The continually advancing near-infrared (NIR) phosphor-converted light-emitting diode (pc-LED) hold pivotal significance in optical imaging and NIR spectroscopy. Cr3+-doped garnet broadband NIR phosphors have attracted considerable attention owing to their high optical performance enabled by the rigid structure. Nonetheless, the emission wavelength is severely restricted, and longer wavelength emissions usually result in inferior quantum efficiency and poor luminescence stability. In this work, the concurrent reconstruction of dodecahedral and octahedral sites by introducing [Na+-Sn4+]C unit in the framework of Na2CaSn2Ge3O12 garnet contributes to the Cr3+ broadband NIR emission spanning 700–1200 nm, with a peak at 820 nm. Utilizing a charge compensation strategy via Ta5+ codoping largely boosts the internal quantum efficiency (IQE) of Na2CaSn2Ge3O12:Cr3+ from 93.06 % up to 95.04 %. Trap-mediated energy compensation is proposed to achieve a record-breaking zero-thermal-quenching behavior (99.39 %@423 K) of Cr3+-doped garnet with such a longer wavelength emission. The encapsulated prototype broadband NIR pc–LED gives rise to an overwhelming NIR output power of 590.9 mW@1300 mA and a photoconversion efficiency (PCE) of 32.62 % at 30 mA, rendering exceptional performance in night vision, detection, and NIR imaging applications.
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