可用于近紫外LED芯片的铕-铱双金属配合物红光共聚荧光粉

王子豪; 杨亚敏; 张爱琴; 贾虎生; 许并社; 贾静

doi:10.37188/CO.EN-2023-0023

可用于近紫外LED芯片的铕-铱双金属配合物红光共聚荧光粉

1.
太原理工大学材料与科学与工程学院, 太原 030024
2.
太原理工大学轻纺工程学院, 太原 030006
3.
太原理工大学航空航天学院, 太原 030006

详细信息

中图分类号: TQ422
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出版历程
- 收稿日期: 2023-09-02
- 修回日期: 2023-10-07
- 录用日期: 2023-11-01
- 网络出版日期: 2023-11-11

A red-emitting copolymer phosphors based on bimetallic Eu-Ir complex for Near-UV chip-based LEDs

doi: 10.37188/CO.EN-2023-0023

1.
College of Materials and Science and Engineering, Taiyuan University of Technology, Taiyuan 030024, China
2.
College of Textile Engineering, Taiyuan University of Technology, Taiyuan 030006, China
3.
College of Aeronautics and Astronautics, Taiyuan University of Technology, Taiyuan 030006, China

Funds: Supported by National Natural Science Foundation of China (No. 21972103); Research and Development Project of New Materials and Chemical Engineering Research Institute of Shanxi Zhejiang University (No. 2021SX-AT010)

More Information

Author Bio:
WANG Zi-hao (1999—), male, born in Jining，Shandong Province. He received his bachelor's degree from the University of Jinan in 2021 and is now a master's candidate in the School of Taiyuan University of Technology. He is mainly engaged in research on LED light-emitting phosphors. E-mail: wangzihao0331@link.tyut.edu.cn

JIA Jing (1987—), female, born in Yuanping, Shanxi Province. She received her doctoral degree from Taiyuan University of Technology in 2017. She is currently an intermediate engineer in the College of Aeronautics and Astronautics of TYUT, mainly engaged in the research of flexible LED lighting for the aircraft industries. E-mail: jiajing.chn@icloud.com

Corresponding author: jiajing.chn@icloud.com

摘要

摘要:
本研究以Ir配合物FIrPic作为Eu离子的配体，合成了一种新的Eu-Ir双金属配合物Eu(FIrPic)₂(Phen)UA，并通过自由基聚合成功制备了红色发光荧光共聚物PM-Eu-Ir，适用于商用近紫外芯片型LED。在不影响 Eu³⁺ 离子的荧光发射特性的前提下，加入 Ir-配合物可以有效地敏化 Eu³⁺ 离子，增强其对 400 nm紫外光的吸收。在 365 nm 紫外光激发下，共聚物 PM-Eu-Ir 在 612 nm 处显示出最强的发射峰，其 CIE 坐标为（0.461，0.254），这与 365 nm 近紫外芯片非常吻合。红色共聚荧光粉 PM-Eu-Ir 的微观形貌为典型的多层空间网络结构，除了表现出明显的红光发射和 634.54 μs 的荧光寿命外，还在 25～250 °C 的宽温范围内具有优异的热稳定性。使用共聚物 PM-Eu-Ir 制作的 LED 发出的红光亮度为 149800 cd/m²。研究结果表明，所制备的共聚荧光粉可作为红光元件用于制造近紫外芯片白光 LED。
- 稀土发光离子 /
- 双金属配合物 /
- 共聚型高分子荧光粉 /
- 近紫外LED
Abstract:
In this paper, a new Eu-Ir bimetallic complex Eu(FIrPic)₂(Phen)UA is synthesized using the Ir complex FIrPic as ligands for Eu ions and red-emitting phosphorescent copolymer PM-Eu-Ir is successfully prepared via radical polymerization for commercial near UV chip-based LEDs. The Eu³⁺ ions were found to be effectively sensitizable by adding Ir-complex with enhanced ultra-violet light absorption at around 400 nm without affecting the fluorescence emission characteristic of the Eu³⁺ ions. The proposed copolymer PM-Eu-Ir exhibits the strongest emission peak at 612 nm with the CIE coordinates (0.461, 0.254) under 365 nm ultra-violet light excitation, which matches well with the 365 nm near-UV chip. The micro-morphology of the red copolymer phosphor PM-Eu-Ir is a typical multilayer spatial network structure; as well as having appreciable red emission and the corresponding fluorescence lifetime of 634.54 μs, it also has excellent thermal stability in a wide range of 25～250 °C. The LEDs fabricated by the copolymer PM-Eu-Ir display red light emission with a 149800 cd/m² luminance. The results support the potential utilization of prepared copolymer phosphor as a red component in the fabrication of near UV chip-based white LEDs.
- rare-earth luminescent ions /
- bimetallic complexes /
- copolymer phosphors /
- NUV LED chips

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Figure 1. Synthetic route of the bimetallic complex Eu(FIrPic)₂(Phen)UA

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Figure 2. Synthesis route of the copolymer PM-Eu-Ir

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Figure 3. FT-IR spectra of the FIrPic, Eu(FIrPic)₂(Phen)UA, and PM-Eu-Ir

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Figure 4. UV-vis absorption spectra of the Ir complex FIrPic, bimetallic complex Eu(FIrPic)₂(Phen)UA, and phosphorescent copolymer PM-Eu-Ir

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Figure 5. FE-SEM images of the bimetallic complex Eu(FIrPic)₂(Phen)UA (a) and phosphorescent copolymer PM-Eu-Ir (b)

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Figure 6. (a) DSC curves and (b) TG-DTG curves of copolymer PM-Eu-Ir

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Figure 7. Fluorescence spectra of (a) the bimetallic complex Eu(FIrPic)₂(Phen)UA, (b) phosphorescent copolymer PM-Eu-Ir and (c) the CIE chromaticity coordinates

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Figure 8. Emission images of (a) Ir complex, (b) Eu-Ir bimetallic complex powder, (c) copolymer phosphors, and (d) the red LED lamp-bead under 365 nm UV irradiation

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Figure 9. Fluorescence decay curve of the copolymer PM-Eu-Ir and Eu(FIrPic)₂(Phen)UA.

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Figure 10. (a) Electroluminescence (EL) spectra and (b) the luminance–voltage curves of the original 365 nm UV-LED chip with and without PM-Eu-Ir. The inserted photograph is the CIE chromaticity coordinates of photoluminescence

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Table 1. FT-IR characteristic peaks of the ligands, complex Eu(FIrPic)₂(Phen)UA

Complex	v_C=O(-COOH)	$\nu_{{\mathrm{as}}({\mathrm{CH}}_2)} $	$\nu_{{\mathrm{s}}({\mathrm{CH}}_2)} $	ν_C-OH	δ_C-H	ν_Eu-N	ν_C=N
FIrPic	1647,1406	-	-	-	−833,762,700	-	1477
Phen	-	-	-	-	864,739	-	1493
UA	1711	2925	2855	910	-	-	-
Eu(FIrPic)₂(Phen)UA	-	2930	2860	-	785,710	581	1414

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