The K2SiF6:Mn4+ (KSFM) phosphor featuring efficient ultranarrow red emissions is an outstanding candidate for white light-emitting diode (WLED) applications. However, poor moisture resistance seriously affects its application performance. In this study, a two-step surface reconstruction strategy is proposed to dramatically enhance the moisture resistance of commercially available KSFM phosphors, involving treatment with H2NbF7 and subsequent hydrothermal treatment. The modified KSFM phosphor exhibits a high internal quantum efficiency (IQE) of 98.9% after the two-step surface treatment. Meanwhile, nearly 100% of the initial emission intensity is retained for the modified KSFM phosphor even after aging in high temperature (85 °C) and high relative humidity (85% RH) environments for 6 days, in sharp contrast to only 18.6% retention for the original KSFM phosphor. The relative emission intensity of the modified KSFM remains at 98.9% even after being immersed in water for 6 h. Additionally, the phosphor-converted LED fabricated with the modified KSFM phosphor demonstrated excellent long-term stability, retaining up to 97.9% of initial luminous efficacy after aging under 85 °C and 85% RH conditions for 500 h. The moisture-resistance mechanism is elucidated on the basis of spectroscopic analysis as well as structural and compositional characterization of the phosphor surface layer, which can be attributed to the formation of a robust Mn4+-rare shell with high crystalline quality following this two-step surface treatment. The findings contribute to the performance improvements of KSFM phosphors for industrial applications.
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