摘要： The intrinsic instability of lead halide perovskite semiconductors in an ambient atmosphere is one of the most critical issues that impedes perovskite solar cell commercialization. To overcome it, the use of bulky organic spacers has emerged as a promising solution. The resulting perovskite thin films present complex morphologies, difficult to predict, which can directly affect the device efficiency. Here, by combining in-depth morphological and spectroscopic characterization, it is shown that both the ionic size and the relative concentration of the organic cation, drive the integration of bulky organic cations into the crystal unit cell and the thin film, inducing different perovskite phases and different vertical distribution, then causing a significant change in the final thin film morphology. Based on these studies, a fine-engineered perovskite is constructed by employing two different large cations, namely, ethyl ammonium and butyl ammonium. The first one takes part in the 3D perovskite phase formation, the second one works as a surface modifier by forming a passivating layer on top of the thin film. Together they lead to improved photovoltaic performance and device stability when tested in air under continuous illumination. These findings propose a general approach to achieve reliability in perovskite-based optoelectronic devices.