硅酸盐学报

共取代策略增强NaLaCaTeO₆：Eu³⁺的发光性能及在白光发光二极管中的应用

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赵兵 ¹ , 茹晶晶 ¹ , 郭飞云 ² , 郭诗莹 ¹

硅酸盐学报 | 研究论文 2025,53(2): 257-266

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硅酸盐学报 |研究论文 2025 , 53 (2) : 257 -266

共取代策略增强NaLaCaTeO₆：Eu³⁺的发光性能及在白光发光二极管中的应用

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赵兵¹, 茹晶晶¹, 郭飞云², 郭诗莹¹

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:

茹晶晶（1983—），女，博士，高级实验师。

作者简介:

赵兵（1982—），男，硕士，副教授。

Co-substitution Strategy to Improve the Luminescence Property of NaLaCaTeO₆:Eu³⁺ Phosphor and Its Application in White Light Emitting Diode

Bing ZHAO¹, Jingjing RU¹, Feiyun GUO², Shiying GUO¹

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:

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

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

出版时间: 2025-02-20 doi: 10.14062/j.issn.0454-5648.20240386

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摘要

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高效和热稳定的红色荧光粉能够有效改善荧光粉转换型白光发光二极管的性能。采用高温固相反应法制备了一系列新型的NaLaCaTeO₆：xEu³⁺荧光粉。在395 nm激发下，NaLaCaTeO₆：Eu³⁺样品呈现出Eu³⁺的特征跃迁峰。通过［Na⁺-La³⁺］取代［Ca²⁺-Ca²⁺］离子对的共取代策略，NaLaCaTeO₆中Eu³⁺的最佳掺杂浓度提高至60%（摩尔分数），该荧光粉的色纯度和内量子效率分别高达99.87%和67.6%。另外，该荧光粉的发光强度和热稳定性比取代前的Ca₃TeO₆：0.2Eu³⁺样品也有明显提升，在420 K时的发射强度仍保持在300 K时的91.7%。所制备的白光LED显色指数R_a为80.6，CIE色度坐标为（0.317 6，0.334 0），表明所制备的NaLaCaTeO₆：0.6Eu³⁺红色荧光粉在固态照明中具有广泛的应用前景。

关键词

共取代 / 发光 / 荧光粉 / 热稳定性

Abstract

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Introduction

As a high-quality light source, the performance of phosphor-converted white light emitting diodes (pc-WLEDs) is closely related to the performance of the selected luminescent materials. The traditional method of combining blue LED chips and yellow phosphors to generate white light has problems of low color rendering index and high color temperature. To address the pressing requirements of lighting and display technologies, the development of novel red phosphors with high efficiency and excellent thermal stability is urgent. Perovskite tellurites have attracted extensive attention due to their elemental diversity and structural tunability. Based on the double perovskite Ca₃TeO₆, a series of NaLaCaTeO₆:xEu³⁺ phosphors that can be effectively excited by near-ultraviolet light have been designed and synthesized by elemental design. Through a co-substitution strategy of [Na⁺-La³⁺] substitution of [Ca²⁺-Ca²⁺] ion pair, the problem of low Eu³⁺ doping concentration in Ca₃TeO₆:Eu³⁺ is effectively improved by regulating the matrix structure. Meanwhile, the luminous intensity and thermal stability of the sample were also significantly improved.

Methods

Series of NLCT:xEu³⁺ (0.05 ≤ x ≤ 1.0) samples were successfully synthesized by a high-temperature solid-state reaction. The stoichiometric amounts of raw materials, including Na₂CO₃ (105.99 g/mol, 99.9%), CaCO₃ (100.09 g/mol, 99.9%), TeO₂ (159.6 g/mol, 99.99%), La₂O₃ (325.84 g/mol, 99.99%) and Eu₂O₃ (351.93 g/mol, 99.99%) purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., were weighed and grounded into homogeneous powder for 30 min. Afterward, the obtained powder was put into crucibles and heated at 1473 K for 12 h in a muffle furnace. Eventually, the target substances were obtained after cooling down and grinding again. A red LED device was assembled using the NLCT:0.6Eu³⁺ phosphor with a 395 nm chip. The WLED device was fabricated by connecting tricolor phosphors including BaMgAl₁₀O₁₇:Eu²⁺ (BAM:Eu²⁺, blue), (Ba, Sr)₂SiO₄:Eu²⁺ (BSS:Eu²⁺, green), along with the prepared NLCT:0.6Eu³⁺ (red) with a 395 nm chip.

Results and discussion

The results of XRD patterns showed that [Na⁺-La³⁺] substituted the [Ca²⁺-Ca²⁺] ion pair, which did not affect the structure of the sample. The diffraction peaks of the samples with x = 0.1-0.6 did not show obvious impurity peaks, indicating that the synthesized samples were pure phases. Eu³⁺ ions tended to occupy the site of La in the matrix rather than Te. DRS results also confirmed that Eu³⁺ ions were successfully introduced into the NLCT matrix. The dominant absorption peak at 395 nm matches well with InGaN-based LED, and the emission intensity reaches the maximum at x = 0.6. The primary mechanism among Eu³⁺ ions in NLCT:xEu³⁺ samples was proved to the dipole-dipole interaction.

The luminous intensity of the prepared NLCT:0.6Eu³⁺ red phosphor is about 1.98 and 3.97 times than that of CT:0.2Eu³⁺ and Y₂O₃:Eu³⁺, confirming the feasibility of the co-substitution strategy. The internal quantum yield and color purity of NLCT:0.6Eu³⁺ are 67.6% and 99.87%, respectively. The CIE color coordinates of this sample (0.658 1, 0.341 0) are closer to the ideal red point (0.670, 0.330) than that of the purchased commercial red phosphor Y₂O₃:Eu³⁺. Compared with CT:0.2Eu³⁺ (about 77.5%), the thermal stability of NLCT:0.6Eu³⁺ is significantly improved. When the temperature rises to 420 K, the emission intensity at 616 nm remains 91.7% of that at 300 K. Furthermore, the sample exhibits excellent color stability by the CIE coordinates shifting only slightly from (0.658 2, 0.340 8) to (0.646 6, 0.351 9) with increasing temperature. The CCT and R_a of the prepared WLED device are 6215 K and 80.6, respectively, and the CIE coordinates (0.317 6, 0.334 0) are located in the white light region.

Conclusions

A series of innovative NaLaCaTeO₆:xEu³⁺ phosphors were synthesized using a high temperature solid-state reaction method. Under 395 nm excitation, the NaLaCaTeO₆:Eu³⁺ samples exhibit a strong red emission at 616 nm (⁵D₀→⁷F₂) of Eu³⁺ ions. Through a co-substitution strategy where [Na⁺-La³⁺] replaced the [Ca²⁺-Ca²⁺] ion pair, the optimized doping concentration of the NaLaCaTeO₆:xEu³⁺ is elevated to 60% (molar fractior), leading to exceptional color purity and high internal quantum efficiency reaching 99.87% and 67.60%, respectively. Furthermore, compared to the Ca₃TeO₆:0.2Eu³⁺ sample pre-substitution, the luminous intensity and thermal stability of NaLaCaTeO₆:0.6Eu³⁺ phosphor witness a notable increase. Even at 420 K, the emission intensity remains at 91.7% compared to 300 K. The resultant WLED displays a color rendering index R_a of 80.6 and CIE chromaticity coordinates of (0.317 6, 0.334 0), underscoring the broad application potential of NaLaCaTeO₆:0.6Eu³⁺ in solid-state lighting.

Key words

co-substitution / luminescence / phosphors / thermal stability

引用本文

赵兵, 茹晶晶, 郭飞云, 郭诗莹. 共取代策略增强NaLaCaTeO₆：Eu³⁺的发光性能及在白光发光二极管中的应用. 硅酸盐学报, 2025 , 53 (2) : 257 -266 . DOI: 10.14062/j.issn.0454-5648.20240386

Bing ZHAO, Jingjing RU, Feiyun GUO, Shiying GUO. Co-substitution Strategy to Improve the Luminescence Property of NaLaCaTeO₆:Eu³⁺ Phosphor and Its Application in White Light Emitting Diode[J]. Journal of the Chinese Ceramic Society, 2025 , 53 (2) : 257 -266 . DOI: 10.14062/j.issn.0454-5648.20240386

基金

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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)

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2025年第53卷第2期

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文章信息

doi: 10.14062/j.issn.0454-5648.20240386

接收时间：2024-06-03
首发时间：2026-10-22
出版时间：2025-02-20

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收稿日期：2024-06-03
修回日期：2024-06-28

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:

茹晶晶（1983—），女，博士，高级实验师。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20240386

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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

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