A low-temperature co-precipitation approach to synthesize fluoride phosphors K2MF6:Mn4+ (M = Ge, Si) for white LED applications†
A new class of Mn4+ activated alkali-metal hexafluoride red phosphors are emerging for white light-emitting diodes because of their sharp red line 2Eg → 4A2g emissions (600–650 nm) excited by irradiation of 4A2g → 4T1g (320–380 nm) and 4A2g → 4T2g (380–500 nm) transitions. However, these phosphors have the drawbacks of difficult control of the Mn valence state during synthesis and lack of underlying mechanisms for structure–photoluminescence relationships. In this study, we explore a novel, highly productive route to the quantifiable synthesis of K2GeF6:Mn4+ by the chemical co-precipitation method at room temperature. The prepared yellowish K2GeF6:Mn4+ powders exhibit a hexagonal shape and high crystallinity without significant defects. The photoluminescence thermal stability and white light-emitting diodes applicability of K2GeF6:Mn4+ suggest that it is a promising commercial red phosphor because of its efficient emission intensity, high color purity and excellent thermal stability. Structural analyses and theoretical calculations reveal that the red shift of the K2GeF6:Mn4+ red phosphor compared with K2SiF6:Mn4+ is due to the longer Ge–F distance and lower effective Mulliken charge of F ions in coordination environments of the MnF62− octahedron. The split feature in K2GeF6:Mn4+ is due to the hexagonal distortion in the host. The structure–photoluminescence mechanism is predicted to be general in hexafluoride red phosphors to tune the optical properties through cationic substitutions and crystal structure adjustments.
- This article is part of the themed collection: JMC C Top Picks collection: Recent progress in light emitting diodes