Lead halide perovskites show excellent optoelectronic properties but are unsatisfactory in terms of stability and toxicity. Herein, bismuth (Bi)‐doped lead‐free inorganic perovskites Cs2SnCl6:Bi are reported as blue emissive phosphors. Upon Bi doping, the originally nonluminous Cs2SnCl6 exhibits a highly efficient deep‐blue emission at 455 nm, with a Stokes shift of 106 nm and a high photoluminescence quantum yield (PLQY) close to 80%. Hybrid density functional theory calculations suggest the preferred formation of [BiSn+VCl] defect complex, which is believed to be responsible for the optical absorption and the associated blue emission. The Cs2SnCl6:Bi also shows impressive thermal and water stability due to its inorganic nature and the formation of protective BiOCl layer. White light‐emitting diodes (LEDs) are constructed using Cs2SnCl6:Bi and commercial yellow phosphors combined with commercial UV LED chips, giving the Commission Internationale de I'Eclairage (CIE) color coordinates of (0.36, 0.37). This work represents a significant step toward the realization of highly efficient, stable, and environmentally benign next‐generation solid‐state lighting.

Lead halide perovskite quantum dots (QDs) possess color-tunable and narrow-band emissions and are very promising for lighting and display applications, but they suffer from lead toxicity and instability. Although lead-free Bi-based and Sn-based perovskite QDs (CsSnX3, Cs2SnX6 and (CH3NH3)3Bi2X9) have been reported, they all showed low photoluminescence quantum yield (PLQY) and poor stability. Here we report the synthesis of Cs3Bi2Br9 perovskite QDs with high PLQY and excellent stability. Via a green and facile process using ethanol as the anti-solvent, as-synthesized Cs3Bi2Br9 QDs show a blue emission at 410 nm with a PLQY up to 19.4%. The whole series of Cs3Bi2X9 (X = Cl, Br, I) QDs by mixing precursors could cover the PL emission range from 393 to 545 nm. Furthermore, Cs3Bi2Br9 QDs show excellent photostability and moisture stability due to the all-inorganic nature and the surface passivation by BiOBr, which enables the one-pot This article is protected by copyright. All rights reserved. 3 synthesis of Cs3Bi2Br9 QDs/silica composite. A lead-free perovskite white light emitting diode (W-LED) is fabricated by simply combine the composite of Cs3Bi2Br9 QDs/silica with Y3Al5O12 (YAG) phosphor. As a new member of lead-free perovskite QDs, Cs3Bi2Br9 QDs open up a new route for the fabrication of optoelectronic devices due to their excellent stability and photophysical characteristics.

Double perovskite Cs 2 AgInCl 6 is newly reported as a stable and environmentally friendly alternative to lead halide perovskites. However, the fundamental properties of this material remain unexplored. Here, we first produced high-quality Cs 2 AgInCl 6 single crystals (SCs) with a low trap density of 8.6 × 10 8 cm −3 , even lower than the value reported in the best lead halide perovskite SCs. Through systematical optical and electronic characterization, we experimentally verified the existence of the proposed parity-forbidden transition in Cs 2 AgInCl 6 and identified the role of oxygen in controlling its optical properties. Furthermore, sensitive (dectivity of ∼10 12 Jones), fast (3 dB bandwidth of 1035 Hz), and stable UV photodetectors were fabricated based on our Cs 2 AgInCl 6 SCs, showcasing their advantages for optoelectronic applications.