硅酸盐学报

CaNaLaZn₃（TeO₆）₂：Eu³⁺发光性能的调控及应用

PDF下载

茹晶晶 ¹ , 赵兵 ¹ , 许元艺 ¹ , 何嘉欣 ¹ , 郭飞云 ²

硅酸盐学报 | 研究论文 2025,53(5): 1066-1077

收起

硅酸盐学报 |研究论文 2025 , 53 (5) : 1066 -1077

CaNaLaZn₃（TeO₆）₂：Eu³⁺发光性能的调控及应用

全屏

茹晶晶¹, 赵兵¹, 许元艺¹, 何嘉欣¹, 郭飞云²

作者信息

^1．（宁德师范学院，绿色能源与环境催化福建省高校重点实验室，福建宁德 352100

^2．福州大学化学学院，福州 350108

通讯作者:

赵兵（1982—），男，硕士，副教授。

作者简介:

茹晶晶（1983—），女，博士，高级实验师。

Regulation of Luminescence Property and Application of CaNaLaZn₃(TeO₆)₂:Eu³⁺ Phosphor

Jingjing RU¹, Bing ZHAO¹, Yuanyi XU¹, Jiaxin HE¹, Feiyun GUO²

Affiliations

^1.Fujian Province University Key Laboratory of Green Energy and Environment Catalysis, Ningde Normal University, Ningde 352100, Fujian, China

^2.College of Chemistry, Fuzhou University, Fuzhou 350108, China

Corresponding Author:

ZHAO Bing (1982-), male, Master, Associate Professor. E-mail: woshizhaobing@outlook.com

RU Jingjing (1983-), female, Ph.D., Senior Experimentalist. E-mail: jing3032357@163.com

出版时间: 2025-05-20 doi: 10.14062/j.issn.0454-5648.20240644

文章导航

摘要

收起

在节能环保的大背景下，构建具有多功能应用的荧光粉已成为迫在眉睫的挑战。采用高温固相法制备了系列能够被近紫外光有效激发的CaNaLaZn₃（TeO₆）₂：xEu³⁺红色荧光粉。利用［Na⁺-La³⁺］离子对取代［Ca²⁺-Ca²⁺］的化学单元共取代策略，将CaNaLaZn₃（TeO₆）₂基质中Eu³⁺的最佳掺杂浓度有效提高至15%（摩尔分数），最佳样品CaNaLaZn₃（TeO₆）₂：0.15Eu³⁺的发光强度提升至取代前Ca₃Zn₃（TeO₆）₂：0.12Eu³⁺样品的1.908倍，且为商用Y₂O₃：Eu³⁺发光强度的1.135倍，该样品的色纯度为99.78%，色坐标为（0.649 2，0.350 4），更接近理想红光点（0.670，0.330），证实了化学单元共取代策略能够有效调控样品的发光性能。变温荧光光谱测试表明，该荧光粉具有良好的颜色稳定性，420 K时，其色度偏移仅为0.008 52。所封装的白光LED色坐标为（0.314 9，0.325 0），显色指数R_a为87.3，该器件在50 mA电流下连续工作100 min，仍能保持良好的性能；所制得的CaNaLaZn₃（TeO₆）₂：0.15Eu³⁺/聚二甲基硅氧烷柔性薄膜具有良好的发光性能，适合用于柔性显示技术。

关键词

共取代 / 发光 / 荧光粉 / 热稳定性

Abstract

收起

Introduction

Amid the growing emphasis on energy conservation and environmental protection, designing phosphors with multifunctional applications has become an urgent challenge. The traditional approach of combining blue light-emitting diode (LED) chips with yellow phosphors to produce white light suffers from drawbacks such as low color rendering index (CRI) and high color temperature. To address the pressing demands of lighting and display technologies, developing high-efficiency red phosphors that can be excited by near-ultraviolet (near-UV) light is crucial for applications in white LEDs and flexible display technologies.

Building upon the garnet-like structure of Ca₃Zn₃(TeO₆)₂, a series of CaNaLaZn₃(TeO₆)₂:xEu³⁺ (CNLZT:xEu³⁺) red phosphors, capable of being effectively excited by near-UV light, were designed and synthesized using a chemical unit co-substitution strategy. In this approach, the [Na⁺-La³⁺] ion pair replaces the [Ca²⁺-Ca²⁺] ions. This co-substitution significantly enhances the luminescence properties of the CNLZT:0.15Eu³⁺ sample. White LED devices fabricated with this material exhibit excellent luminous performance and stability. Moreover, the CNLZT:0.15Eu³⁺/polydimethylsiloxane (PDMS) flexible film demonstrates promising luminance, making it well-suited for applications in flexible display technologies.

Methods

A series of CNLZT:xEu³⁺ red phosphors were synthesized using a high-temperature solid-state reaction method. Raw materials were accurately weighed according to stoichiometric ratios and thoroughly ground in an agate mortar for 25 min. The resulting mixture was loaded into alumina crucibles and sintered for 10 h in an air atmosphere at 1323 K. After cooling, the samples were reground to obtain fine powders.

The prepared CNLZT:0.15Eu³⁺ red phosphor was then mixed with BaMgAl₁₀O₁₇:Eu²⁺ (BAM:Eu²⁺, blue) and (Ba,Sr)₂SiO₄:Eu²⁺(BSS:Eu²⁺, green) in a specific mass ratio. This mixture, along with ZWL8820 organic silicone gel, was applied to a 395 nm near-UV chip and encapsulated to fabricate a white LED device. Additionally, a CNLZT:0.15Eu³⁺/PDMS flexible film was prepared by combining the CNLZT:0.15Eu³⁺ phosphor with PDMS in a predetermined mass ratio and cutting it to the desired size for subsequent testing.

Results and discussion

X-ray diffraction (XRD) analysis and Rietveld structural refinements reveal that substituting [Ca²⁺-Ca²⁺] ion pairs with [Na⁺-La³⁺] does not alter the matrix structure. The Eu³⁺ replace La³⁺ in the matrix, causing lattice contraction and a slight shift in XRD diffraction peaks toward higher angles. The main absorption peak at 394 nm aligns well with the near-UV LED chip.

When x=0.15, the luminescence intensity of the optimal sample CNLZT:0.15Eu³⁺ reaches its maximum, 1.135 times higher than the commercial red phosphor Y₂O₃:Eu³⁺ and 1.908 times greater than the pre-substitution Ca₃Zn₃(TeO₆)₂:0.12Eu³⁺. The color purity is 99.78%, and the CIE color coordinates are (0.649 2, 0.350 4), close to the ideal red light point (0.670, 0.330), demonstrating excellent red luminescence. This confirms that the chemical unit co-substitution strategy effectively enhances luminescence properties.

At elevated temperatures, the CNLZT:0.15Eu³⁺ sample exhibits good color stability. The packaged white LED device has a correlated color temperature (CCT) of 6414 K and a CRI (R_a) of 87.3. Its CIE coordinates (0.314 9, 0.325 0) lie in the white light region. Even after 100 minutes of continuous operation at 50 mA, the white LED maintains stable performance and luminescence. Furthermore, the CNLZT:0.15Eu³⁺/PDMS film remains intact and efficiently luminescent after bending tests, demonstrating potential for flexible display applications.

Conclusions

A series of CNLZT:xEu³⁺ red phosphors, excitable by near-UV light, were synthesized using a high-temperature solid-state reaction method. By employing the chemical unit co-substitution strategy of [Na⁺-La³⁺] replacing [Ca²⁺-Ca²⁺], the optimized doping concentration of Eu³⁺ in the CNLZT matrix was effectively elevated to 15% (in mole). The luminous intensity of the CNLZT:0.15Eu³⁺ sample is 1.908 times that of the pre-substitution Ca₃Zn₃(TeO₆)₂:0.12Eu³⁺ sample and 1.135 times that of the commercial Y₂O₃:Eu³⁺.

The color purity of the CNLZT:0.15Eu³⁺ sample is 99.78%, and its color coordinates (0.649 2, 0.350 4) are close to the ideal red point (0.670, 0.330). The chemical unit co-substitution strategy effectively regulates the luminescent properties. Temperature-dependent fluorescence spectroscopy confirms that CNLZT:0.15Eu³⁺ possesses excellent color stability, with a chromaticity shift of only 0.008 52 at 420 K.

The packaged white LED achieves CIE coordinates of (0.314 9, 0.325 0) with a CRI (R_a) of 87.3, demonstrating precise color rendering and stable performance after 100 min of continuous operation at 50 mA. Moreover, the CNLZT:0.15Eu³⁺/PDMS flexible film shows promising luminance, making it suitable for applications in flexible display technologies.

Key words

co-substitution / luminescence / phosphors / thermal stability

引用本文

茹晶晶, 赵兵, 许元艺, 何嘉欣, 郭飞云. CaNaLaZn₃（TeO₆）₂：Eu³⁺发光性能的调控及应用. 硅酸盐学报, 2025 , 53 (5) : 1066 -1077 . DOI: 10.14062/j.issn.0454-5648.20240644

Jingjing RU, Bing ZHAO, Yuanyi XU, Jiaxin HE, Feiyun GUO. Regulation of Luminescence Property and Application of CaNaLaZn₃(TeO₆)₂:Eu³⁺ Phosphor[J]. Journal of the Chinese Ceramic Society, 2025 , 53 (5) : 1066 -1077 . DOI: 10.14062/j.issn.0454-5648.20240644

基金

收起

福建省自然科学基金项目(2021J011149)
宁德师范学院专项资助计划科研项目(2023ZX409)

参考文献

收起

文献

收起

参考文献引证文献

排序方式：

2025年第53卷第5期

PDF下载

引用本文

BibTeX

文章信息

doi: 10.14062/j.issn.0454-5648.20240644

接收时间：2024-10-08
首发时间：2026-10-22
出版时间：2025-05-20

补充材料

相关文章

文章信息

作者

出版历史

收稿日期：2024-10-08
修回日期：2024-11-01

基金

福建省自然科学基金项目(2021J011149)

宁德师范学院专项资助计划科研项目(2023ZX409)

作者信息

^1．（宁德师范学院，绿色能源与环境催化福建省高校重点实验室，福建宁德 352100

^2．福州大学化学学院，福州 350108

通讯作者:

赵兵（1982—），男，硕士，副教授。

参考文献

分享链接

https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20240644

分享至

全文二维码

扫描看全文

引用本文

BibTeX

本文的引用情况

2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

关闭全屏

BibTeX
EndNote
RefWorks
TxT