Near-infrared (NIR)-emitting phosphors with high quantum efficiency and thermal stability are crucial to NIR pc-LEDs. Garnet-structured (GdLuCa)(Al4-zSiCrz)O12 (z = 0.01-0.2) and (Gd2-xLuCax)(Al4.95-xSixCr0.05)O12 (x = 0.2-1.0) new phosphors with promising NIR luminescence under blue light excitation were designed and fabricated by a solid-state reaction in this work. It was analyzed that the Ca2+, Cr3+, and Si4+ ions would replace Gd3+ in [GdO8], Al1 in [Al1O6], and Al2 in [Al2O4], respectively, and the optimal Cr3+ content is z = 0.05, above which concentration quenching would occur via an electric dipole-dipole interaction. Increasing Ca2+/Si4+ substitution up to x = 1.0 led to luminescence enhancement by a factor of up to 1.85 and internal/external quantum efficiency (%) increment from ∼25.9/10.7 to 63.4/27.5, and all of the phosphors showed excellent thermal stability (I423K/I298K ≥ 87.6%). The luminescence properties of Cr3+ were discussed in detail through systematic investigation of the effects of Cr3+ and Ca2+/Si4+ contents on the crystal structure, local coordination, and crystal field. With the NIR pc-LED device integrated from the optimal phosphor (x = 1.0) and a blue LED chip, electroluminescence manifested potential applications in night vision and medical diagnosis.
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