Tetrafluoroborate‐Induced Reduction in Defect Density in Hybrid Perovskites through Halide Management

Abstract Hybrid‐perovskite‐based optoelectronic devices are demonstrating unprecedented growth in performance, and defect passivation approaches are highly promising routes to further improve properties. Here, the effect of the molecular ion BF 4 − , introduced via methylammonium tetrafluoroborate (MABF 4 ) in a surface treatment for MAPbI 3 perovskite, is reported. Optical spectroscopy characterization shows that the introduction of tetrafluoroborate leads to reduced non‐radiative charge‐carrier recombination with a reduction in first‐order recombination rate from 6.5 × 10 6 to 2.5 × 10 5 s −1 in BF 4 − ‐treated samples, and a consequent increase in photoluminescence quantum yield by an order of magnitude (from 0.5 to 10.4%). 19 F, 11 B, and 14 N solid‐state NMR is used to elucidate the atomic‐level mechanism of the BF 4 − additive‐induced improvements, revealing that the BF 4 − acts as a scavenger of excess MAI by forming MAI–MABF 4 cocrystals. This shifts the equilibrium of iodide concentration in the perovskite phase, thereby reducing the concentration of interstitial iodide defects that act as deep traps and non‐radiative recombination centers. These collective results allow us to elucidate the microscopic mechanism of action of BF 4 − .