基于喹喔啉及三苯胺骨架的电储存材料的设计合成及其性能研究

发布时间：2018-07-14 14:46

【摘要】：随着信息量的不断快速增长,研究多进制电存储信息材料及纳米器件的意义重大。2010年,我们课题组通过分子结构的调控实现了基于有机小分子的三进制电存储,即实现有机小分子多进制信息存储“零”的突破。随着近年来有机小分子三进制电存储研究的不断深入,纵观其研究现状,尽管理论上更接近未来超高密度信息存储的需求(~1015 bits/cm2),但要获得高效、稳定、方便及大存储容量的信息存储器件并最终走向应用,有机小分子电存储材料及器件的研究现状还远不能满足上述要求。因此,通过分子结构的设计来对有机电存储性能进行优化依然任重而道远,机遇和挑战并存。结合有机电子学器件性能的优化策略,关于同分异构效应、不同的间隔基团及电子效应等对有机小分子电存储器件性能调控的报道仍然较少,因此进一步设计合成相关分子并研究其对器件性能的影响具有重要意义。本论文主要从以下几方面展开:(1)研究同分异构体对多进制存储器件性能的影响:合成了两个基于喹喔啉的互为同分异构体的有机小分子QU-1和QU-2,考察了其对光电性能、薄膜形貌及器件存储性能的影响。基于这两个小分子的器件均表现出三进制WORM存储性能,研究结果表明与QU-1相比,直线型的QU-2具有更紧密的堆积、较小的表面粗糙度及好的层状堆积,所制备的器件表现出较低的阈值电压和高的电流比。通过对基于喹喔啉的两个同分异构体的比较研究,为后续优化设计合成新型的小分子存储材料提供了有利的参考。(2)研究电子给体N原子取代基对多进制存储器件性能的影响:合成了两个有机小分子Qu-Ph和Qu-Oct,其中喹喔啉和丙二腈作为受体基团,咔唑作为供体基团,不同的是咔唑N原子上的取代基分别为苯基(Qu-Ph)和烷基链(Qu-Oct)。结果显示组装的ITO/有机小分子/Al三明治结构器件均具有三进制WORM存储性能,当咔唑N原子上的烷基被芳香族苯环取代后,由于取代基的自由空间随之变小,刚性增强最终导致分子的薄膜形貌更加规整,堆积变得更加紧密。规整的形貌和紧密的堆积有力地降低了载流子的迁移能垒,从而使Qu-Ph表现出较低的开启电压。我们相信,使用芳香族苯环取代烷基链可以作为一个有效的策略去优化超高密度信息存储器件的性能。(3)研究两个受体单元间芳香间隔基对存储器件性能的影响:合成了两个三苯胺-喹喔啉-π-次甲基丙二腈衍生物TPAQPh和TPAQFu。两个分子具有相同的给体和受体,不同之处在于两个给体间的间隔基团分别为苯基和呋喃基。结果显示制备的ITO/有机小分子/Al三明治结构器件均具有三进制WORM存储性能,但间隔基呋喃取代苯环之后,分子的薄膜形貌变得更加的规整,堆积变得紧密有序,从而利于载流子的迁移,最终导致器件的开启电压降低,而原因在于呋喃环的引入有效的弱化了喹喔啉片段与丙二腈片段的扭曲角度。通过对间隔基团的研究表明该策略可以有效的调控分子的薄膜形貌、堆积及开启电压,从而为后续设计合成新型的小分子存储材料及对器件的精细调控提供了有利的参考。(4)研究了中心功能团所连支链数目对存储器件性能的影响:成功合成了三个基于三苯胺的具有不同数目的苯基-苯并噻二唑支链的有机小分子(TPA-nBBT n=1,2,3)。组装的ITO/有机小分子/Al三明治结构器件均表现出二进制易失性(SRAM)电存储特性。结果显示中心功能团三苯胺所连支链数目的多少对器件性能具有重要的影响。随着支链数目的的不断增加,器件的热稳定性增加,重现性增强,同时器件的开启电压也明显降低。其中TPA-3BBT分子表现出了最优异的性能,随着温度的不断升高,其薄膜依然保持很好的稳定性,同时器件的稳定性也得以保持。研究结果表明通过调节三苯胺所连支链的数目可以有效的对器件的各项性能进行调节,这将为日后设计新的性能更加优异的材料分子提供强有力的支持。
[Abstract]:With the rapid growth of the amount of information, it is important to study the significance of the storage of information materials and nanoscale devices in the.2010. We have achieved a breakthrough in the realization of the "zero" of organic small molecule information storage and storage by the regulation of molecular structure by the regulation of molecular structure. The research of sub three power storage is going deep and deeply, looking at the current research status, although it is more close to the demand for the future ultra high density information storage (~1015 bits/cm2), the information memory parts with high efficiency, stability, convenience and large storage capacity are needed, and the research status of organic small molecule electrical storage materials and devices is still far from now. Therefore, it is still a long way to go through the design of molecular structure to optimize the performance of mechanical and electrical storage. Opportunities and challenges coexist. Combined with the optimization strategy of organic electronics device performance, the performance modulation of organic small molecule electrical memory parts on isomeric effects, different spacer groups and electronic effects. There are still few reports on control, so it is of great significance to further design and study the influence of the related molecules on the performance of the devices. This paper mainly starts from the following aspects: (1) the study of the effects of isomers on the performance of the multi system memory parts: the synthesis of two organic small molecules QU-1 based on the isomers of the isomers And QU-2, the effects on the photoelectric performance, the film morphology and the memory performance of the device are investigated. The devices based on these two small molecules show the performance of the three WORM storage. The results show that the linear QU-2 has more compact accumulation, smaller surface roughness and good layer stacking compared with QU-1, and the devices prepared have shown a better performance. Low threshold voltage and high current ratio. By comparing the two isomers based on the two isomers, it provides a favorable reference for the subsequent optimization of the synthesis of new small molecular storage materials. (2) the study of the effects of the substituents of the electron donor N atoms on the property of the M-ary memory: the synthesis of two organic small molecules Qu-Ph and Q U-Oct, in which the carbazole as the donor group, carbazole as the donor group, the different substituents on carbazole N atoms are phenyl (Qu-Ph) and alkyl chain (Qu-Oct). The results show that the assembled ITO/ organic small molecule /Al sandwich structure devices all have the three inlet WORM storage property, and the alkyl alkyl on the carbazole N atom is aromatic. After the substitution of the benzene ring, the free space of the substituents becomes smaller, and the rigid enhancement eventually leads to the more compact morphology of the molecules and the more compact accumulation. The regular morphology and compact accumulation can effectively reduce the transfer energy barrier of the carrier, so that the Qu-Ph shows a lower opening voltage. We believe that aromatic benzene rings are used. The substitution of alkyl chains can be used as an effective strategy to optimize the performance of ultrahigh density information storage devices. (3) study the effect of aromatic septum between two receptor units on the performance of memory parts: two three aniline - pion - pion - methylpropyl two nitrile derivatives, TPAQPh and TPAQFu., have the same donor and receptor, The difference is that the spacer groups of the two INTERBODIES are respectively phenyl and furanolyl. The results show that the ITO/ organic small molecule /Al sandwich structure devices all have three WORM storage properties, but the film morphology of the molecules becomes more regular after the replacement of the benzene ring with the septal furan, and the accumulation becomes compact and orderly, which is beneficial to the carrier flow. The migration of the subunit leads to the decrease of the opening voltage of the device, and the reason is that the introduction of the furan ring effectively weakens the distortion angle of the fragment of the azoline and the two nitrile fragment. The small molecular storage materials and the fine control of the devices have provided favorable references. (4) the effect of the number of branches connected to the central function group on the performance of the memory parts was studied. Three organic small molecules (TPA-nBBT n=1,2,3) with different number of phenyl benzothiazole branched chains based on three aniline were successfully synthesized. The ITO/ organic fraction of the assembly was assembled. The sub /Al sandwich structure devices all exhibit binary volatile (SRAM) electrical storage characteristics. The results show that the number of three aniline chains in the central functional group has an important effect on the performance of the device. With the increase of the number of branched chains, the thermal stability of the device increases, the weight is more repeatable, and the opening voltage of the device is also significantly reduced. The TPA-3BBT molecule shows the best performance. With the increase of temperature, the film remains stable and the stability of the device is maintained. The results show that the performance of the device can be adjusted effectively by adjusting the number of the chain of three aniline. This will be a new design for the future. It provides strong support for material molecules with better performance.
【学位授予单位】：苏州大学
【学位级别】：博士
【学位授予年份】：2016
【分类号】：TP333;O621.1

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