A red-emitting phosphor Na3AlF6:Mn4+: Green synthesis, optical characteristics, thermal stability and application in high-performance warm WLED

Abstract

Mn⁴⁺-doped fluoride red phosphors have been widely used in warm WLEDs, but the preparation of such phosphor requires the use of a large amount of HF as a fluorine source and an acidic environment. How to reduce the excessive use of highly toxic HF in the preparation process and achieve green synthesis has become a hot research topic. Therefore, a simple green synthesis strategy is proposed in this work to synthesize a series of red-emitting phosphors Na₃AlF₆:Mn⁴⁺. The highly toxic HF solution is replaced by using a low toxicity reaction system (HCl/HNO₃ + NH₄F), which reduces the direct use of HF. X-ray powder diffraction, energy-dispersive X-ray spectrometer and scanning electron microscope are employed to determine the crystal structure, composition and morphology of all samples. Optical properties are characterized using excitation spectra, emission spectra and fluorescence lifetime curves. The calculation results indicate that the red-light has low correlated color temperature and the excellent color purity, and Na₃AlF₆ host can provide a strong crystal field environment for Mn⁴⁺. In addition, different aluminum sources and Mn⁴⁺ doping concentrations are used to explore the optimal preparation condition. The mechanisms of concentration quenching and thermal quenching have also been systematically explored. The stabilities of red-light emission intensity and color are investigated under the high temperature. The integral PL intensity at 423 K is 47 % of the initial value at 298 K. The activation energy, the chromaticity shift and the chromaticity coordinate variation are also systematically calculated. More importantly, a high-performance warm WLED with low correlated color temperature (CCT = 3296 K) and high color rendering index (R_a = 94.7) is achieved by using Na₃AlF₆:Mn⁴⁺ as a red-emitting material. Not only that, the warm WLED exhibits strong output stability under high driving current. The discovery of this work provides a comprehensive understanding for the rational design of high-performance Mn⁴⁺-activated fluoride red phosphors via a simple green synthesis strategy.