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Abstract: 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. [ABSTRACT FROM AUTHOR]

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) are reported, they all show low photoluminescence quantum yield (PLQY) and poor stability. Here, the synthesis of Cs3Bi2Br9 perovskite QDs with high PLQY and excellent stability is reported. Via a green and facile process using ethanol as the antisolvent, 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, and I) QDs by mixing precursors can cover the photoluminescence 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 synthesis of Cs3Bi2Br9 QD/silica composite. A lead-free perovskite white light-emitting diode is fabricated by simply combining the composite of Cs3Bi2Br9 QD/silica with Y3Al5O12 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. [ABSTRACT FROM AUTHOR]