Morphology evolution and pure red upconversion mechanism of β-NaLuF(4) crystals

A series of β-NaLuF(4) crystals were synthesized via a hydrothermal method. Hexagonal phase microdisks, microprisms, and microtubes were achieved by simply changing the amount of citric acid in the initial reaction solution. Pure red upconversion (UC) luminescence can be observed in β-NaLuF(4):Yb(3+), Tm(3+), Er(3+) and Li(+) doped β-NaLuF(4):20% Yb(3+), 1% Tm(3+), 20% Er(3+). Based on the rate equations, we report the theoretical model about the pure red UC mechanism in Yb(3+)/Tm(3+)/Er(3+) doped system. It is proposed that the pure red UC luminescence is mainly ascribed to the energy transfer UC from Tm(3+):(3)F(4) → (3)H(6) to Er(3+):(4)I(11/2) → (4)F(9/2) and the cross-relaxation (CR) effect [Er(3+):(4)S(3/2) + (4)I(15/2) → (4)I(9/2) + (4)I(13/2)] rather than the long-accepted mechanism [CR process among Er(3+):(4)F(7/2) + (4)I(11/2) → (4)F(9/2) + (4)F(9/2)]. In addition, compared to the Li(+)-free counterpart, the pure red UC luminescence in β-NaLuF(4):20% Yb(3+), 1% Tm(3+), 20% Er(3+) with 15 mol% Li(+) doping is enhanced by 13.7 times. This study provides a general and effective approach to obtain intense pure red UC luminescence, which can be applied to other synthetic strategies.