苯并噻二唑类给受体型纳米格子的设计、合成及忆阻性能研究

发布时间：2018-03-14 15:06

本文选题：苯并噻二唑　切入点：给-受体　出处：《南京邮电大学》2017年硕士论文　论文类型：学位论文

【摘要】：有机忆阻器作为有机光电子学中新兴电子器件,被认为是模拟生物突触,实现人工智能的关键元件。然而,到目前为止,有机忆阻器的报道还很少,忆阻机制模糊不清等问题急需解决,因此,开发新型有机忆阻材料,澄清机制是当前有机忆阻器领域的核心课题。系统总结当前已报道的有机忆阻材料,我们发现有机忆阻效应的实现与活性层中电荷传输和离子迁移两个过程相关,基于此,我们借鉴有机大环分子传输离子的特性,以具有纳米孔径的芴基纳米格子分子为研究对象,引入电子受体苯并噻二唑基团调控格子分子的前线轨道和载流子传输方式,从而构筑了一系列具有离子传输通道和带隙可调的苯并噻二唑类给受体型纳米格子分子,研究其合成和忆阻性能。本论文第二章中,以“口”字形格子为框架,在芴基横梁上引入苯并噻二唑基团,调控噻吩桥的长度,设计合成了三种不同孔径的D-A型纳米格子分子(Grid-Th、Grid-DTh、Grid-TTh),考察D-A型纳米格子的π-桥效应,随着π-桥长度的增加,“口”字形纳米格子的合成产率增加,结构刚性减弱,荧光量子产率降低,Grid-TTh相对于Grid-Th和Grid-DTh具有较高的HOMO和LUMO能级。基于Grid-DTh掺杂四丁基六氟磷酸铵作为活性层的两端型二极管器件展现出电压依赖的忆阻特性,成功地模拟了突触的“兴奋”和“抑制”功能,这为设计格子半导体应用于有机忆阻器提供了实验基础。第三章在高产率互握式纳米格子分子的横梁(crossbeam)中分别引入苯并噻二唑和苯基基团,成功制备了苯并噻二唑基纳米格子(Grid-BT-Cz)与苯基纳米格子(Grid-Ph-Cz)。互握式纳米格子的横梁效应在能带结构和光学性能被观察到,Grid-BT-Cz相对于Grid-Ph-Cz具有更低的带隙和更小的异构体光谱差异性。以互握式纳米格子(Grid-BT-CzGrid-Ph-Cz)为活性层的两端型二极管器件展现出类似忆阻I-V特性的阻变性能。以掺杂型互握式纳米格子(Grid-BT-Cz/Bu4NPF6Grid-Ph-Cz/Bu4NPF6)为活性层的两端型二极管器件显示出电压依赖的忆阻特性。第四章以三苯胺为π电子桥,合成了可扩展的BT类“口”字形纳米格子分子,并通过Stille聚合反应构建了D-A型纳米聚合物。紫外-可见吸收光谱测试和电化学测试表明P(Grid-TPA-DPP)具有三个特征吸收峰的窄带隙纳米聚合物(Eg opt=1.41 eV)。以P(Grid-TPA-DPP)为活性层的两端型器件展现出符合忆阻特性的I-V曲线。苯并噻二唑类D-A型纳米格子/纳米聚合物的构建以及基此的有机二极管器件I-V特性的研究验证为开发新型有机忆阻材料提供了理论和实验基础。
[Abstract]:Organic amnesia, as an emerging electronic device in organic optoelectronics, is considered to be a key element in simulating biological synapses and realizing artificial intelligence. However, so far, there have been few reports of organic memory devices. Therefore, the development of new organic memory materials and the clarification mechanism are the core issues in the field of organic memory devices. We found that the realization of organic memory effect is related to charge transport and ion migration in the active layer. Based on this, we learn from the characteristics of organic macromolecular ion transport. The forward orbital and carrier transport modes of the lattice molecules were regulated by the introduction of benzothiadiazole groups, which were based on the fluorescein nanolattice molecules with nano-pore size, and the electron receptors were introduced to regulate the frontier orbital and carrier transport modes of the lattice molecules. Therefore, a series of benzothiadiazoles with ion transport channels and bandgap tunable have been constructed, and their synthesis and memory properties have been studied. In the second chapter of this thesis, the "mouth" lattice is used as the framework. Benzothiadiazole group was introduced into the fluorene beam to regulate the length of thiophene bridge. Three kinds of D-A nanolattice molecules with different pore sizes were designed and synthesized, and the 蟺 -bridge effect of D-A nanolattice was investigated. With the increase of 蟺 -bridge length, the synthetic yield of "mouth" shaped nano-lattice increases and the structural rigidity decreases. Grid-TTh has higher HOMO and LUMO energy levels than Grid-Th and Grid-DTh. Based on Grid-DTh doped with tetra#china_person0# ammonium hexafluorophosphate as a two-end diode device with active layer, it exhibits voltage-dependent amnesia characteristics. Successfully mimicking synaptic "excitatory" and "inhibitory" functions, In chapter 3, benzothiadiazole and phenyl groups were introduced into the crossbeam crossbeam crossbeam of high yield and mutual gripping nanolattice molecules, respectively. Benzothiadiazolyl nano-lattice Grid-BT-Cz) and phenyl nano-lattice Grid-Ph-Czng were successfully prepared. The cross beam effect of the intergripping nanogold was observed to have lower band gap and smaller isomer light than that of Grid-Ph-Cz in the energy band structure and optical properties. Spectral differences. Two-end diode devices with a grid-BT-CzGrid-Ph-Cz-Czech as the active layer exhibit resistive properties similar to those of amnesia I-V. Two-end diodes with doped intergripping nano-lattices Grid-BCz-Bu4NPF6Grid-Ph-Cz-Cz4NPF6 are used as active layers. Voltage-dependent amnesia characteristics. Chapter 4th, with Trianiline as a 蟺 electron bridge, An extensible BT "mouth" shaped nano-lattice molecule was synthesized. D-A type nanopolymers were constructed by Stille polymerization. UV-Vis absorption spectra and electrochemical measurements showed that there were three characteristic absorption peaks in the narrow band gap nano-polymer, Eg opt=1.41 EV, and the two ends of the active layer were composed of Pen Grid-TPA-DPP. The devices exhibit I-V curves consistent with the amnesia characteristics. The construction of benzothiadiazole D-A nanolattices / nanopolymers and the study of I-V characteristics of organic diode devices based on these materials provide a basis for the development of novel organic memory materials. The theoretical and experimental basis are given.
【学位授予单位】：南京邮电大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TB383.1;O633.5

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