Enhancing Structural Rigidity via a Strategy Involving Protons for Creating Water-Resistant Mn4+-Doped Fluoride Phosphors

The poor water resistance property of a commercial Mn⁴⁺-activated narrow-band red-emitting fluoride phosphor restricts its promising applications in high-performance white LEDs and wide-gamut displays. Herein, we develop a structural rigidity-enhancing strategy using a novel KHF₂:Mn⁴⁺ precursor as a Mn source to construct a proton-containing water-resistant phosphor K₂(H)TiF₆:Mn⁴⁺ (KHTFM). The parasitic [HMnF₆]^- complexes in the interstitial site from the fall off the KHF₂:Mn⁴⁺ are also transferred to the K₂TiF₆ host by ion exchange to form KHTFM with rigid bonding networks, improving the water resistance and thermostability of the sample. The KHTFM sample retains at least 92% of the original emission value after 180 min of water immersion, while the non-water-resistant K₂TiF₆:Mn⁴⁺(KTFM) phosphor maintains only 23%. Therefore, these findings not only illustrate the effect of protons on fluoride but also provide a novel insight into commercial water-resistant fluoride phosphors.