Direct Characterization of Type‐I Band Alignment in 2D Ruddlesden–Popper Perovskites

Abstract 2D Ruddlesden–Popper halide perovskites have attracted considerable attention due to their desirable optoelectronic properties, high chemical and structural tunability, and improved environmental stability. However, the understanding of their structure–properties relationships is still limited. In particular, the energy level positions and band alignments at interfaces involving these materials, which are important features to control in the context of any applications, are still under debate. Here, the electronic structure of high‐purity films of BA₂MA_n−1Pb_nI_3n+1 for n = 1–5 (where BA stands for butylammonium and MA for methylammonium) is investigated, using optical absorption, ultraviolet, and inverse photoemission spectroscopies, and density functional theory calculations. This study determines the ionization energy and electron affinity of each compound and demonstrates a type‐I band alignment for the BA₂MA_n−1Pb_nI_3n+1 series. This study further describes the evolution of the exciton binding energy as a function of the thickness of the inorganic layers.