面向光电子器件的功能化侧链盘状液晶聚合物分子工程

Under the guidance of positive coupling effect, the system molecular engineering of functionalized side-chain discotic liquid crystalline polymers will be systematically carried out with the performance orientation of thus prepared optoelectronic devices. With the introduction of p-type porphyrin and n-type perylene diimide discotic mesogen side groups through shorter spacers, novel side-chain discotic liquid crystalline polymers with polyacrylate, polynorbornene or polyoxyethylene ether as the main chain, respectively, will be controllably synthesized via RAFT polymerization, ring-opening metathesis polymerization (ROMP) or ring-opening anionic polymerization. The stereoregular side-chain polymers substituted with high-density discotic mesogens are going to be synthesized via rhodium-catalyzed carbenes. Then the functionalized system terminated with C60 and the block copolymers with p-type and n-type discotic side groups will also be prepared. The phase behavior, columnar stacking order, orientation characteristic and thin film morphology of the synthesized semiconducting polymers will be systematically studied by employing advanced characterization techniques such as POM, DSC, variable temperature SAXS/WAXS, AFM and TEM. And the carrier mobility will be investigated by TOF. The large-scale synthesis of preferred semiconducting polymers will be purified according to electronical grade requirements, and mainly OPV/PSC and OFET thin film optoelectronic devices will be fabricated and in-depth investigated. The project will provide a possible solution and a reference basis for the rational design and controllable synthesis of organic polymer semiconducting electronic materials and the optoelectronic devices application based on a liquid crystalline polymer route different from the usual heteroatom-containing conjugated polymers.

在正耦合效应指引下，以光电子器件性能导向，开展功能化侧链盘状液晶聚合物的系统分子工程。以较短的间隔基引入p-型卟啉和n-型苝二酰亚胺盘状侧基，经由RAFT聚合、ROMP开环易位聚合、开环阴离子聚合可控合成分别以聚丙烯酸酯、聚降冰片烯、聚氧乙烯醚为主链的新颖侧链盘状液晶聚合物，以及通过铑催化卡宾合成高取代侧基密度的立构规整聚合物。进一步制备了端接C60的功能化体系以及p-型和n-型盘状侧基的嵌段共聚物。利用POM、DSC、变温SAXS/WAXS、AFM及TEM等多种先进分析技术，对合成聚合物的液晶相行为、柱状堆积有序性、取向特性、薄膜形貌等进行深入系统研究，以及TOF测试载流子迁移率。放量合成优选的聚合物经电子级深度纯化，开展OPV/PSC以及OFET光电子器件加工制作与性能研究。为推进有机聚合物半导体电子材料的理性设计和可控合成及光电子器件应用提供液晶聚合物途径的可能解决方案和参考依据。

我们紧密围绕项目提出的目标任务，在采用多种可控合成方法的侧链液晶聚合物的设计合成，基于p-型苯并菲(TP)和n-型苝二酰亚胺等多种不同侧基的聚合物体系以及引入C60的功能化体系与嵌段共聚物制备等都开展了系统的探索，利用DSC、POM、变温SAXS/WAXS、TEM、SEM以及AFM等多种先进分析技术，对其液晶相行为、柱状堆积有序性、取向特性、薄膜形貌等开展了较为深入系统的研究，以及采用飞行时间谱(TOF)技术测试电子/空穴载流子迁移率和带热台的电化学工作站交流阻抗模式测试其各向异性离子电导率。通过超分子组装策略以及微分相调控，制备了基于苯并菲TP盘状液晶基元的两类“双缆型”双极性载流子传导的功能有机电子材料, 可形成多层级有序柱状相结构，表现出良好的光电性能。采用铑催化卡宾聚合制备的基于TP液晶基元的高侧基取代密度高立构规整C1型侧链盘状液晶聚合物，表现出比通常C2型聚合物高出40K以上更宽温区范围的有序柱状液晶相，为设计制备高取代密度侧链液晶聚合物有机半导体材料提供了新的思路。可控合成含偶氮苯(Azo)的侧链液晶聚合物光响应材料，以及采用可控自由基聚合结合点击化学偶联策略设计制备了基于侧挂TP盘状液晶基元和Azo棒状液晶基元的嵌段共聚物。还开展了基于可逆动态共价键体系的液晶弹性体LCEs纳米复合材料的可重新赋形的光/热驱动的多种模式的驱动器制备。进一步开展了侧链盘状液晶聚合物的基于粗粒化模型的耗散粒子动力学(DPD)理论模拟合作研究。该项目研究进展及取得的成果为推进有机聚合物半导体电子材料的理性设计和可控合成及光电子器件应用提供参考依据。