A red-emitting copolymer phosphors based on bimetallic Eu-Ir complex for Near-UV chip-based LEDs
doi:10.37188/CO.EN-2023-0023
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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。
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/m2luminance. The results support the potential utilization of prepared copolymer phosphor as a red component in the fabrication of near UV chip-based white LEDs.
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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
Figure 5.FE-SEM images of the bimetallic complex Eu(FIrPic)2(Phen)UA (a) and phosphorescent copolymer PM-Eu-Ir (b)
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
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
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
Table 1.FT-IR characteristic peaks of the ligands, complex Eu(FIrPic)2(Phen)UA
Complex vC=O(-COOH) $\nu_{{\mathrm{as}}({\mathrm{CH}}_2)} $ $\nu_{{\mathrm{s}}({\mathrm{CH}}_2)} $ νC-OH δC-H νEu-N νC=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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