Fluorene-based Functionalized D-A Stretchable Electroluminescent Polymers and Their Light-emitting Diodes

doi:10.6023/A25060214

Abstract

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

Cite this article

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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Fig. & Tab. 10

Figure 1. Synthesis steps of PAC1~PAC4

Figure 2. Infrared spectra of PAC1~PAC4

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

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

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)

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

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

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)

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

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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