芴基功能化D-A型可拉伸电致发光聚合物及其发光二极管

doi:10.6023/A25060214

摘要/Abstract

可拉伸有机发光二极管(OLEDs)凭借高机械应变性、可调光电特性和生物相容性等优势, 在可穿戴电子、生物医疗监测与智能显示领域展现出广阔应用潜力. 开发兼具优异力学性能和光电特性的本征可拉伸电致发光聚合物对高效可拉伸OLEDs开发具有重要意义. 本研究利用不同分子量的聚(四氢呋喃)(PTMEG)软段与芴基功能化给体-受体(D-A)型发光体进行聚合, 制备出系列新型可拉伸电致发光聚合物PAC1~PAC4. 其中, 基于高分子量PTMEG的PAC3和PAC4聚合物表现出较低的弹性模量以及优异的伸长率, 其弹性模量最低仅为0.85 MPa、韧性约为1.97 MJ•m⁻³、拉伸伸长率可达2700%. 基于PAC3和PAC4聚合物的器件均呈现绿光发射, 其CIE坐标分别为(0.27, 0.48)和(0.29, 0.54). 本工作为高拉伸性发光聚合物的构筑提供了一种简易可行的设计思路.

关键词: 可拉伸有机发光二极管, 电致发光聚合物, 芴基功能化, 给体-受体(D-A)型发光体

Stretchable organic light-emitting diodes (OLEDs), due to their excellent mechanical strain properties, tunable optoelectronic properties, and good biocompatibility, show irreplaceable application prospects in cutting-edge fields such as wearable electronic devices, biomedical real-time monitoring systems, and flexible smart displays. The development of intrinsically stretchable electroluminescent polymers with excellent mechanical and optoelectronic properties is important for the development of highly efficient stretchable OLEDs. In this study, a series of novel stretchable electroluminescent polymers PAC1~PAC4 were synthesized through simple molecular design. These polymers incorporate poly(tetrahydrofuran) (PTMEG) soft segments of varying molecular weights and are polymerized with functionalized donor-acceptor (D-A) emitters. In this system, fluorenyl-functionalized carbazole serves as the electron donor, while the phenolic hydroxyl group formed by demethylation is introduced into PTMEG (terminated with isocyanate groups of different molecular weights), enabling its application in OLEDs. PTMEGs of different molecular weights were introduced through demethylation, thus realizing the modulation of stretchable properties. At the same time, long-chain alkyl-functionalized phthalimide is used as the electron acceptor, and the stretchable property of the polymer is enhanced by introducing long-chain alkyl groups. Among them, the PAC3 and PAC4 polymers based on high molecular weight PTMEG exhibited low elastic modulus as well as excellent elongation, with elastic modulus as low as 0.85 MPa, toughness of about 1.97 MJ•m⁻³, and tensile elongation up to 2700%. The devices based on PAC3 and PAC4 polymers both exhibit green light emission with CIE coordinates of (0.27, 0.48) and (0.29, 0.54), respectively. The devices prepared on the basis of 0.3DT (DMeOPFDMACTRZ)＋PAC3 and 0.3DT＋PAC4 have good spectral stability, which lays the groundwork for their application in optoelectronic devices. In this study, the synergistic optimization of the mechanical properties and optoelectronic characteristics of polymers was achieved through simple molecular structure modulation, which provides a practical new idea for the design and preparation of high-performance stretchable light-emitting materials and is expected to promote the further development of stretchable OLEDs in the field of flexible electronics

Key words: stretchable organic light-emitting diode, electroluminescent polymers, fluorenyl-functionalization, donor-acceptor luminophores

引用此文

朱韵飞, 郭可威, 王子路, 李昊, 朱爱云, 马靖尧, 祝守加, 冯全友, 解令海. 芴基功能化D-A型可拉伸电致发光聚合物及其发光二极管[J]. 化学学报, 2025, 83(11): 1300-1308.

Zhu Yunfei, Guo Kewei, Wang Zilu, Li Hao, Zhu Aiyun, Ma Jingyao, ZhuShoujia, Feng Quanyou, Xie Linghai. Fluorene-based Functionalized D-A Stretchable Electroluminescent Polymers and Their Light-emitting Diodes[J]. Acta Chimica Sinica, 2025, 83(11): 1300-1308.

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图/表 10

图1. PAC1~PAC4的合成路线

Figure 1. Synthesis steps of PAC1~PAC4

图2. PAC1~PAC4的红外谱图

Figure 2. Infrared spectra of PAC1~PAC4

图3. PAC1~PAC4在薄膜状态下(a)和甲苯稀溶液中(b) UV-PL光谱

Figure 3. UV-PL spectra of PAC1~PAC4 in thin films status (a) and in dilute toluene solution (b)

图4. (a) PAC3在甲苯溶液中、掺杂30% (w) mCP和掺杂30% (w) DPEPO主体材料的溶液的瞬态荧光衰减曲线; (b) PAC3的薄膜、掺杂30% (w) mCP主体材料的薄膜和掺杂30% (w) DPEPO主体材料的薄膜的瞬态荧光衰减曲线; (c) DMeOPFCZAI16C在甲苯溶液和掺杂30% (w) DPEPO主体材料的溶液的瞬态荧光衰减曲线; (d) DMeOPFCZAI16C的薄膜与掺杂30% (w) DPEPO主体材料的薄膜的瞬态荧光衰减曲线

Figure 4. (a) Delayed fluorescence lifetime decay curves of PAC3 in toluene solution, solution doped with 30% (w) mCP and doped with 30% (w) DPEPO host material; (b) Delayed fluorescence lifetime decay curves of thin films of PAC3, thin films doped with 30% (w) mCP host material and thin films doped with 30% (w) DPEPO host material; (c) Delayed fluorescence lifetime decay curves of DMeOPFCZAI16C in toluene solution and solution doped with 30% (w) DPEPO host material; (d) Delayed fluorescence lifetime decay curves of thin films of DMeOPFCZAI16C and thin films doped with 30% (w) DPEPO host material

图5. PAC2 (a)、PAC3 (b)、PAC4 (c)的自支撑弹性体的拉伸应力-应变曲线比较以及弹性体PAC3、PAC4拉伸前后的照片(d, e)

Figure 5. Comparison of tensile stress-strain curves of self-supporting elastomers of PAC2 (a), PAC3 (b), and PAC4 (c) and before and after tensile photographs of elastomers PAC3 and PAC4 (d, e)

图6. PAC1~PAC4的剪切应力变化曲线和黏度变化曲线

Figure 6. Shear stress change curves and viscosity change curves of PAC1~PAC4

图7. (a) 0.3DT＋PAC1, (b) 0.3DT＋PAC2, (c) 0.3DT＋PAC3和(d) 0.3DT＋PAC4的原子力显微镜(AFM)

Figure 7. Atomic force microscopy (AFM) of (a) 0.3DT＋PAC1, (b) 0.3DT＋PAC2, (c) 0.3DT＋PAC3 and (d) 0.3DT＋PAC4

图8. (a)基于PAC1~PAC4掺杂30% DMeOPFDMACTRZ的OLED的配置结构; (b)基于系列发光材料的OLED的电压亮度特性; (c)施加电压为8 V的基于系列发光材料的OLED器件的EL光谱; (d)基于系列发光材料的OLED的电压电流密度特性; (e)基于系列发光材料的外量子效率(EQE); (f)基于系列发光材料的OLED的CIE

Figure 8. (a) Configuration structure of OLED based on PAC1~PAC4 doped 30% DMeOPFDMACTRZ; (b) Voltage brightness characteristics of series-emitting material-based OLED; (c) EL spectra of series-emitting material-based OLED devices with an applied voltage of 8 V; (d) Voltage-current density characteristics of series-emitting material-based OLEDs; (e) External quantum efficiency (EQE) of series-emitting material-based OLEDs; (f) CIE of series-emitting material-based OLEDs

Compound	V_on/V	λ_EL/nm	L_max/(cd•m⁻²)	EQE_max/%	CIE
0.3DT＋PAC1	4.9	508	1276.9	0.35	(0.27, 0.52)
0.3DT＋PAC2	4.9	512	295.2	0.33	(0.26, 0.46)
0.3DT＋PAC3	4.9	512	361.4	0.08	(0.27, 0.48)
0.3DT＋PAC4	4.9	516	140.2	0.02	(0.29, 0.54)

表1. 0.3DT＋PAC1~PAC4的器件性能参数

Table 1. Device performance parameters for 0.3DT＋PAC1~PAC4

图9. 基于(a) 0.3DT＋PAC1, (b) 0.3DT＋PAC2, (c) 0.3DT＋PAC3和(d) 0.3DT＋PAC4的OLED在不同电压下的EL光谱

Figure 9. EL spectra of OLEDs based on (a) 0.3DT＋PAC1, (b) 0.3DT＋PAC2, (c) 0.3DT＋PAC3 and (d) 0.3DT＋PAC4 at different voltages

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