Origin of strong red emission in Er³⁺-based upconversion materials: role of intermediate states and cross relaxation

Among the various upconversion (UC) materials, sodium yttrium fluoride doped with ytterbium and erbium (NaYF₄:Yb³⁺,Er³⁺) is the most widely studied owing to its high UC efficiency. Nonetheless, UC mechanisms are not yet fully understood and, in particular, near-infrared-to-red UC mechanisms are still under debate. Herein, we examine UC mechanisms in Er³⁺-based UC materials. Most importantly, the ⁴F_3/2 and ⁴F_5/2 states of Er³⁺ were found to be important intermediate states for strong red emission, for the first time. The cross relaxation between the Er³⁺ ions, back energy transfer from Er³⁺ to Yb³⁺, and relative doping concentrations of Er³⁺ and Yb³⁺ in NaYF₄:Yb³⁺,Er³⁺ were found to play important roles in the relative intensity between red and green emissions. The proposed UC mechanism will provide design principles for various Er³⁺-based UC materials.