基于三键键连的萘二酰亚胺给—受体共聚物的合成及性质研究

发布时间：2018-05-23 17:43

本文选题：乙炔基 + 1　；参考：《聊城大学》2017年硕士论文

【摘要】：有机场效应晶体管(OFETs)具有柔性、质轻和可大面积制备等优点,使其在有机电子领域具有广泛的应用前景。有机半导体材料作为OFETs的活性层,起着载流子传输的作用。材料分子及分子聚集态结构决定器件的操作/空气稳定性和载流子迁移率的大小。因此,设计合成高性能的新型有机半导体材料具有重要意义。萘二酰亚胺(NDIs)是一类重要的电子受体,该类材料往往通过选择不同的给体单元,来实现对目标分子的HOMO/LUMO能级、带隙以及载流子传输特性的调控。因此本文设计合成了一系列基于萘二酰亚胺的炔烃共聚物,并研究其相关的物理化学性质以及结构与性能关系。论文主要包括以下两个部分:1.通过选择1,2,5,6-萘二酰亚胺(Iso-NDI)作为受体,设计合成了一系列基于Iso-NDI的π-共轭炔烃聚合物P1,P2和P3,其连接的单元分别为苯并噻二唑、苯和1,4-双十二烷氧链-苯。我们研究了三种聚合物的热力学、光学、电化学及载流子传输特性。研究结果表明,三种聚合物无论是在溶液状态下还是在薄膜状态下,均可观测到发射荧光现象。三种聚合物的光学带隙(2.02~2.25 eV)均小于聚乙炔的带隙(~2.5eV)。P1,P2和P3的LUMO能级相近约为-3.5 eV,P1和P3的HOMO能级相对于P2的HOMO能级分别提高了0.11和0.21 eV.我们制备了基于这三种聚合物的底栅顶接触的OFETs器件,以研究其载流子传输特性。聚合物P1和P2均表现为以电子传输为主的n-型半导体行为且电子迁移率高达10-3 cm2 v-1 s-1,聚合物P3则表现为以空穴传输为主的p-型半导体行为。聚合物P1和P2是首次报道的两例基于Iso-NDI的n-型有机半导体材料。上述结果表明,基于1,2,5,6-NDI的炔烃共聚物通过选择不同的连接单元可以调控相应的能级和载流子的传输行为。2.通过选择具有结构异构的1,4,5,8-NDI和1,2,5,6-NDI单元分别作为受体,二苯并磷杂环戊二烯类单元作为给体,合成了两种主链含磷原子的π-共轭炔烃聚合物P4和P5。我们研究了两种聚合物的物理化学性质,发现二者的光学和电化学性质有着显著的不同。两种聚合物的紫外吸收光谱呈现互补特性。无论是在溶液状态下还是薄膜状态下,P4的荧光强度比较微弱而P5的荧光强度则较强。通过双光子荧光光谱可知,P5还具有二阶非线性光学特性。我们制备了基于这两种聚合物的底栅顶接触的OFETs器件,以研究其载流子传输特性。基于P4的OFETs表现为以电子传输为主的n-型半导体行为,遗憾的是基于P5的OFETs并未检测出FET信号。
[Abstract]:With the advantages of flexibility, light weight and large area preparation, OFETs have a wide application prospect in the field of organic electronics. As the active layer of OFETs, organic semiconductors play the role of carrier transport. The structure of molecular and molecular aggregates determines the operating / air stability and carrier mobility of the device. Therefore, it is of great significance to design and synthesize new organic semiconductor materials with high performance. Naphthalenediimide (Ndis) is a kind of important electron acceptor. This kind of material can control the HOMO/LUMO energy level, band gap and carrier transport characteristics of the target molecule by selecting different donor units. In this paper, a series of naphthalenediimide based copolymers of alkynes were designed and synthesized, and their physical and chemical properties and relationship between structure and properties were studied. The thesis includes two parts as follows: 1: 1. A series of 蟺 -conjugated alkynes based on Iso-NDI have been designed and synthesized by selecting Iso-NDI as the receptor. The connecting units are benzothiadiazole, benzene and 1-didodecane oxy-benzene, respectively. We have studied the thermodynamic, optical, electrochemical and carrier transport properties of three polymers. The results show that the emission fluorescence can be observed in the solution state and the thin film state of the three polymers. The optical band gap of the three polymers (2.02 ~ 2.25 EV) is smaller than the band gap of polyacetylene (2.5 EV). The LUMO energy levels of P2 and P3 are similar to those of P3. The HOMO energy levels of P1 and P3 are increased by 0.11 and 0.21 EV, respectively, compared with the HOMO level of P2. We have fabricated the bottom gate top contact OFETs devices based on these three polymers to study their carrier transport characteristics. Both P _ 1 and P _ 2 exhibit n-type semiconductor behavior dominated by electron transport, and the electron mobility is as high as 10-3 cm2 v-1 s-1.The polymer P3 exhibits p-type semiconductor behavior dominated by hole transport. Polymers P1 and P2 are two examples of Iso-NDI-based organic semiconductor materials reported for the first time. The above results show that the alkynes copolymer based on 1H _ 2O _ 5N _ (DI) can regulate the transport behavior of the corresponding energy levels and carriers by selecting different connecting units. Two kinds of 蟺 -conjugated alkyne polymers, P4 and P5, were synthesized by selecting the structural isomerization units of 1H4 (58-NDI) and 1O2H5 (6-NDI) units as receptors and dibenzophosphorus heterocyclopentadiene units as donors, respectively. The two kinds of 蟺 -conjugated alkynes containing phosphorous atoms in the main chain, P4 and P5, were synthesized. We have studied the physical and chemical properties of the two polymers and found that their optical and electrochemical properties are significantly different. The UV absorption spectra of the two polymers are complementary. The fluorescence intensity of P4 is weaker than that of P5 in solution or thin film. The two-photon fluorescence spectra show that P5 also has second-order nonlinear optical properties. We have fabricated the bottom gate top contact OFETs devices based on these two polymers to study their carrier transport characteristics. OFETs based on P4 exhibits n- type semiconductor behavior dominated by electronic transmission. Unfortunately, OFETs based on P5 does not detect FET signals.
【学位授予单位】：聊城大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O631

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