硅酸盐学报

三维立体显示用稀土掺杂纯红色上转换发光氟氧化物玻璃陶瓷

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尤凤銮 ¹ , 王少雄 ¹ , 郑嵩 ¹ , 张年丰 ¹ , 林世盛 ¹ , 陈大钦 ¹^,²

硅酸盐学报 | 微晶玻璃专题—研究论文 2024,52(8): 2455-2462

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硅酸盐学报 |微晶玻璃专题—研究论文 2024 , 52 (8) : 2455 -2462

三维立体显示用稀土掺杂纯红色上转换发光氟氧化物玻璃陶瓷

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尤凤銮¹, 王少雄¹, 郑嵩¹, 张年丰¹, 林世盛¹, 陈大钦¹^,²

作者信息

^1．福建师范大学物理与能源学院，福州 350117

^2．福建省先进高温超导材料工程研究中心，福州 350117

通讯作者:

林世盛（1994—），男，博士，副教授；

陈大钦（1978—），男，博士，教授。

作者简介:

尤凤銮（2000—），女，硕士研究生。

Rare-Earth Doped Pure Red Upconversion Luminescent Oxyfluoride Glass Ceramics for Three-Dimensional Stereoscopic Displays

Fengluan YOU¹, Shaoxiong WANG¹, Song ZHENG¹, Nianfeng ZHANG¹, Shisheng LIN¹, Daqin CHEN¹^,²

Affiliations

^1.College of Physics and Energy, Fujian Normal University, Fuzhou 350117, China

^2.Fujian Province Engineering Research Center for Advanced High-Temperature Superconducting Materials, Fuzhou 350117, China

Corresponding Author:

LIN Shisheng (1994-), male, Ph.D., Associate Professor. E-mail: linshisheng@fjnu.edu.cn;

CHEN Daqin (1978-), male, Ph.D., Professor. dqchen@fjnu.edu.cn

YOU Fengluan (2000-), female, Master candidate. E-mail: you.f.l@foxmail.com

出版时间: 2024-08-20 doi: 10.14062/j.issn.0454-5648.20230895

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摘要

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三维立体显示技术图像逼真，因能够实现实时交互和全视景、多角度观察而备受关注。在各项三维立体显示技术中，基于透明上转换发光材料的静态体成像技术优势最为显著。鉴于此，本工作中，利用熔融-冷却-热处理制备方法，得到了一种Er³⁺和Tm³⁺共掺α-NaYF₄纳米晶氟氧化物透明玻璃陶瓷；利用Er³⁺与Tm³⁺之间的能量传递过程，使得电子选择性布居，Er³⁺红光发射增强，实现了980 nm近红外激光器激发下的纯红光发射。借助自主搭建的三维立体显示原型器件，可实现高色纯、高稳定纯红光三维静态/动态显示，体现了所研发材料在新一代三维立体显示技术中的应用潜力。

关键词

三维立体显示 / 上转换发光材料 / 稀土离子 / 氟氧化物玻璃陶瓷

Abstract

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Introduction

With the development of society, two-dimensional displays can no longer meet people's needs. Three-dimensional displays can completely reproduce the scene of world, showing the depth of the object, the sense of hierarchy, and reality because the real world is also three-dimensional. At present, there are a lot of techniques to realize three-dimensional displays, including two-dimensional analog three-dimensional displays, binocular parallax stereoscopic displays, and three-dimensional stereoscopic displays. Nevertheless, two-dimensional simulation three-dimensional display does not produce physical depth of field; Binocular parallax stereoscopic display is limited because of the disadvantages of small angle zoom, causing visual fatigue, and needing to assistant equipment. In contrast, three-dimensional stereoscopic display technology has attracted attention due to its realistic display effect, real-time interaction, and multi-angle observation. Among the related technologies, the static volume display technology based on transparent upconversion luminescent materials shows the most significant advantages.

Methods

Appropriate composition design is a necessary condition for the nucleation and growth of fluoride nanocrystals in glass. In this study, rare earth doped pure red upconversion luminescent oxyfluoride transparent glass ceramics were obtained via the conventional melt-quenching-thermal annealing method. The glass compositions (in mole) are 60SiO₂-6Al₂O₃-7Na₂CO₃-19NaF-xErF₃-yTmF₃-(8-x-y)YF₃ (x=0-1.6%, y =0-0.4%). The raw materials are SiO₂, Al₂O₃, Na₂CO₃(Sinopharm Chemical Reagents Co., Ltd.), and high-purity NaF, ErF₃, TmF₃, YF₃(Shanghai Macklin Biochemical Technology Co., Ltd), which were weighed, mixed and ground in an agate mortar. The obtained mixtures were then placed in a sealed alumina crucible and melted at 1 550 ℃ for 45 min under ambient atmosphere. Subsequently, the glass melt was poured into a 200 ℃ preheated copper mould and annealed at 400 ℃ for 5 h to relinquish the internal stress. Finally, the obtained bulk glass was heat-treated at 650 ℃ for 2 h to induce in-situ fluoride crystallization inside the glass to obtain oxyfluoride glass ceramics containing NaYF₄ nanocrystals (NaYF₄@glass).

Results and discussion

For Er³⁺/Tm³⁺ co-doped NaYF₄@glass, the influence of Er³⁺ doped content was explored and an optimal Er³⁺ concentration of 15% was confirmed. Meanwhile, with the increase of co-doped Tm³⁺ content, the red emission of Er³⁺ gradually enhanced due to the energy transfer process between Er³⁺ and Tm³⁺. Correspondingly, the color purity of red emission increased to realize the pure red emission upon the 980 nm near-infrared laser excitation. In addition, the temperature dependent spectra (from 80 K to 470 K) of 15%Er-2%Tm∶NaYF₄@glass were tested. Owing to the electrons at the ²H_11/2, ⁴S_3/2 and ⁴F_9/2 levels of Er³⁺ were populated independently, there was no direct temperatures-dependent electron correlation between the green (²H_11/2, ⁴S_3/2) and red (⁴F_9/2) levels of Er³⁺ ions. With the increase of temperature, the shape of the emission peak remained basically unvaried, indicating excellent chromatic stability. Ultimately, the Er³⁺/Tm³⁺ co-doped NaYF₄@glass-based three-dimensional prototype display device showed three-dimensional static/dynamic designed red patterns with high color purity and high stability, providing its potential use in new-generation three-dimensional stereoscopic display technology.

Conclusions

In summary, Er³⁺/Tm³⁺ co-doped NaYF₄@glass can be successfully prepared via conventional melt-quenching-thermal annealing method. The optimized 15%Er-2%Tm co-doped NaYF₄@glass can achieve pure red upconversion luminescence due to the energy transfer process between Er³⁺ and Tm³⁺. Owing to that the electrons in the ²H_11/2, ⁴S_3/2 and ⁴F_9/2 levels of Er³⁺ are independently populated, there is not direct temperature-dependent electron correlation between the green energy level (²H_11/2, ⁴S_3/2) and the red energy level (⁴F_9/2) of Er³⁺. Moreover, the Er³⁺/Tm³⁺ co-doped NaYF₄@glass-based three-dimensional prototype display device is constructured. This study can provide a new idea for the development of pure color transparent upconversion materials for three-dimensional stereoscopic display.

Key words

three-dimensional stereoscopic displays / upconversion materials / rare earth / oxyfluoride glass ceramics

引用本文

尤凤銮, 王少雄, 郑嵩, 张年丰, 林世盛, 陈大钦. 三维立体显示用稀土掺杂纯红色上转换发光氟氧化物玻璃陶瓷. 硅酸盐学报, 2024 , 52 (8) : 2455 -2462 . DOI: 10.14062/j.issn.0454-5648.20230895

Fengluan YOU, Shaoxiong WANG, Song ZHENG, Nianfeng ZHANG, Shisheng LIN, Daqin CHEN. Rare-Earth Doped Pure Red Upconversion Luminescent Oxyfluoride Glass Ceramics for Three-Dimensional Stereoscopic Displays[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (8) : 2455 -2462 . DOI: 10.14062/j.issn.0454-5648.20230895

基金

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国家自然科学基金(52272141; 51972060; 12074068; 52102159; 22103013; 12304442)
福建省自然科学基金(2022J05091; 2020J02017; 2021J06021; 2021J01190; 2020J01931; 2020H0026)

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2024年第52卷第8期

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文章信息

doi: 10.14062/j.issn.0454-5648.20230895

接收时间：2023-11-21
首发时间：2026-10-22
出版时间：2024-08-20

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出版历史

收稿日期：2023-11-21
修回日期：2023-12-07

基金

国家自然科学基金(52272141; 51972060; 12074068; 52102159; 22103013; 12304442)

福建省自然科学基金(2022J05091; 2020J02017; 2021J06021; 2021J01190; 2020J01931; 2020H0026)

作者信息

^1．福建师范大学物理与能源学院，福州 350117

^2．福建省先进高温超导材料工程研究中心，福州 350117

通讯作者:

林世盛（1994—），男，博士，副教授；

陈大钦（1978—），男，博士，教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20230895

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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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