ⟨n⟩ = 5 Pb–Sn mixed perovskites (iso-BA(2)MA(4)(Pb(x)Sn(1–x))(5)I(16), x = 0.7), by optimizing the crystal orientation through a regulation of the Pb/Sn ratio. We find that Sn-rich precursors give rise to a mixture of horizontal and vertical 2D phases. Interestingly, increasing the Pb content can not only entirely suppress the unwanted horizontal 2D phase in the film but also enhance the growth of vertical 2D phases, thus significantly improving the device performance and stability. It is suggested that an increase of the Pb content in the Pb–Sn mixed systems facilitates the incorporation of iso-butylammonium (iso-BA(+)) ligands in vertically oriented perovskites because of the reduced lattice strain and increased interaction between the organic ligands and inorganic framework. Our work sheds light on the optimal conditions for fabricating stable and efficient 2D Pb–Sn mixed perovskite solar cells.