Cr3+-activated Ca2GdZrSnGa3O12 garnet phosphors: structural reconstruction and crystal-field engineered broadband near-infrared emitters for LD/LED-driven light sources

IF 4.2 3区工程技术 Q2 CHEMISTRY, APPLIED

Dyes and Pigments Pub Date : 2025-09-17 DOI:10.1016/j.dyepig.2025.113255

Chengda Wu , Yahong Jin

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Abstract

Broadband near-infrared (NIR) phosphor-converted light sources (pc-LSs) are indispensable for emerging technologies that exploit the 700–1100 nm biological transparency window, yet their performance is critically limited by the scarcity of phosphors that simultaneously deliver red-shifted emission, high quantum efficiency, and thermal robustness. Here, we report a Cr³⁺-activated garnet Ca₂GdZrSnGa₃O₁₂ engineered by Ca–Zr/Sn cooperative substitution and M⁵⁺ charge compensation. The incorporation of Cr³⁺ into host lattice with a weak-field octahedral environment produces broadband NIR emission (⁴T₂ → ⁴A₂) centered at 801 nm with bandwidth of 168 nm under 466 nm excitation. M⁵⁺ cations codoping suppresses non-radiative pathways, elevating IQE to 51.58 % and retaining 81.58 % of the room-temperature intensity at 423 K. A low Huang-Rhys factor (S = 0.94) and enlarged activation energy (E_a = 0.25 eV) corroborate the suppressed electron–phonon coupling. Prototype phosphor-converted laser diode (pc-LD) and light-emitting diode (pc-LED) packages deliver optical output powers up to 381.2 mW@1500 mW mm⁻² and 51.2 mW@300 mA with photoelectric conversion efficiencies approaching 25.4 % and 4.48 %, respectively. These findings provide a materials-by-design route that reconciles the long-standing trade-off between spectral red-shift, quantum efficiency, and thermal robustness in Cr³⁺-activated NIR systems, and constitute a decisive advance toward compact, high-power NIR light engines for next-generation photonic applications.

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Cr3+活化Ca2GdZrSnGa3O12石榴石荧光粉：用于LD/ led驱动光源的结构重建和晶体场工程宽带近红外发射体

宽带近红外（NIR）磷转换光源（pc-LSs）对于利用700 - 1100nm生物透明窗口的新兴技术是必不可少的，但其性能受到同时提供红移发射，高量子效率和热鲁棒性的荧光粉的稀缺性的严重限制。本文报道了一种由Ca-Zr /Sn协同取代和M5+电荷补偿设计的Cr3+活化石榴石Ca2GdZrSnGa3O12。在弱场八面体环境下，Cr3+掺入主晶格，在466 nm激发下产生以801 nm为中心的宽带近红外发射（4T2→4A2），带宽为168 nm。M5+阳离子共掺杂抑制了非辐射途径，使IQE提高到51.58%，并在423 K时保持了81.58%的室温强度。较低的黄里斯因子（S = 0.94）和增大的活化能（Ea = 0.25 eV）证实了电子-声子耦合受到抑制。原型磷转换激光二极管（pc-LD）和发光二极管（pc-LED）封装的光输出功率高达381.2 mW@1500 mW mm - 2和51.2 mW@300 mA，光电转换效率分别接近25.4%和4.48%。这些发现提供了一条材料设计路线，调和了Cr3+激活的近红外系统中光谱红移、量子效率和热鲁棒性之间长期存在的权衡，并构成了下一代光子应用的紧凑、高功率近红外光引擎的决定性进展。

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来源期刊

Dyes and Pigments 工程技术-材料科学：纺织

CiteScore

8.20

自引率

13.30%

发文量

933

审稿时长

33 days

期刊介绍： Dyes and Pigments covers the scientific and technical aspects of the chemistry and physics of dyes, pigments and their intermediates. Emphasis is placed on the properties of the colouring matters themselves rather than on their applications or the system in which they may be applied. Thus the journal accepts research and review papers on the synthesis of dyes, pigments and intermediates, their physical or chemical properties, e.g. spectroscopic, surface, solution or solid state characteristics, the physical aspects of their preparation, e.g. precipitation, nucleation and growth, crystal formation, liquid crystalline characteristics, their photochemical, ecological or biological properties and the relationship between colour and chemical constitution. However, papers are considered which deal with the more fundamental aspects of colourant application and of the interactions of colourants with substrates or media. The journal will interest a wide variety of workers in a range of disciplines whose work involves dyes, pigments and their intermediates, and provides a platform for investigators with common interests but diverse fields of activity such as cosmetics, reprographics, dye and pigment synthesis, medical research, polymers, etc.