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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
Published:05 February 2023,
Received:27 August 2022,
Revised:15 September 2022,
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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.
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。
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.
Mn4+掺杂氟化物CaTiF6·2H2O∶Mn4+极强零声子线高显色指数暖白光LED
Mn4+-doped fluoridesCaTiF6·2H2O∶Mn4+strong zero-phonon linehigh color rendering indexwarm WLED
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