Doping of perovskite semiconductor¹ and passivation of its grain boundaries² remain challenging but essential for advancing high-efficiency perovskite solar cells. Particularly, that’s crucial to build the perovskite/indium tin oxide (ITO) Schottky contact based inverted devices without pre-depositing a layer of hole-transport material^3-5. Here we report a dimethylacridine-based molecular doping process to construct a well matched p-perovskite/ITO contact along with all-round passivation of grain boundaries, achieving a certified power conversion efficiency (PCE) of 25.39%. The molecules are shown to be extruded from the precursor solution to the grain boundaries and the film bottom surface in the chlorobenzene-quenched crystallization process, which we call a molecule-extrusion process. The core coordination complex between the deprotonated phosphonic acid group of the molecule and lead polyiodide of perovskite is responsible for both mechanical absorption and electronic charge transfer, and leads to p-type doping of the perovskite film. We achieve a champion device with a PCE of 25.86% (reverse scan), and devices that maintain 96.6% of the initial PCE after 1000 h light soaking.

钙钛矿半导体¹的掺杂及其晶界²的钝化仍然具有挑战性，但对于推进高效钙钛矿太阳能电池至关重要。特别是，这对于构建基于钙钛矿/氧化铟锡（ITO）肖特基接触的倒置器件至关重要，而无需预先沉积空穴传输材料层^3-5。在这里，我们报告了一种基于二甲基吖啶的分子掺杂工艺，构建了匹配良好的p-钙钛矿/ITO接触以及晶界的全面钝化，实现了25.39%的认证功率转换效率（PCE）。在氯苯淬火结晶过程中，分子从前驱体溶液中挤出到晶界和薄膜底面，我们称之为分子挤出过程。分子的去质子化膦酸基团与钙钛矿的聚碘化铅之间的核心配位络合物负责机械吸收和电子电荷转移，并导致钙钛矿薄膜的p型掺杂。我们获得了 PCE 为 25.86%（反向扫描）的冠军器件，以及在 1000 小时光浸泡后仍保持初始 PCE 96.6% 的器件。