【摘要】：傳統(tǒng)的微電子器件是以硅基半導(dǎo)體集成電路為主導(dǎo),而物理性能以及經(jīng)濟等因素限制了其存儲器件尺寸的繼續(xù)縮小,難以滿足未來市場的需求。由于聚合物存儲器件具有低成本、良好的加工性能、3D堆疊能力、尺寸伸縮性、可折疊以及大型數(shù)據(jù)存儲能力等優(yōu)異性能,使其成為研究的熱點。其中,功能化的聚酰亞胺憑借其耐高低溫性能、成膜性、低介電常數(shù)等一系列優(yōu)良性能在光電信息存儲方面有著重要的應(yīng)用。研究其分子結(jié)構(gòu)與存儲特性之間的相互關(guān)系已經(jīng)成為高分子材料研究領(lǐng)域的熱點之一。本文以咔唑和芴酮為原料,合成兩個系列不對稱的芳香二胺單體,并對二胺單體進(jìn)行了~1H NMR,~(13)C NMR,FT-IR和元素分析等表征。在所得二胺的基礎(chǔ)上,利用制備得到的新型芳香二胺分別與兩種芳香二酐—均苯四甲酸酐(PMDA)與2,2',3,3'-聯(lián)苯二酸酐(BPDA)進(jìn)行聚合反應(yīng),得到了兩個全新系列的聚酰亞胺材料。通過紅外光譜、元素分析等手段對所合成的聚酰亞胺的分子結(jié)構(gòu)進(jìn)行了表征;利用紫外-可見光譜、熒光光譜、TGA、循環(huán)伏安法、元素分析等測試手段對相應(yīng)聚酰亞胺材料的性能進(jìn)行了研究。采用密度泛函理論對聚酰亞胺的HOMO和LUMO軌道能級進(jìn)行計算(計算方法為gaussian 09,結(jié)構(gòu)優(yōu)化方式為wb97XD/6-31G(D,P))。將聚酰亞胺制成器件,測試其電化學(xué)性能。本論文的主要研究工作如下:1.以咔唑為原料,經(jīng)過若干步反應(yīng)成功制備出9-(2'-芳基)-3,6-二氨基咔唑,并與芳基硼酸反應(yīng),生成一系列結(jié)構(gòu)新穎的二胺單體,中間體和目標(biāo)產(chǎn)物均通過FT-IR、~1H NMR、~(13)C NMR和元素分析表征。2.以芴酮為原料,經(jīng)過溴代、親核取代等反應(yīng)制備了2-溴-9,9′-二(4-氨基苯基)芴,再經(jīng)過Suzuki偶聯(lián)反應(yīng)得到五種新型二胺單體,中間體和目標(biāo)產(chǎn)物均通過FT-IR、~1H NMR、~(13)C NMR和元素分析表征。3.設(shè)計合成出的十二種新型芳香二胺單體與實驗室現(xiàn)有的兩種芳香二酐通過“兩步法”聚合制備了新型可溶性聚酰亞胺,所得聚酰亞胺有著良好的熱穩(wěn)定性,5%質(zhì)量損失溫度大于350oC,氮氣中900oC下物質(zhì)殘存量大于35%。不對稱二胺單體的引入,溶解性能有著較大的提高。通過GPC、FT-IR和元素分析表征。4.將所合成的聚酰亞胺制備成ITO/PI/Al存儲器件,探究不同聚合物的存儲性能及其開啟閾值電壓。
[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.
【學(xué)位授予單位】：南京航空航天大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2016
【分類號】：O633.22;TP333

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本文編號：2391618