Interplay of Consecutive Energy Transfer and Negative Thermal Expansion Property for Achieving Superior Anti‐Thermal Quenching Luminescence

Luminescence thermal quenching (TQ) is one of the most critical problems to be solved for further improvement of phosphors’ applications in lighting and many other fields. Herein, a novel strategy is demonstrated to achieve outstanding anti‐TQ performance with a substantial enhancement of Eu3+ red emission at 613 nm from Sc2MO3O12:Tb3+,Eu3+ phosphor. Its anti‐TQ performance is endowed by dual energy transfer (ET) pathways and intensified by the negative thermal expansion (NTE) property of the Sc2MO3O12 host. Remarkably, the photoluminescence (PL) emission intensity of Eu3+ from Sc2MO3O12:20%Eu3+,2%Tb3+ phosphor at 648 K reaches 507.3% of the initial intensity taken at 298 K. The lifetime of Eu3+ emission at 613 nm elongates with increasing measurement temperature. The experimental data and density functional theory (DFT) calculations reveal that the host structure shrinkage via NTE leads to the thermally boosted Eu3+ red emission by intensifying the consecutive ET and confinement of the absorption light. The potential of this phosphor as a dual‐mode high temperature thermometer based on both emission lifetime and intensity ratio read‐out modes is realized. This work provides inspiration to combine multiple strategies to achieve broad and dramatic anti‐TQ phosphors with enhanced performance for various optical applications.