Millimeter-Sized K 2 MnF 6 :Si 4+ , NH 4 + Red-Luminescent Crystals with High Absorption Efficiency (AE max of 93.5%) and External Quantum Efficiency (EQE max of 68.9%) Grown by Cooling-Induced Crystallization.

Luminescent bulk crystals exhibit fewer grain boundaries and defects compared with conventional microsized powdery ones. Herein, targeting Mn 4+ -activated fluoride crystals with a sharp line-type red luminescence spectrum, we propose a new cooling-induced crystallization method to grow the fluoride crystals. By this new method, we successfully grew millimeter-sized K 2 MnF 6 :Si 4+ , NH 4 + crystals, featuring an AE max (absorption efficiency) of 93.5% and an EQE max (external quantum efficiency) of 68.9%, which are among the best values for Mn 4+ -activated fluoride red phosphors. The influence of doping Si 4+ and/or NH 4 + in K 2 MnF 6 on the local coordination structure and luminescence properties was studied. The anomalous thermal quenching behaviors were discussed, the luminescence decay from the excited state was compared, and the origin for the high quantum efficiencies was analyzed.