Multiple‐ion Management of Perovskites by Regulating Spatial Distribution of Hydroxyls in Oligosaccharides

Abstract Suppressing migrations of intrinsic and extrinsic ions (e.g., Pb 2+ , I ‐ , FA + /MA + , and Li + ) in organic–inorganic hybrid perovskites is critical for alleviating the hysteresis and degradation of perovskite solar cells (PSCs). However, various additives reported for that purpose usually interact with one or two types of those ions, not inhibiting multiple‐ion migrations simultaneously. Two oligosaccharides (β‐cyclodextrin (β‐CD) and maltotetraose (G4)), containing 14 hydroxyls (−OH) with different spatial distributions, for the suppression of multiple‐ion migrations in PSCs is herein employed. Compared to linear arrangement of −OH in G4, annular distribution of −OH around wide and narrow rims of β‐CD can form supramolecular multi‐site interactions in a focal manner with various ions, more effectively capturing and immobilizing these migrated ions. With this multiple‐ion management strategy, β‐CD‐based PSCs exhibit an impressive efficiency of 24.22% with negligible hysteresis and excellent device stability. This work highlights the significances of multi‐site interactions and molecular configuration of the additive for inhibiting multi‐ion migrations in PSCs.