Luminescence Properties of Narrow‐band Red Phosphor CaTiF6·2H2O∶Mn4+ for Warm White Light-emitting Diodes with High Color Rendering Index

CHEN Konglan; ZHANG Xueliang; SONG Enhai; ZHOU Yayun; YUAN Jian; FAN Ting; DENG Tingting

doi:10.37188/CJL.20220310

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Luminescence Properties of Narrow‐band Red Phosphor CaTiF₆·2H₂O∶Mn⁴⁺ for Warm White Light-emitting Diodes with High Color Rendering Index

Synthesis and Properties of Materials | 更新时间：2023-03-13

- Luminescence Properties of Narrow‐band Red Phosphor CaTiF₆·2H₂O∶Mn⁴⁺ for Warm White Light-emitting Diodes with High Color Rendering Index
  增强出版
- Chinese Journal of Luminescence Vol. 44, Issue 2, Pages: 259-270(2023)
- 作者机构：
  
  1.佛山科学技术学院物理与光电工程学院，粤港澳智能微纳光电技术联合实验室，广东佛山　528225
  2.华南理工大学发光材料与器件国家重点实验室，广东省光纤激光材料与应用技术重点实验室，广东广州　510640
- 作者简介：
- 基金信息：
  
  National Natural Science Foundation of China(51902053);Natural Science Foundation of Guangdong province(2019A1515011988);Research Fund of Guangdong-Hong Kong-Macao Joint Laboratory for Intelligent Micro-Nano Optoelectronic Technology(2021KTSCX119);Project of Department of Education of Guangdong Province(2020B1212030010);Open Fund of the Guangdong Provincial Key Laboratory of Fiber Laser Materials and Applied Techniques（South China University of Technology, 2021‐07）
- DOI：10.37188/CJL.20220310
  CLC：
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陈孔岚,张学亮,宋恩海等.CaTiF₆·2H₂O∶Mn⁴⁺窄带红色荧光粉的发光性能及其高显指暖白光LED应用[J].发光学报,2023,44(02):259-270.

CHEN Konglan,ZHANG Xueliang,SONG Enhai,et al.Luminescence Properties of Narrow‐band Red Phosphor CaTiF₆·2H₂O∶Mn⁴⁺ for Warm White Light-emitting Diodes with High Color Rendering Index[J].Chinese Journal of Luminescence,2023,44(02):259-270.
陈孔岚,张学亮,宋恩海等.CaTiF₆·2H₂O∶Mn⁴⁺窄带红色荧光粉的发光性能及其高显指暖白光LED应用[J].发光学报,2023,44(02):259-270. DOI： 10.37188/CJL.20220310.

CHEN Konglan,ZHANG Xueliang,SONG Enhai,et al.Luminescence Properties of Narrow‐band Red Phosphor CaTiF₆·2H₂O∶Mn⁴⁺ for Warm White Light-emitting Diodes with High Color Rendering Index[J].Chinese Journal of Luminescence,2023,44(02):259-270. DOI： 10.37188/CJL.20220310.

摘要

报道了一种新型的Mn,4+,掺杂水合六氟钛酸钙CaTiF,6,·2H,2,O∶Mn,4+,红色荧光粉，详细研究了基质的结构转变和荧光粉的发光性能及高显色指数（显指）暖白光LED应用。CaTiF,6,·2H,2,O∶Mn,4+,在130~200 ℃间脱水转化为CaTiF,6,∶Mn,4+,，荧光光谱发生改变，重新吸附水分子可恢复到CaTiF,6,·2H,2,O∶Mn,4+,，发光性能不可逆。重要的是，该荧光粉在较长波626 nm和635 nm处分别发射锐线极强的零声子线（ZPL）和ν,6,振动峰，色坐标为（0.701， 0.299），更接近人眼敏感的红光边界650 nm（色坐标,x,~0.72，,y,~0.28），有助于提高暖白光LED的显色指数、拓宽背光源的色域。晶体结构和晶体场强度计算指出，Mn,4+,在CaTiF,6,·2H,2,O∶Mn,4+,中占据低对称性的格位，所受到的晶体场强度较弱，Mn—F键的共价性较强。另外，通过表面疏水化显著提升了荧光粉耐湿性能，共掺小离子半径的Si,4+,增强了荧光粉发光热稳定性。以CaTiF,6,·2H,2,O∶Mn,4+,作为红光成分，获得了高显色指数（,R,a,=90，,R,9,=68）的暖白光LED，在高品质的暖白光照明中具有潜在的应用。

Abstract

Herein， a new Mn,4+,-doped hydrate calcium hexafluorotitanic CaTiF,6,·2H,2,O∶Mn,4+ ,red phosphor is reported. Physical properties of host， luminescence properties and warm white LED application of this phosphor are studied carefully. CaTiF,6,·2H,2,O∶Mn,4+, removes H,2,O to be CaTiF,6,∶Mn,4+, with changed emission spectrum. CaTiF,6,∶Mn,4+, could adsorb H,2,O and recover to CaTiF,6,·2H,2,O∶Mn,4+, except emission intensity. Importantly， it emits extremely strong zero phonon line（ZPL） and ν,6, vibration peaking at longer wavelength of 626 nm and 635 nm in sequence. This unique emission gives color coordinates of （0.701， 0.299）， more closing to the red-light boundary of human eyes sensibility（650 nm， chromaticity coordinate ,x,~0.72， ,y,~0.28）， which could enhance the color rendering index（,R,a,） of WLED and widen the color gamut of backlight display. The combination of crystal structure and crystal field strength calculation demonstrates that Mn,4+, ion locates at a highly unsymmetric lattice and experiences weak crystal field strength with strongly covalent Mn—F bond in CaTiF,6,·2H,2,O∶Mn,4+,. Moreover， coating with hydrophobic layer enhances the moisture resistant of CaTiF,6,·2H,2,O∶Mn,4+,. Codoping small ionic radius Si,4+, improves its thermal stability. Using CaTiF,6,·2H,2,O∶Mn,4+ ,as red-light component， a warm white LED with high ,R,a, ~90 and ,R,9, ~ 68 was achieved， showing potential in high color quality warm white lighting applications.

关键词

Mn4+掺杂氟化物CaTiF6·2H2O∶Mn4+极强零声子线高显色指数暖白光LED

Keywords

Mn4+-doped fluoridesCaTiF6·2H2O∶Mn4+strong zero-phonon linehigh color rendering indexwarm WLED

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State Key Laboratory of Luminescent Materials and Devices，Guangdong Provincial Key Laboratory of Fiber Laser Materials and Applied Techniques，South China University of Technology

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