Defect assisted self-reduction and post annealing of Mn ions activated garnet transparent ceramics

Transition-metal Mn2+ ion-doped transparent ceramics (TCs) are promising color-convertors to improve color rendition for solid-state lighting. However, the stabilization of Mn2+ remains a challenge owing to the changeable atmosphere in the specific preparation of TC. In this work, the variations of valence states of Mn ions in typical garnet lattice host (YAG and LuAG) throughout the TC fabrication were demonstrated. By combined first principles calculation and experimental investigation, an enhanced self-reduction of Mn ions was clarified in LuAG host, which was originated from the higher concentration of oxygen vacancy defects. Moreover, the air annealing treatment could significantly weaken and enhance the absorption of Mn2+ and Mn3+ respectively, degrading the orange-red emission peaking at 594 nm. On account of the oxidation of Mn2+ ions, a photoluminescence spectra redshift of 9 nm was observed with increasing air annealing temperature and oxygen content, owing to strengthened crystal field strength surrounding Mn2+ ions. Finally, a high color rendering index of 74.5 of resultant white laser diodes device structured by single-phase LuAG:Ce,Mn TCs was obtained based on an efficient energy transfer process from Ce3+ to Mn2+. This study will deepen the understanding of the crystal defects inside TCs on luminescence properties, as well as inspiring more exploration on defect control to develop high performance ceramic color-convertor.