电活性聚酰亚胺的制备及其电双稳态信息存储行为的表征和机理研究
发布时间：2018-07-16 20:56
【摘要】：信息时代数据总量的爆炸式增长,要求新型的存储材料及元件具有超高的存储密度、超快的读写和响应速度、低的启动电压以及低成本易加工等优点。传统的半导体存储技术以硅和锗为主要原料,但是在器件的线宽和存储点的大小上已经接近上限,难以满足新时代的要求。而新开发的聚合物基信息存储材料,由于其柔性、低成本、易加工,超大容量,超低能耗及可通过分子剪裁实现性能调控等优点而成为研究的热点。考虑到存储器件在使用中的发热问题和对机械性能的要求,具有优异的热稳定性、化学稳定性和尺寸稳定性的聚酰亚胺成为重点研究的对象。对于聚酰亚胺基信息存储材料,近年的研究热点主要在于设计合成分子链中同时具有电子给体和电子受体的新型聚酰亚胺,以利于施加电压后发生微观上的电子给受体间的电荷转移和宏观上的电双稳态现象。到目前为止,学者们已经合成出多种具有不同化学结构的聚酰亚胺并获得了不同的存储性能,如易失的动态随机存储(DRAM)和静态随机存储(SRAM),以及非易失的一次写入多次读取(WORM)和闪存型(Flash)存储性能。但是,多种影响因素的存在,如分子轨道能级、前线轨道能级差、分子空间构型、电子给受体的给电子和吸电子能力、电荷捕捉位点的空间分布及捕获电荷的能力、活性层厚度、材料表面形貌以及电极种类等,导致聚酰亚胺基存储器件内部的存储机理十分复杂。因此,虽然该领域已经出现较多的研究成果,但是仍然需要更加深入的研究和详尽的分析。其中尤其重要的是,如何探索聚酰亚胺分子结构和存储性能的关系以实现对存储行为的调控,并分析材料内部的存储机理。在本文中,我们设计合成了三个系列的新型电活性聚酰亚胺,研究了其信息存储性能,并结合其光物理性能、电化学性能和分子模拟的结果,分别研究了电子给体的给电子能力、分子链中给受体的空间结构、电荷捕捉位点的深度以及给受体空间分布对存储性能和存储机理的影响。本论文的主要研究内容和成果如下:(1)合成了含有给电子基团-芘-的新型二胺DAPAP (N,N-二(4-氨基)苯基-1-芘胺),并将之与BAPF(9,9'-对(4-氨基)苯基芴)和DSDA(3,3',4,4'-二苯砜四酸二酐)共聚,通过调节DAPAP和BAPF的比例,制备了一系列新型功能化共聚聚酰亚胺(coPI-DAPAPx,x=100, 50, 20, 10, 5, 1, 0,其中x代表DAPAP占总的二胺单体的摩尔比例)。产物表现出良好的溶解性和优异的热稳定性。通过旋转涂膜和真空蒸镀制备了具有ITO/聚酰亚胺/Au结构的存储器件,并对其存储性能进行研究。结果表明,DAPAP在该系列共聚型聚酰亚胺中作为主要的电子给体。随着DAPAP含量的降低,对应的聚酰亚胺的存储特性由非易失向易失型转变。DAPAP含量为100%、50%、20%和10%的聚酰亚胺表现出非易失的WORM型存储特性,而DAPAP含量为5%和1%的聚酰亚胺表现出易失的SRAM型存储特性。DAPAP含量为0%的聚酰亚胺不具有双稳态存储性能。对表征结果和分子模拟结果进行分析后认为,随着DAPAP含量的降低,聚酰亚胺分子的HOMO (最高已占据轨道)轨道能级和Eg(前线轨道能级差)降低,导致施加电压后聚酰亚胺分子中形成的电荷转移络合物稳定性降低,因而出现非易失到易失型存储性能的转变。(2)合成了三种含电子给体-蒽-的新型二胺,1-DAPAA (N,N-二(4-氨基)苯基-1 -蒽胺)、2-DAPAA(N,N-二(4-氨基)苯基-2-蒽胺)和 9-DAPAA (N,N-二(4-氨基)苯基-9-蒽胺),将其与6FDA (4,4'-(六氟异丙基)二酞酸酐)聚合,采用两步法合成了三种含有相似电子给体的电活性聚酰亚胺,1-DAPAA-6FDA、2-DAPAA-6FDA 和 9-DAPAA-6FDA。三种聚酰亚胺的唯一区别在于,蒽作为侧基,和聚酰亚胺主链相连接的位点不同(1-,2-,9-)。半导体分析结果表明,1-DAPAA-6FDA和9-DAPAA-6FDA具有非易失的WORM型存储行为,而2-DAPAA-6FDA表现出易失的SRAM型存储行为。分子模拟结果表明,三种二胺具有相似的给电子能力,Mulliken电荷分布结果也证明,三种聚酰亚胺中从基态到激发态发生电荷转移的电量几乎相同,因而排除了电子效应对存储性能造成的影响。空间结构分析表明,上述的不同连接位点导致蒽基所在平面和主链间二面角(θ1)大小的不同,其中2-DAPAA-6FDA中的θ1最小,整个分子的平面性相对更好,利于电荷转移和反向的电荷传输,因而表现出易失的SRAM型存储性能。而1-D APAA-6FDA和9-DAPAA-6FD A因为蒽基和主链间较大的二面角不利于电荷转移,而呈现出非易失的WORM型存储性能。(3)合成了两种新型的含不同长度非共轭脂肪链结构的二胺,DATP6Cz(N,N-二(4-氨基)苯基-6-(9-咔唑基)己胺)和DATP2Cz (N,N-二(4-氨基)苯基-2-(9-咔唑基)乙胺),并采用二步法,将其分别与两种二酐,DSDA和NTDA (1,4,5,8-萘四甲酸二酐)缩聚,得到四种不同的聚酰亚胺,DATP6Cz-DSDA,DATP6Cz-NTDA,DATP2Cz-DSDA,DATP2Cz-NTDA。咔唑和聚酰亚胺主链之间亚乙基和亚己基的引入,成功改变了电子给体和分子链间的相对空间位置。半导体分析结果表明,含DSDA的两种聚酰亚胺,DATP6Cz-DSDA和DATP2Cz-DSDA均呈现出非易失的WORM型存储行为,而含NTDA的两种聚酰亚胺,DATP6Cz-NTDA和DATP2Cz-NTDA分别呈现出易失的SRAM和DRAM型存储行为。分子模拟结果表明,相比于NTDA中的羰基,DSDA中的砜基具有更强的电荷捕获能力,且捕获电荷之后形成的缔合物不易解离,而NTDA捕获电荷后形成的缔合物容易解离,因而含DSDA和NTDA的聚酰亚胺分别呈现出非易失和易失的存储性能。而不同长度的非共轭脂肪链导致解离过程中电荷从受体到给体之间的传输过程不同,要克服的能垒也不同,因而宏观上表现出不同的保留时间,并分别呈现出SRAM和DRAM的存储行为。综上所述,本论文的设计思路及研究结果证明,通过分子模拟手段对电子给受体的结构进行有目的的设计和调节,以调整电子给体的给电子能力、分子链中给受体的空间结构、电荷捕捉位点的深度以及给受体空间分布等,以实现对聚酰亚胺基存储材料存储性能的调节。这种理论结合实践的研究方法和多项研究结论为新型聚合物基存储材料的研究提供了具有指导意义的准则,对我国信息存储材料和技术的发展具有重要意义。
[Abstract]:The explosive growth of the total amount of data in the information age requires that new storage materials and components have super high storage density, ultra fast reading and writing and response speed, low start voltage and low cost and easy processing. The traditional semiconductor storage technology is mainly made of silicon and germanium, but the size of the line width and the storage point of the device has been already made. It is difficult to meet the requirements of the new age, and the newly developed polymer based information storage materials have become the focus of research because of their flexibility, low cost, easy processing, super capacity, ultra-low energy consumption and performance control through molecular cutting. Polyimides with excellent thermal stability, chemical stability and dimensional stability have become the focus of research. In recent years, the focus of research on polyimide based information storage materials is to design a new polyimide with both electron donor and electron acceptor in the molecular chain to facilitate the application of voltage. The charge transfer between the electrons and the macroscopic electric bihomeostasis on the microcosmic electron acceptor. So far, scholars have synthesized a variety of Polyimides with different chemical structures and obtained different storage properties, such as volatile random storage (DRAM) and static random storage (SRAM), and non volatile one write times. Read (WORM) and flash memory (Flash) storage performance. However, there are many factors such as the molecular orbital energy level, the front orbital energy level, the molecular space configuration, the electron and electron absorption capacity of the electron to the receptor, the space distribution of the charge capture loci, the ability to capture the charge, the thickness of the active layer, the surface morphology of the material and the type of the electrode. The mechanism of storage in polyimide based memory is very complex. So, although many research results have been found in this field, more in-depth research and detailed analysis are needed, especially, how to explore the relationship between the molecular structure and storage performance of polyimide in order to achieve the storage behavior. In this paper, we designed and synthesized three series of new electroactive polyimides, and studied their information storage performance. In combination with their photophysical properties, electrochemical properties and molecular simulation results, we studied the electron donor capacity and the spatial junction of the molecules to the receptors in the molecular chain. The main research contents and results in this paper are as follows: (1) a new two amine DAPAP (N, N- two (4- amino) phenyl -1- pyrene) containing the electron group pyrene, and BAPF (9,9'- pair (4- amino) phenyl fluorene) and DSDA (3,3', 4,4) A series of new functional copolymerized polyimides (coPI-DAPAPx, x=100, x=100, 50, 20, 10, 5, 1, 0, and X representing DAPAP accounted for the total of the total two amine monomer) were prepared by adjusting the ratio of DAPAP and BAPF. The product showed good solubility and excellent thermal stability. Through rotating coating and vacuum, the product showed good thermal stability. The storage devices with ITO/ polyimide /Au structure were prepared by steam plating and their storage properties were studied. The results showed that DAPAP was the main electron donor in this series copolymerized polyimide. With the decrease of DAPAP content, the corresponding storage properties of polyimide were 100%, 50%, 20% from non-volatile and easy to lose type. And 10% polyimide showed nonvolatile WORM storage properties, while Polyimides with DAPAP content of 5% and 1% showed a loss of SRAM type storage properties of 0% polyimide with no bistable storage performance. The analysis of characterization results and molecular simulation results showed that polyimide decreased with the decrease of DAPAP content. The HOMO (the highest occupied orbital) orbital energy level and the Eg (front-line orbital energy difference) decrease, resulting in a decrease in the stability of the charge transfer complex formed in the polyimide molecules after the application of the voltage. Therefore, there is a change in the non volatile storage properties of the easily lost type. (2) three new two amines containing electron donor anthracene, 1-DAPAA (N, N- two (4), 4) have been synthesized. - amino) phenyl -1 - anthracene), 2-DAPAA (N, N- two (4- amino) phenyl -2- anthracene) and 9-DAPAA (N, N- two (4- amino) phenyl -9- anthracene), and polymerized with 6FDA (six fluoroisopropyl) two phthalic anhydride), and three kinds of electroactive polyimides containing similar electric subgroups were synthesized by two steps. Three kinds and three kinds of electroactive polyimides were synthesized. The only difference in polyimides is that anthracene is the side group and the site of the main chain of polyimide is different (1-, 2-, 9-). The result of semiconductor analysis shows that 1-DAPAA-6FDA and 9-DAPAA-6FDA have a nonvolatile WORM type storage behavior, while 2-DAPAA-6FDA shows a volatile SRAM type storage behavior. The molecular simulation results show that three kinds of two amines have phase. The Mulliken charge distribution results also show that the charge transfer from the ground state to the excited state in the three polyimides is almost the same, so the effect of the electron effect on the storage performance is excluded. ) the difference in size, in which the 2-DAPAA-6FDA is the smallest of theta 1, and the plane of the whole molecule is relatively better, which is beneficial to the charge transfer and the reverse charge transfer, thus showing the loss of SRAM type storage performance. The 1-D APAA-6FDA and 9-DAPAA-6FD A are not favorable for the charge transfer because the anthracene and the main chain between the main chains are not favorable for the charge transfer, and the non volatile WORM is presented. (3) two new types of amines, DATP6Cz (N, N- two (4- amino) phenyl -6- (9- carbazole) hexylamine) and DATP2Cz (N, N- two (4- amino) phenyl -2- (9- carbazole) ethylamine) are synthesized, and two step method is used to polycondensation with two kinds of two anhydride and two anhydride, two anhydride, four formic acid two anhydride, The introduction of four different polyimides, DATP6Cz-DSDA, DATP6Cz-NTDA, DATP2Cz-DSDA, DATP2Cz-NTDA. carbazole and polyimide chain, has successfully changed the relative space position between the electron donor and the molecular chain. The results of semiconductor analysis showed that two polyimides, DATP6Cz-DSDA and DATP2Cz-DSDA containing DSDA were found. The non volatile WORM type storage behavior is presented, and two kinds of polyimides containing NTDA, DATP6Cz-NTDA and DATP2Cz-NTDA exhibit the loss of SRAM and DRAM type storage behavior respectively. The molecular simulation results show that the sulfone group in DSDA has a stronger charge capture ability than the carbonyl group in NTDA, and the associates formed after the capture of the charge are not. It is easy to dissociate, and the associates formed after the NTDA capture the charge are easily dissociated, thus the polyimides containing DSDA and NTDA exhibit a non-volatile and volatile storage performance, and the different lengths of the non conjugated fat chains lead to the different transfer of the charge from the receptor to the donor during the dissociation process, and the energy barrier to be overcome is different, thus macroscopically. The storage behavior of SRAM and DRAM is presented with different retention times. To sum up, the design ideas and research results of this paper prove that the structure of electron donor is designed and regulated by molecular simulation, in order to adjust the electronic capacity of the electron donor and the spatial structure of the receptor in the molecular chain, The depth of the charge capture site and the spatial distribution of the receptor are used to regulate the storage properties of the polyimide based storage materials. This theory provides a guiding principle for the study of the new polymer based storage materials, which combines practical research methods and many research conclusions. Development is of great significance.
【学位授予单位】：北京化工大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O633.22
本文编号：2127646
[Abstract]:The explosive growth of the total amount of data in the information age requires that new storage materials and components have super high storage density, ultra fast reading and writing and response speed, low start voltage and low cost and easy processing. The traditional semiconductor storage technology is mainly made of silicon and germanium, but the size of the line width and the storage point of the device has been already made. It is difficult to meet the requirements of the new age, and the newly developed polymer based information storage materials have become the focus of research because of their flexibility, low cost, easy processing, super capacity, ultra-low energy consumption and performance control through molecular cutting. Polyimides with excellent thermal stability, chemical stability and dimensional stability have become the focus of research. In recent years, the focus of research on polyimide based information storage materials is to design a new polyimide with both electron donor and electron acceptor in the molecular chain to facilitate the application of voltage. The charge transfer between the electrons and the macroscopic electric bihomeostasis on the microcosmic electron acceptor. So far, scholars have synthesized a variety of Polyimides with different chemical structures and obtained different storage properties, such as volatile random storage (DRAM) and static random storage (SRAM), and non volatile one write times. Read (WORM) and flash memory (Flash) storage performance. However, there are many factors such as the molecular orbital energy level, the front orbital energy level, the molecular space configuration, the electron and electron absorption capacity of the electron to the receptor, the space distribution of the charge capture loci, the ability to capture the charge, the thickness of the active layer, the surface morphology of the material and the type of the electrode. The mechanism of storage in polyimide based memory is very complex. So, although many research results have been found in this field, more in-depth research and detailed analysis are needed, especially, how to explore the relationship between the molecular structure and storage performance of polyimide in order to achieve the storage behavior. In this paper, we designed and synthesized three series of new electroactive polyimides, and studied their information storage performance. In combination with their photophysical properties, electrochemical properties and molecular simulation results, we studied the electron donor capacity and the spatial junction of the molecules to the receptors in the molecular chain. The main research contents and results in this paper are as follows: (1) a new two amine DAPAP (N, N- two (4- amino) phenyl -1- pyrene) containing the electron group pyrene, and BAPF (9,9'- pair (4- amino) phenyl fluorene) and DSDA (3,3', 4,4) A series of new functional copolymerized polyimides (coPI-DAPAPx, x=100, x=100, 50, 20, 10, 5, 1, 0, and X representing DAPAP accounted for the total of the total two amine monomer) were prepared by adjusting the ratio of DAPAP and BAPF. The product showed good solubility and excellent thermal stability. Through rotating coating and vacuum, the product showed good thermal stability. The storage devices with ITO/ polyimide /Au structure were prepared by steam plating and their storage properties were studied. The results showed that DAPAP was the main electron donor in this series copolymerized polyimide. With the decrease of DAPAP content, the corresponding storage properties of polyimide were 100%, 50%, 20% from non-volatile and easy to lose type. And 10% polyimide showed nonvolatile WORM storage properties, while Polyimides with DAPAP content of 5% and 1% showed a loss of SRAM type storage properties of 0% polyimide with no bistable storage performance. The analysis of characterization results and molecular simulation results showed that polyimide decreased with the decrease of DAPAP content. The HOMO (the highest occupied orbital) orbital energy level and the Eg (front-line orbital energy difference) decrease, resulting in a decrease in the stability of the charge transfer complex formed in the polyimide molecules after the application of the voltage. Therefore, there is a change in the non volatile storage properties of the easily lost type. (2) three new two amines containing electron donor anthracene, 1-DAPAA (N, N- two (4), 4) have been synthesized. - amino) phenyl -1 - anthracene), 2-DAPAA (N, N- two (4- amino) phenyl -2- anthracene) and 9-DAPAA (N, N- two (4- amino) phenyl -9- anthracene), and polymerized with 6FDA (six fluoroisopropyl) two phthalic anhydride), and three kinds of electroactive polyimides containing similar electric subgroups were synthesized by two steps. Three kinds and three kinds of electroactive polyimides were synthesized. The only difference in polyimides is that anthracene is the side group and the site of the main chain of polyimide is different (1-, 2-, 9-). The result of semiconductor analysis shows that 1-DAPAA-6FDA and 9-DAPAA-6FDA have a nonvolatile WORM type storage behavior, while 2-DAPAA-6FDA shows a volatile SRAM type storage behavior. The molecular simulation results show that three kinds of two amines have phase. The Mulliken charge distribution results also show that the charge transfer from the ground state to the excited state in the three polyimides is almost the same, so the effect of the electron effect on the storage performance is excluded. ) the difference in size, in which the 2-DAPAA-6FDA is the smallest of theta 1, and the plane of the whole molecule is relatively better, which is beneficial to the charge transfer and the reverse charge transfer, thus showing the loss of SRAM type storage performance. The 1-D APAA-6FDA and 9-DAPAA-6FD A are not favorable for the charge transfer because the anthracene and the main chain between the main chains are not favorable for the charge transfer, and the non volatile WORM is presented. (3) two new types of amines, DATP6Cz (N, N- two (4- amino) phenyl -6- (9- carbazole) hexylamine) and DATP2Cz (N, N- two (4- amino) phenyl -2- (9- carbazole) ethylamine) are synthesized, and two step method is used to polycondensation with two kinds of two anhydride and two anhydride, two anhydride, four formic acid two anhydride, The introduction of four different polyimides, DATP6Cz-DSDA, DATP6Cz-NTDA, DATP2Cz-DSDA, DATP2Cz-NTDA. carbazole and polyimide chain, has successfully changed the relative space position between the electron donor and the molecular chain. The results of semiconductor analysis showed that two polyimides, DATP6Cz-DSDA and DATP2Cz-DSDA containing DSDA were found. The non volatile WORM type storage behavior is presented, and two kinds of polyimides containing NTDA, DATP6Cz-NTDA and DATP2Cz-NTDA exhibit the loss of SRAM and DRAM type storage behavior respectively. The molecular simulation results show that the sulfone group in DSDA has a stronger charge capture ability than the carbonyl group in NTDA, and the associates formed after the capture of the charge are not. It is easy to dissociate, and the associates formed after the NTDA capture the charge are easily dissociated, thus the polyimides containing DSDA and NTDA exhibit a non-volatile and volatile storage performance, and the different lengths of the non conjugated fat chains lead to the different transfer of the charge from the receptor to the donor during the dissociation process, and the energy barrier to be overcome is different, thus macroscopically. The storage behavior of SRAM and DRAM is presented with different retention times. To sum up, the design ideas and research results of this paper prove that the structure of electron donor is designed and regulated by molecular simulation, in order to adjust the electronic capacity of the electron donor and the spatial structure of the receptor in the molecular chain, The depth of the charge capture site and the spatial distribution of the receptor are used to regulate the storage properties of the polyimide based storage materials. This theory provides a guiding principle for the study of the new polymer based storage materials, which combines practical research methods and many research conclusions. Development is of great significance.
【学位授予单位】：北京化工大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O633.22
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