Visualizing the Low-Energy Electronic Structure of Prototypical Hybrid Halide Perovskite through Clear Band Measurements.

Organic-inorganic hybrid perovskites (OIHPs) are a promising class of materials that rival conventional semiconductors in various optoelectronic applications. However, unraveling the precise nature of their low-energy electronic structures continues to pose a significant challenge, primarily due to the absence of clear band measurements. Here, we investigate the low-energy electronic structure of CH 3 NH 3 PbI 3 (MAPI 3 ) using angle-resolved photoelectron spectroscopy combined with ab initio density functional theory. We successfully visualize the electronic structure of MAPI 3 near the bulk valence band maximum by using a laboratory photon source (He I α , 21.2 eV) at low temperature and explore its fundamental properties. The observed valence band exhibits a highly isotropic and parabolic band characterized by small effective masses of 0.20-0.21 m e , without notable spectral signatures associated with a large polaron or the Rashba effect, subjects that are intensely debated in the literature. Concurrently, our spin-resolved measurements directly disprove the giant Rashba scenario previously suggested in a similar perovskite compound by establishing an upper limit for the Rashba parameter ( α R ) of 0.28 eV Å. Our results unveil the unusually complex nature of the low-energy electronic structure of OIHPs, thereby advancing our fundamental understanding of this important class of materials.