Santos Daniela Corrêa, Barros Gabriel de Sousa, Marques Maria de Fátima Vieira
Instituto de Macromoléculas Professora Eloisa Mano, Universidade Federal do Rio de Janeiro (IMA/UFRJ), Rio de Janeiro, Rio de Janeiro 21941-598, Brazil.
ACS Omega. 2025 Aug 21;10(34):39250-39262. doi: 10.1021/acsomega.5c06357. eCollection 2025 Sep 2.
This study reports the synthesis and functionalization of poly-(-vinylcarbazole) (PVK) with anthracene units to enhance its blue photoluminescence properties. Structural and thermal analyses confirmed successful incorporation of anthracene moieties into the PVK backbone at an approximate 3:1 ratio of PVK repeat unit to anthracene. Photophysical characterization showed that anthracene-functionalized PVK (PVK-An) retained blue-region emission (432 nm), although with reduced emission efficiency due to π-π stacking interactions. Incorporating PVK-An into an inert poly-(methyl methacrylate) (PMMA) matrix mitigated aggregation-caused quenching (ACQ), increasing the photoluminescence quantum yield (PLQY) from 0.5% to 28.9% in the optimized 70:30 wt % PMMA/PVK-An blend. Time-resolved photoluminescence (TRPL) analysis revealed that the emission in both neat PVK and PVK-An arises from two decay pathways, S → S and S* → S, corresponding to singlet excimer states emissions, respectively. Notably, PVK-An exhibited reduced excimer formation, as indicated by shorter fluorescence lifetimes (τ ≈ 5 ns) and a lower contribution from the longer decay component (τ ≈ 15 ns, Rel. 54.80%) compared to pristine PVK (τ ≈ 25 ns, Rel. 74.33%). These findings demonstrate the synergistic benefits of side-chain engineering and morphological control in the design of high-performance blue-emitting polymers for OLED applications.
本研究报道了带有蒽单元的聚(-乙烯基咔唑)(PVK)的合成与功能化,以增强其蓝光光致发光性能。结构和热分析证实,蒽部分以大约3:1的PVK重复单元与蒽的比例成功并入PVK主链。光物理表征表明,蒽功能化的PVK(PVK-An)保留了蓝光区域发射(432 nm),尽管由于π-π堆积相互作用发射效率降低。将PVK-An掺入惰性聚(甲基丙烯酸甲酯)(PMMA)基质中可减轻聚集诱导猝灭(ACQ),在优化的70:30 wt% PMMA/PVK-An共混物中,光致发光量子产率(PLQY)从0.5%提高到28.9%。时间分辨光致发光(TRPL)分析表明,纯PVK和PVK-An中的发射均来自两条衰减途径,S→S和S*→S,分别对应于单线态激基缔合物态发射。值得注意的是,与原始PVK(τ≈25 ns,相对含量74.33%)相比,PVK-An表现出激基缔合物形成减少,表现为荧光寿命更短(τ≈5 ns),且较长衰减成分(τ≈15 ns,相对含量54.80%)的贡献更低。这些发现证明了在用于OLED应用的高性能蓝光发射聚合物设计中,侧链工程和形态控制的协同优势。