Band-Edge Orbital Engineering of Perovskite Semiconductors for Optoelectronic Applications

Lead (Pb) halide perovskites have achieved great success in recent years because of their excellent optoelectronic properties, which is largely attributed to the lone-pair s orbital-derived antibonding states at the valence band edge. Guided by the key band-edge orbital character, a series of ns²-containing (i.e., Sn²⁺, Sb³⁺, and Bi³⁺) Pb-free perovskite alternatives have been explored as potential photovoltaic candidates. On the other hand, based on the band-edge orbital components (i.e., M²⁺ s and p/X^- p orbitals), a series of strategies have been proposed to optimize their optoelectronic properties by modifying the atomic orbitals and orbital interactions. Therefore, understanding the band-edge electronic features from the recently reported halide perovskites is essential for future material design and device optimization. This Perspective first attempts to establish the band-edge orbital-property relationship using a chemically intuitive approach and then rationalizes their superior properties and explains the trends in electronic properties. We hope that this Perspective will provide atomic-level guidance and insights toward the rational design of perovskite semiconductors with outstanding optoelectronic properties.