硅酸盐学报

Ce³⁺、Cr³⁺掺杂宽带近红外发光材料Y₂CaAl₄SiO₁₂的发光性能以及能量传递

PDF下载

米晓云 ¹^,² , 刘宇洁 ² , 汪德岩 ² , 董雅玲 ² , 刘秀玲 ¹^,² , 王艳平 ¹^,²

硅酸盐学报 | 研究论文 2024,52(12): 3728-3736

收起

硅酸盐学报 |研究论文 2024 , 52 (12) : 3728 -3736

Ce³⁺、Cr³⁺掺杂宽带近红外发光材料Y₂CaAl₄SiO₁₂的发光性能以及能量传递

全屏

米晓云¹^,², 刘宇洁², 汪德岩², 董雅玲², 刘秀玲¹^,², 王艳平¹^,²

作者信息

^1．长春理工大学重庆研究院，重庆 401120

^2．长春理工大学材料科学与工程学院，长春 130022

作者简介:

米晓云（1979—），女，博士，教授。

Luminescence Properties and Energy Transfer of Ce³⁺, Cr³⁺ Doped Wideband Near-Infrared Luminescent Material Y₂CaAl₄SiO₁₂

Xiaoyun MI¹^,², Yujie LIU², Deyan WANG², Yaling DONG², Xiulin LIU¹^,², Yanping WANG¹^,²

Affiliations

^1.Research Institute of Changchun University of Science and Technology in Chongqing, Chongqing 401120, China

^2.School of Materials Science and Engineering, Changchun University of Science and Technology, Changchun 130022, China

MI Xiaoyun (1979-), female, Ph.D., Professor. E-mail: mixiaoyun@126.com

出版时间: 2024-12-20 doi: 10.14062/j.issn.0454-5648.20240318

文章导航

摘要

收起

发射波长范围在700~1100 nm的近红外发光因其可在无损检测、生物识别、夜视等领域发挥重要作用而倍受到关注。采用高温固相法合成了Cr³⁺单掺以及Ce³⁺、Cr³⁺共掺的Y₂CaAl₄SiO₁₂发光材料。在438 nm光激发下，Cr³⁺可以产生位于740 nm的近红外宽带发射以及690 nm的R线窄带发射。测量出单掺Cr³⁺的量子效率为24%，且通过激发光谱分析计算得出晶体场强度为2.429。通过变温光谱分析Y₂CaAl₄SiO₁₂：Cr³⁺的热稳定性，在150 ℃的发光强度可以达到初始强度的77.6%。在此基础上制备Y₂CaAl₄SiO₁₂：Ce³⁺，Cr³⁺发光材料，存在Ce³⁺到Cr³⁺的能量传递，其能量传递机制为四极-四极作用，且Y₂CaAl₄SiO₁₂：0.005Ce³⁺，0.007Cr³⁺的发光强度约为单掺Cr³⁺样品的3倍，同时测出共掺样品的量子效率为45%。

关键词

铬离子 / 石榴石 / 近红外发光 / 能量传递

Abstract

收起

Introduction

Near-infrared (NIR) luminescence with emission wavelengths ranging from 700 nm to 1100 nm has attracted much attention in the fields of nondestructive testing, biometrics, and night vision. In this paper, high-temperature solid-phase method was used to synthesize Cr³⁺ single-doped and Ce³⁺, Cr³⁺ co-doped Y₂CaAl₄SiO₁₂ luminescent materials. Under 438 nm light excitation, Cr³⁺ could produce a near-infrared broadband emission at 740 nm and R-line narrowband emission at 690 nm. The quantum efficiency of mono-doped Cr³⁺ was calculated to be 24%, and the crystal field intensity was calculated to be 2.429 by excitation spectral analysis. The thermal stability and the luminescence intensity of Y₂CaAl₄SiO₁₂∶ Cr³⁺ were analyzed by variable-temperature spectroscopy. In addition, Y₂CaAl₄SiO₁₂∶ Ce³⁺, Cr³⁺ luminescent materials were also prepared, and the luminescence intensity and the quantum luminescence efficiency of Y₂CaAl₄SiO₁₂∶ 0.005Ce³⁺, 0.007Cr³⁺ were analyzed.

Methods

In accordance with the stoichiometric ratios, Y_2-_xCaAl₄SiO₁₂∶ xCe³⁺ (where x = 0.001-0.011 mol) and Y₂CaAl_4-_ySiO₁₂∶0.005 Ce³⁺, y Cr³⁺ (where y = 0.001-0.011 mol) were prepared via solid-state reactions with raw materials of CaCO₃, Cr₂O₃, CeO₂, Al₂O₃, SiO₂, and Y₂O₃. The mixture with anhydrous ethanol was then ground in a mortar. Subsequently, the ground material was dried in an oven at 80 ℃ before being transferred to a square crucible for sintering in a reducing atmosphere at 1550 ℃ for 4 h. Afterwards, the sample was removed and allowed to cool to room temperature for the coming analysis.

Results and discussion

Y₂CaAl₄SiO₁₂∶ Cr³⁺ belongs to a cubic structure, the space group is $I a \overline{3} d$, the number of molecules Z=8. The optimal doping concentration of Y₂CaAl_4-_ySiO₁₂∶ yCr³⁺(y = 0-0.01) is 0.007, and the quenching mechanism of concentration is dipole-dipole interaction. After co-doping of Cr³⁺ and Ce³⁺ (Cr³⁺ is 0.007), the luminescence intensity is about 3 times greater than that of single-doped Cr³⁺, and the quantum efficiency is 45%. This indicates that the co-blending improves the luminescence performance of the material. When co-doped with Y₂CaAl₄SiO₁₂∶Ce³⁺ and Cr³⁺, the luminescence properties of the sample can reach 77.6% of the room temperature at 423 K (150 ℃), and the thermal stability is good.

Conclusions

Near-infrared luminescent materials of Y_2-_xCaAl₄SiO₁₂∶ Cr³⁺ and Y₂CaAl₄SiO₁₂∶ Ce³⁺, Cr³⁺ were synthesized via soild-state reactions. The luminescence properties and thermal stability of the samples were thoroughly analyzed, and Ce³⁺ was incorporated as a sensitizer to investigate the energy transfer mechanism between Ce³⁺ and Cr³⁺ within the matrix. The results indicated that Y₂CaAl₄SiO₁₂ exhibits a garnet structure, Cr³⁺ generated a broad near-infrared emission spectrum peaking at 740 nm alongside a sharp peak at 690 nm, achieving a quantum efficiency of 24% when doped alone. Y₂CaAl₄SiO₁₂∶ Ce³⁺, Cr³⁺ prepared had an energy transfer from Ce³⁺ to Cr³⁺. The energy transfer mechanism of this system was elucidated through IS0 and c fitting analyses. The luminous intensity of Y_1.995CaAl_3.993SiO₁₂∶ 0.005Ce³⁺ and 0.007Cr³⁺ was threefold greater than that of Y₂CaAl_3.993SiO₁₂∶0.007Cr³⁺. At this juncture, the quantum efficiency for co-doping reached 45%. When y was 0.011, the energy transfer efficiency measured was 30.01%. The thermal stability of Y₂CaAl₄SiO₁₂∶ 0.007Cr³⁺ revealed that its luminous intensity at 150 ℃ retained 77.6% of its value at room temperature, with a thermal activation energy calculated of 0.207 eV. This work could provide essential data for future applications of this material.

Key words

chromium ion / garnet / near-infrared luminescence / energy transfer

引用本文

米晓云, 刘宇洁, 汪德岩, 董雅玲, 刘秀玲, 王艳平. Ce³⁺、Cr³⁺掺杂宽带近红外发光材料Y₂CaAl₄SiO₁₂的发光性能以及能量传递. 硅酸盐学报, 2024 , 52 (12) : 3728 -3736 . DOI: 10.14062/j.issn.0454-5648.20240318

Xiaoyun MI, Yujie LIU, Deyan WANG, Yaling DONG, Xiulin LIU, Yanping WANG. Luminescence Properties and Energy Transfer of Ce³⁺, Cr³⁺ Doped Wideband Near-Infrared Luminescent Material Y₂CaAl₄SiO₁₂[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (12) : 3728 -3736 . DOI: 10.14062/j.issn.0454-5648.20240318

基金

收起

重庆市自然科学基金面上项目(cstc2021jcyj-msxmX1001; cstc2021jcyj-msxmX0936; cstc2021jcyj-msxmX0930)

参考文献

收起

文献

收起

参考文献引证文献

排序方式：

2024年第52卷第12期

PDF下载

引用本文

BibTeX

文章信息

doi: 10.14062/j.issn.0454-5648.20240318

接收时间：2024-05-09
首发时间：2026-10-22
出版时间：2024-12-20

补充材料

相关文章

文章信息

作者

出版历史

收稿日期：2024-05-09
修回日期：2024-05-28

基金

重庆市自然科学基金面上项目(cstc2021jcyj-msxmX1001; cstc2021jcyj-msxmX0936; cstc2021jcyj-msxmX0930)

作者信息

^1．长春理工大学重庆研究院，重庆 401120

^2．长春理工大学材料科学与工程学院，长春 130022

参考文献

分享链接

https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20240318

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