Boosting Red Luminescence of Mn⁴⁺ in Tantalum Heptafluoride Based on an Ab Initio-Facilitated Sensitizer and Hydrophobic Surface Modification

A narrow-band red-light component is critical to establish high color rendition and a wide color gamut of phosphor-converted white-light-emitting diodes (pc-WLEDs). In this sense, Mn 4+ -doped K 2 SiF 6 fluoride is the most successful material that has been commercialized. As with K 2 SiF 6:Mn 4+ phosphors, Mn 4+ -doped tantalum heptafluoride (K 2 TaF 7:Mn 4+ ) fulfills a similar luminescence behavior and has been brought in a promising narrow-band red phosphor. But the limited brightness and low moisture-resistant performances have inevitably blocked its practical application. Herein, we employed the density functional theory (DFT)-based ab initio estimation approach to quickly identify the proper sensitizer by systematically investigating the electronic-band coupling between the several possible sensitizers (Rb, Hf, Zr, Sn, Nb, and Mo) and the luminescent center (Mn). Combined with experimental results, Mo was demonstrated to be the optimal sensitizer, which resulted in a 60% enhancement of the emission. On the side, the moisture sensitivity has been effectively improved via grafting the hydrophobic octadecyltrimethoxysilane (ODTMS) layer on the phosphor surface. Through employing the K 2 TaF 7:Mn 4+,Mo 6+ @ODTMS composite as a red component, warm WLEDs with good performance were achieved with a correlated color temperature (CCT) of 4352 K, a luminous efficacy (LE) of 90.1 lm/W, and a color rendering index (Ra) of 83.4. In addition, a wide color gamut reaching up to 102.8% of the NTSC 1953 value could be realized. Aging tests at 85 °C and 85% humidity for 120 h on this device manifested that the ODTMS-modified phosphor had much better moisture stability than that of the unmodified one. These studies provided viable tools for optimizing Mn 4+ luminescence in fluoride hosts.