Designing High-Performance LED Phosphors by Controlling the Phase Stability via a Heterovalent Substitution Strategy

Phosphor‐converted white light‐emitting diodes (LEDs) are currently playing key roles in the lighting and display industries and trigger urgent demands for the discovery of “good” phosphors with high quantum efficiency, improved thermal stability, and controllable excitation/emission properties. Herein, a general and efficient heterovalent substitution strategy is demonstrated in K₂HfSi₃O₉:Eu²⁺ achieved by Ln³⁺ (Ln = Gd, Tb, Dy, Tm, Yb, and Lu) doping to optimize luminescence properties, and as an example, the Lu³⁺ substitution leads to improvement of emission intensity and thermal stability, as well as tunable emission color from blue to cyan. The structural stability and Eu²⁺ occupation via Lu³⁺ doping have been revealed by the structural elaboration and density functional theory calculations, respectively. It is shown that heterovalent substitution allows predictive control of site preference of luminescent centers and therefore provides a new method to optimize the solid‐state phosphors for LEDs.