Extending Absorption of Cs2AgBiBr6 to Near‐Infrared Region (≈1350 nm) with Intermediate Band

Abstract The toxicity of lead‐based halide perovskites hampers broad application in optoelectronics. Lead‐free perovskite Cs 2 AgBiBr 6 is considered a promising candidate, owing to the long carrier lifetime and great stability. However, the relatively large bandgap of 1.98 eV limits its absorption in the visible region. Herein, Fe 2+ is chosen as the dopant to alloy into Cs 2 AgBiBr 6 single crystals, and results in an absorption range broadening to ≈1350 nm, which is the longest near‐infrared (NIR) response recorded among lead‐free perovskites. About 1% of Fe ions are alloyed into the Cs 2 AgBiBr 6 lattice to cause lattice shrink age. Instead of narrowing the bandgap, Fe doping would introduce a new intermediate band inside the pristine bandgap of Cs 2 AgBiBr 6 to strongly absorb NIR light, as confirmed by third harmonic generation results. Moreover, considerable photogenerated carriers are produced in Fe doped Cs 2 AgBiBr 6 crystals with NIR irradiation. This work has provided a new way to extend the optical response of lead‐free perovskites for NIR photodetectors and intermediate band photovoltaics.