Solid-state white-light-emitting diodes (WLEDs) have attracted more and more attention for its long lifetime, high efficiency, low cost, and environment-friendly relative to incandescent and fluorescent of traditional lighting. 1−4 At present, the white light of commercial WLED is mainly obtained through the combination of blue InGaN chip and Y 3 Al 5 O 12 :Ce 3+ (YAG:Ce 3+) yellow phosphor. Due to the deficiency of red emission, the inherent disadvantages of these WLEDs, such as low color rendering index (CRI, Ra<80) and high color temperature (CCT>6000K), limit their application in illuminating system. 5−8 Fortunately, some red-emitting phosphors that can be added directly to commercial WLED to improve the quality of LEDs have been developed. The non-rare-earth ion Mn 4+ has attracted our attention because its emission peak is located in the red region of 620 to 750 nm under blue and ultraviolet light excitation. 9−11 Among the Mn 4+-doped red phosphors, the emission peak of the Mn 4+-doped fluoride is located at 620 to 640 nm due to the weak coordination bond. In recent years, various Mn 4+activated fluoride phosphors such as A 2 XF 6 :Mn 4+ (A = K, Na, Cs, etc X = Si, Ge, Ti, etc) are gradually replacing the Eu 2+-doped nitride as red phosphors for manufacture the WLEDs because of their superior thermal stability, optical properties, and facile synthetic condition. 12−18