基于PVK的新型π-堆积聚合物半导体材料的合成及光电性质研究

发布时间：2018-09-07 16:03

【摘要】：聚合物半导体材料因具有可以实现低成本溶液加工的优势而推进了光电子器件的发展和商业化应用。与传统的共轭聚合物不同,π-堆积聚合物具有独特的载流子传输通道,而被应用于有机光电子领域。PVK是经典的π-堆积聚合物,具有独特的分子构象、较高的三线态能级和良好的空穴传输性能,而被广泛用作蓝色电致磷光器件的主体材料和有机存储材料。为了进一步改善材料的稳定性及拓展π-堆积聚合物的应用领域,我们在组内工作基础上,通过位阻和电子结构对PVK进行功能性修饰,设计合成了一系列基于PVK的新型π-堆积聚合物,对其热力学、光物理及电化学等性质进行了研究,并应用于蓝色磷光器件和晶体管存储器件,主要研究结果如下两大类:第一,PVK是优异的聚合物主体材料,但是由于咔唑基团3,6-位的高度活性,使其在紫外光和电场刺激下,容易发生老化降解,这可能会导致器件的本征衰减。我们采用双位阻封端策略,设计合成具哑铃型刚性PVKDPF,不仅保持高的三线态能级和合适的HOMO、LUMO能级,且大大提高了材料的热力学、光化学、电化学和形貌稳定性。应用于蓝色磷光原型器件,得到良好的器件性能,电流效率和功率效率分别达17.3 cd A-1和9.0 lm W-1。第二,PVK具有好的成膜性和宽的带隙,应用于晶体管存储器的绝缘层和半导体层之间,可显著改善界面形貌,相比无PVK修饰的器件,迁移率大大提高。但是器件的稳定性不是很好,尤其是擦除态的维持稳定性。我们将吸电子基团磷氧和氰基通过sp3杂化碳的芴基链接到PVK骨架上,设计合成了刚性p-n结构π-堆积聚合物PVKFPO、PVKFDPO和PVKDCNPPF。通过TGA、DSC、UV、PL、CV等测试研究了他们热力学、光物理和电化学等性质,应用于晶体管存储器件中,有效改善了器件的稳定性,尤其是氰基的引入,不仅显著抑制了擦除态的衰减,保持电流开关比不低于105,还可以实现双向存储及多阶存储。
[Abstract]:Polymer semiconductor materials have promoted the development and commercial application of optoelectronic devices because of their advantages of low cost solution processing. Unlike conventional conjugated polymers, 蟺-stacked polymers have unique carrier transport channels, while those used in organic optoelectronics. PVK is a classical 蟺-stacked polymer with unique molecular conformation. Because of its high three-wire energy level and good hole transport performance, it is widely used as the main material and organic storage material for blue electrophosphorescence devices. In order to further improve the stability of the materials and expand the application of 蟺-stacked polymers, we modified PVK functionally by steric resistance and electronic structure on the basis of in-group work. A series of new 蟺-stacked polymers based on PVK have been designed and synthesized. Their thermodynamics, photophysical and electrochemical properties have been studied and applied to blue phosphorescence devices and transistor memory devices. The main results are as follows: first, PVK is an excellent polymer host material. However, due to the high activity of the carbazole group at 3 ~ 6- position, it is easy to be aged and degraded under the stimulation of ultraviolet light and electric field. This may lead to intrinsic attenuation of the device. The design and synthesis of dumbbell rigid PVKDPF, with double steric blocking end strategy not only keep high three-wire energy level and appropriate HOMO,LUMO energy level, but also greatly improve the thermodynamics, photochemistry, electrochemical and morphologic stability of the materials. Good performance, current efficiency and power efficiency of 17.3 cd A-1 and 9.0 lm W-1 were obtained for blue phosphorescence prototype devices. The second PVK has good film-forming property and wide band gap. It can significantly improve the interface morphology between the insulator layer and semiconductor layer of the transistor memory. Compared with the devices without PVK modification, the mobility is greatly improved. However, the stability of the device is not very good, especially the stability of the erasure state. We designed and synthesized rigid p-n 蟺 -stacked polymers PVKFPO,PVKFDPO and PVKDCNPPF. by linking phosphoxide and cyanide groups to the framework of PVK via fluorenyl group of sp3 hybrid carbon. Their thermodynamics, photophysical and electrochemical properties have been studied by means of TGA,DSC,UV,PL,CV et al. Their application in transistor memory devices has effectively improved the stability of the devices, especially the introduction of cyanide, which not only significantly inhibits the decay of the erasure state, but also improves the stability of the devices. Holding current switch ratio is not less than 105, can also achieve two-way storage and multi-stage storage.
【学位授予单位】：南京邮电大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TN304

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