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Valence conversion and site reconstruction in near-infrared-emitting chromium-activated garnet for simultaneous enhancement of quantum efficiency and thermal stability
Achievement of high photoluminescence quantum efficiency and thermal stability is challenging for near-infrared (NIR)-emitting phosphors. Here, we designed a “kill two birds with one stone” strategy to simultaneously improve quantum efficiency and thermal stability of the NIR-emitting Ca 3 Y 2-2 x (ZnZr) x Ge 3 O 12 :Cr garnet system by chemical unit cosubstitution, and revealed universal structure-property relationship and the luminescence optimization mechanism. The cosubstitution of [Zn 2+ –Zr 4+ ] for [Y 3+ –Y 3+ ] played a critical role as reductant to promote the valence transformation from Cr 4+ to Cr 3+ , resulting from the reconstruction of octahedral sites for Cr 3+ . The introduction of [Zn 2+ –Zr 4+ ] unit also contributed to a rigid crystal structure. These two aspects together realized the high internal quantum efficiency of 96% and excellent thermal stability of 89%@423 K. Moreover, information encryption with “burning after reading” was achieved based on different chemical resistance of the phosphors to acid. The developed NIR-emitting phosphor-converted light-emitting diode demonstrated promising applications in bio-tissue imaging and night vision. This work provides a new perspective for developing high-performance NIR-emitting phosphor materials.