Structure and luminescence properties of single-component melilite Sr2MgSi2O7:Ce/Tb/Sm for n-UV wLEDs

Abstract

Phosphor-converted white light-emitting diodes (pc-wLEDs) have attracted attention in the field of solid-state lighting. Selection and study of suitable single-phase phosphor and packaging modes are currently the main research hotspots. Herein, color-tunable photoluminescence (PL) and thermally stable tri-doped Melitite Sr₂MgSi₂O₇:Ce/Tb/Sm are systematically studied via structural and static/dynamic spectral analyses. All dopants could only be accommodated in the Sr site due to similar ionic radii. Previous studies have concluded that green and red PL could be obtained from singly doped Tb and Sm phosphors with excellent reproduction, and color tunable PL can be achieved from Ce/Tb co-doped phosphors. The forbidden 4f–4f transitions of Tb/Sm cause low efficiency and Ce/Tb co-doping cannot achieve white light emissions. Alternatively, co-doping allowed 5d–4f transition sensitizer with emissions in the UV-blue region (i.e., Ce), color-tunable PL (including the white light); high efficiency of Sr₂MgSi₂O₇:Ce/Tb/Sm could be achieved via energy transfer (ET) from Ce → Tb → Sm. The impossibly direct ET from Ce → Sm is associated with the side metal–metal charge transfer (MMCT) effect. Due to chemically nonequivalent substitutions, two positive Ce(Tb,Sm)_Sr and one negative V′′_Sr were created to maintain the whole charge balance. To reduce the defects and allow more dopants to enter into the Sr site, Na⁺ was added as a charge balancer to enhance PL efficiency. Furthermore, an alkaline-earth-metal-ions blending strategy via partial replacement of Sr with Ba was investigated to regulate PL owing to the change in crystal field splitting. PL blue-shifted by Ba-co-doping, which could increase the degree of overlapping and enhance ET efficiency. As a proof-of-concept experiment, the pc-wLED fabricated via a combination of the optimal Sr(Ba)₂MgSi₂O₇:Ce/Tb/Sm/Na and an n-UV LED chip based on a remote ‘capping’ packaging mode shows excellent performances, indicating its strong potential application in the field of solid-state lighting.