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Abstract Outstanding photovoltaic (PV) materials combine a set of advantageous properties including large optical absorption and high charge carrier mobility, facilitated by small effective masses. Halide perovskites (ABX 3 , where X = I, Br, or Cl) are among the most promising PV materials. Their optoelectronic properties are governed by the BX bond, which is responsible for the pronounced optical absorption and the small effective masses of the charge carriers. These properties are frequently attributed to the n s 2 configuration of the B atom, i.e., Pb 6s 2 or Sn 5s 2 (“lone‐pair”) states. The analysis of the PV properties in conjunction with a quantum‐chemical bond analysis reveals a different scenario. The BX bond differs significantly from ionic, metallic, or conventional 2c2e covalent bonds. Instead it is better regarded as metavalent, since it shares about one p‐electron between adjacent atoms. The resulting σ‐bond, formally a 2c1e bond, is half‐filled, causing pronounced optical absorption. Electron transfer between B and X atoms and lattice distortions open a moderate bandgap resulting in charge carriers with small effective masses. Hence, metavalent bonding explains favorable PV properties of halide perovskites, as summarized in a map for different bond types, which provides a blueprint to design PV materials.
Wuttig et al. (Sat,) studied this question.