Anti-Defect engineering toward high luminescent efficiency in whitlockite phosphors

Lacking an effective strategy to simultaneously address the challenges of quantum efficiency, luminescence intensity and thermal stability has become the key bottleneck for further development and large-scale application of solid-state lighting technology. Herein, inspired by the defect-engineering used in photoelectrocatalytic and photovoltaic materials, we acted in a diametrically opposite way and unprecedentedly proposed an anti-defect engineering strategy to develop high-efficiency phosphors. By constructing a rigid structure and introducing alkali metals M to remove cation vacancy defects, similar to building blocks and jigsaw puzzle, we developed three groups of whitlockite phosphors, namely Ca3-xSrx(PO4)2:Ce3+, Ca3(PO4)2:Ce3+,M and (Ca0.5Sr0.5)3(PO4)2:Ce3+,Na+,Mn2+, and synchronously realized the significant enhancement of photoluminescence intensity (2.46 times), thermal stability (87.92% at 150 °C), cathodoluminescence intensity (3.34 times), quantum yield (from 38.90% to 99.07%). We characterized the defect concentration by positron annihilation technique (PAT), and calculated Debye temperature (ΘD) and simulated the occupation of M according to DFT theory to reveal the improvement mechanism. Some advanced applications were also explored in this work, including warm-white LEDs, plant growth lighting and information security. The anti-defect engineering proposed in this work may contribute to the further development of high-efficiency phosphors for the next-generation smart solid-state lighting technologies.