长石型 LED 荧光粉中独特畸变 Mn4+ 八面体的超高效率窄带红色发光,Laser & Photonics Reviews

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长石型 LED 荧光粉中独特畸变 Mn4+ 八面体的超高效率窄带红色发光
Laser & Photonics Reviews ( IF 9.8 ) Pub Date : 2023-03-06 , DOI: 10.1002/lpor.202200940
Yiyang Liu ₁ , Rong Zhang ₁ , Kaiyi Yan ₁ , Jian‐Feng Sun ₁

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受矿物结构启发而发现的红色荧光粉已成为研究热点，有助于弥补冷白光发光二极管 (WLED) 中缺失的红色成分。本文首先利用长石型结构开发了窄带红光CaAl ₂ Si ₂ O ₈ :Mn ⁴⁺ /Mn ⁴⁺ , Mg ²⁺荧光粉。Rietveld精修结果证实了Mn ⁴⁺占据了扭曲的[Ca1O ₆ ]八面体，产生了强烈的霞拉效应，从而表现出半峰全宽较窄（43 nm）的亮红色发光。与CaAl ₂ Si ₂ O _8比较:Mn ^{4+ , CaAl}₂ Si ₂ O ₈ :Mn ⁴⁺ , Mg ²⁺的荧光强度进一步增强高达 210%，原因是从² E _g激发态开始的非辐射衰变率降低，减弱了浓度猝灭沿相邻聚集的Mn ⁴⁺的能量迁移产生的效应。CaAl ₂ Si ₂ O ₈ :Mn ⁴⁺ , Mg ²⁺显示出良好的热稳定性，具有超高的量子效率（90.3%），超过了现有的其他Mn ⁴⁺掺杂氧化物荧光粉和UCr₄ C ₄型氮化物荧光体。制造的 WLED 原型获得了理想的暖白光，具有低相关色温 (3081 K) 和覆盖国家电视系统委员会标准 112% 的宽色域。在天然矿物型结构原型的指导下，这项研究证明了设计独特的扭曲局部结构的可能性，以实现 Mn ⁴⁺在暖色 WLED 中的卓越发光性能。

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Ultrahighly Efficient Narrowband Red Luminescence of Uniquely Distorted Mn4+ Octahedron in the Feldspar-Type LED Phosphor

The mineral structure-inspired discovery of red phosphors has become a research hotspot that can help compensate for the missing red components in cold white light-emitting diodes (WLEDs). Herein, first the feldspar-type structure is utilized to develop narrowband red-emitting CaAl₂Si₂O₈:Mn⁴⁺/Mn⁴⁺, Mg²⁺ phosphors. Rietveld refinement results confirm the Mn⁴⁺ occupation of the distorted [Ca1O₆] octahedron, resulting in a strong nephelauxetic effect, and thus exhibits bright red luminescence with a narrow full width at half maximum (43 nm). Compared with CaAl₂Si₂O₈:Mn⁴⁺, the fluorescence intensity of CaAl₂Si₂O₈:Mn⁴⁺, Mg²⁺ is further enhanced by up to 210% owing to the decreasing nonradiative decay rate from ²E_g excited state, which weakens the concentration quenching effect resulting from energy migration along the adjacently aggregated Mn⁴⁺. CaAl₂Si₂O₈:Mn⁴⁺, Mg²⁺ shows preferable thermal stability with an ultrahigh quantum efficiency (90.3%), surpassing other current Mn⁴⁺-doped oxide phosphors and UCr₄C₄-type nitride phosphors. A fabricated prototype WLED obtains ideal warm white light with a low correlated color temperature (3081 K) and a wide color gamut covering 112% of the National Television System Committee standard. Guided by natural mineral-type structural prototypes, this study demonstrates the possibility of designing a uniquely distorted local structure to achieve a superior luminescence performance of Mn⁴⁺ for warm WLEDs.

更新日期：2023-03-06

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