基于不对称芳香二胺的新型可溶性聚酰亚胺的制备及其存储性能研究
发布时间：2018-12-25 20:39
【摘要】：传统的微电子器件是以硅基半导体集成电路为主导,而物理性能以及经济等因素限制了其存储器件尺寸的继续缩小,难以满足未来市场的需求。由于聚合物存储器件具有低成本、良好的加工性能、3D堆叠能力、尺寸伸缩性、可折叠以及大型数据存储能力等优异性能,使其成为研究的热点。其中,功能化的聚酰亚胺凭借其耐高低温性能、成膜性、低介电常数等一系列优良性能在光电信息存储方面有着重要的应用。研究其分子结构与存储特性之间的相互关系已经成为高分子材料研究领域的热点之一。本文以咔唑和芴酮为原料,合成两个系列不对称的芳香二胺单体,并对二胺单体进行了~1H NMR,~(13)C NMR,FT-IR和元素分析等表征。在所得二胺的基础上,利用制备得到的新型芳香二胺分别与两种芳香二酐—均苯四甲酸酐(PMDA)与2,2',3,3'-联苯二酸酐(BPDA)进行聚合反应,得到了两个全新系列的聚酰亚胺材料。通过红外光谱、元素分析等手段对所合成的聚酰亚胺的分子结构进行了表征;利用紫外-可见光谱、荧光光谱、TGA、循环伏安法、元素分析等测试手段对相应聚酰亚胺材料的性能进行了研究。采用密度泛函理论对聚酰亚胺的HOMO和LUMO轨道能级进行计算(计算方法为gaussian 09,结构优化方式为wb97XD/6-31G(D,P))。将聚酰亚胺制成器件,测试其电化学性能。本论文的主要研究工作如下:1.以咔唑为原料,经过若干步反应成功制备出9-(2'-芳基)-3,6-二氨基咔唑,并与芳基硼酸反应,生成一系列结构新颖的二胺单体,中间体和目标产物均通过FT-IR、~1H NMR、~(13)C NMR和元素分析表征。2.以芴酮为原料,经过溴代、亲核取代等反应制备了2-溴-9,9′-二(4-氨基苯基)芴,再经过Suzuki偶联反应得到五种新型二胺单体,中间体和目标产物均通过FT-IR、~1H NMR、~(13)C NMR和元素分析表征。3.设计合成出的十二种新型芳香二胺单体与实验室现有的两种芳香二酐通过“两步法”聚合制备了新型可溶性聚酰亚胺,所得聚酰亚胺有着良好的热稳定性,5%质量损失温度大于350oC,氮气中900oC下物质残存量大于35%。不对称二胺单体的引入,溶解性能有着较大的提高。通过GPC、FT-IR和元素分析表征。4.将所合成的聚酰亚胺制备成ITO/PI/Al存储器件,探究不同聚合物的存储性能及其开启阈值电压。
[Abstract]:Traditional microelectronic devices are dominated by silicon based semiconductor integrated circuits, but physical properties and economic factors limit the continuous reduction of memory device size, which is difficult to meet the future market demand. Because of its low cost, good processing performance, 3D stacking ability, dimensional scalability, collapsible and large data storage ability, polymer memory has become a hot research topic. Among them, functionalized polyimide has important applications in optoelectronic information storage by virtue of its high and low temperature resistance, film forming, low dielectric constant and so on. The study of the relationship between molecular structure and storage properties has become one of the hotspots in the field of polymer materials. Two series of asymmetric aromatic diamine monomers were synthesized from carbazole and fluorenone and characterized by ~ 1H NMR,~ (13) C NMR,FT-IR and elemental analysis. Based on the obtained diamines, the novel aromatic diamines were polymerized with two kinds of aromatic dianhydride (PMDA) and two kinds of aromatic dianhydride (BPDA), respectively. Two new series of polyimide materials were obtained. The molecular structure of the synthesized polyimide was characterized by IR and elemental analysis. The properties of the polyimide materials were studied by UV-Vis spectra, fluorescence spectra, TGA, cyclic voltammetry and elemental analysis. The energy levels of HOMO and LUMO orbitals of polyimide were calculated by density functional theory (gaussian 0 9) and the structure was optimized by wb97XD/6-31G (DDP). Polyimide was made into a device and its electrochemical performance was tested. The main work of this thesis is as follows: 1. A series of novel diamine monomers were synthesized from carbazole by several steps of reaction, and a series of novel diamine monomers were synthesized by reaction with aryl boric acid. The intermediate and the target product were all passed through FT-IR,. ~ 1H NMR,~ (13) C NMR and elemental analysis). 2-bromo-9- (4-aminophenyl) fluorene was synthesized from fluorenone by bromination and nucleophilic substitution reaction. Five new diamine monomers were obtained by Suzuki coupling reaction. The intermediate and the target product were all passed through FT-IR,~1H NMR,. ~ (13) C NMR and elemental analysis. Twelve new aromatic diamine monomers were designed and synthesized, and two kinds of aromatic dianhydride in laboratory were polymerized to prepare new soluble polyimide by "two-step" polymerization. The obtained polyimide has good thermal stability. The mass loss temperature of 5% is more than 350 OC, and the residual amount of 900oC in nitrogen is more than 35%. With the introduction of asymmetric diamine monomer, the solubility has been greatly improved. Characterized by GPC,FT-IR and elemental analysis. 4. The synthesized polyimides were fabricated into ITO/PI/Al memory devices to investigate the storage performance and threshold voltage of different polymers.
【学位授予单位】：南京航空航天大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O633.22;TP333
本文编号：2391618
[Abstract]:Traditional microelectronic devices are dominated by silicon based semiconductor integrated circuits, but physical properties and economic factors limit the continuous reduction of memory device size, which is difficult to meet the future market demand. Because of its low cost, good processing performance, 3D stacking ability, dimensional scalability, collapsible and large data storage ability, polymer memory has become a hot research topic. Among them, functionalized polyimide has important applications in optoelectronic information storage by virtue of its high and low temperature resistance, film forming, low dielectric constant and so on. The study of the relationship between molecular structure and storage properties has become one of the hotspots in the field of polymer materials. Two series of asymmetric aromatic diamine monomers were synthesized from carbazole and fluorenone and characterized by ~ 1H NMR,~ (13) C NMR,FT-IR and elemental analysis. Based on the obtained diamines, the novel aromatic diamines were polymerized with two kinds of aromatic dianhydride (PMDA) and two kinds of aromatic dianhydride (BPDA), respectively. Two new series of polyimide materials were obtained. The molecular structure of the synthesized polyimide was characterized by IR and elemental analysis. The properties of the polyimide materials were studied by UV-Vis spectra, fluorescence spectra, TGA, cyclic voltammetry and elemental analysis. The energy levels of HOMO and LUMO orbitals of polyimide were calculated by density functional theory (gaussian 0 9) and the structure was optimized by wb97XD/6-31G (DDP). Polyimide was made into a device and its electrochemical performance was tested. The main work of this thesis is as follows: 1. A series of novel diamine monomers were synthesized from carbazole by several steps of reaction, and a series of novel diamine monomers were synthesized by reaction with aryl boric acid. The intermediate and the target product were all passed through FT-IR,. ~ 1H NMR,~ (13) C NMR and elemental analysis). 2-bromo-9- (4-aminophenyl) fluorene was synthesized from fluorenone by bromination and nucleophilic substitution reaction. Five new diamine monomers were obtained by Suzuki coupling reaction. The intermediate and the target product were all passed through FT-IR,~1H NMR,. ~ (13) C NMR and elemental analysis. Twelve new aromatic diamine monomers were designed and synthesized, and two kinds of aromatic dianhydride in laboratory were polymerized to prepare new soluble polyimide by "two-step" polymerization. The obtained polyimide has good thermal stability. The mass loss temperature of 5% is more than 350 OC, and the residual amount of 900oC in nitrogen is more than 35%. With the introduction of asymmetric diamine monomer, the solubility has been greatly improved. Characterized by GPC,FT-IR and elemental analysis. 4. The synthesized polyimides were fabricated into ITO/PI/Al memory devices to investigate the storage performance and threshold voltage of different polymers.
【学位授予单位】：南京航空航天大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O633.22;TP333
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