D-A型含氮过渡金属配合物阻变存储材料的设计、合成及性能

Resistive random access memory (RRAM) is a new high density electrical memory developed in recent years. Those coordination compounds with bistable properties and potentialities of being made into three dimensional stack array are potential excellent resistive switching materials. This project aims to design and synthesize a series of transition metal complex materials which can be applied to the RRAM. Based on the switching mechanism of charge transfer and redox activity, this project constructs D-A type transition metal complex materials using terpyridine derivants as ligands by density functional theory(DFT) calculating the complexes' HOMO and LUMO. The terpyridine derivates are changed by grafting the different memory organic molecular subunits or functional groups, such as triphenylamine, thiophene, and cynogroup on the terpyridines. This project uses the transition metal and terpyridine derivants as ligands to synthesize D-A type transition metal complexes by solution way. Their structures, thermal stability and redox activity properties will be characterized. Transition metal complex films and ITO/D-A type transition metal complexes/Al devices will be prepared in conventional way, and characterization of current On/Off ratio of devices and other resistive switching properties will be tested. At the same time, the law and relation between molecular structures of D-A type transition metal complexes and resistive switching properties of devices would be summarized on the basis of a great deal of structural designs and property tests. The design theory about metal complex materials with resistive switching memory is developed and provides theoretical guidance and experimental basis for searching new metal complex materials which are suitable for the RRAM.

阻变存储器是近年开发的新型高密度电存储器。金属配合物具有有双稳态特性，且有被制成高密度三维堆栈存储阵列的潜能，是潜在的优秀阻变存储材料。本项目以设计合成一类应用于阻变存储器件的过渡金属配合物材料为研究目标；基于电荷转移和氧化还原的存储机制，运用三苯胺、噻吩和氰基等有机存储分子单元或官能团嫁接调控联三吡啶结构的设计思路，采用密度泛函（DFT）等理论方法设计构筑D-A型联三吡啶衍生物过渡金属配合物存储材料；通过分步溶液法合成目标配合物，表征其结构，研究其热稳定和氧化还原活性等性能；再选用常规法制备ITO/D-A型含氮过渡金属配合物/Al器件，测试器件的开关比等阻变存储性能。在大量设计合成、性能测试工作的基础上，总结器件存储功能与配合物结构之间的关系与规律，发展金属配合物阻变存储材料的设计理论，为寻找适用于阻变存储的新型金属配合物材料提供理论指导和实验基础。

金属配合物具有有双稳态特性，且有被制成高密度三维堆栈存储阵列的潜能，是潜在的优秀阻变存储材料。但是阵列中的交叉串扰是存储器误读的重要因素，自整流材料能有效消除存储误读。设计优化出自整流优异的金属配合物分子材料对组变存储器的进一步发展应用具有重要意义。项目采用理论设计优化与实验验证相结合的方法进行研究，研究主要成果如下所列：.1） 采用第一原理和非平衡格林函数方法优化出整流效应非常优秀，整流比均超10的11方数量级以上，且没有漏电流的含芳香环基团异氰基锰、镍和铁配合物材料构成的D-A型分子结，其中锰合物分子材料构成的D-A型分子结还存在非常完美的负微分电阻现象。整流器是电路中不可缺少的单元，含芳香环基团异氰基锰配合物材料构成的D-A型分子结是构筑整流器的理想分子材料，在整流领域应用上具有良好的前景。.2）采用第一原理和非平衡格林函数方法研究一系列金属卟啉衍生配合物.分子组成的D-A型三明治器件模型Au/S(CH2)9MporphyrinS/Au，得出Mn-卟啉分子结具有优秀的自整流效应，最大整流比高达10的11方数量级以上，且Au/S(CH2)9MnporphyrinS/Au还存在非常完美的负微分电阻现象。采用理论方法筛选出具有优秀自整流性能的Mn-卟啉分子材料，对实际应用选取自整流存储材料提供理论指导和支持，具有为新型存储材料的开发和利用的科学意义。.3）制作Al/SC6H5-N≡C-Au-C6H5S/ITO、Al/ SH2nCn-ZnporphyrinS /ITO和Al/ Pr-P2-3/ITO三明治存储器件。制作Al/ Pr-P2-3/ITO三明治电存储器件，测试分析了器件的电存储性能，测试表明器件电流开关比ON/OFF为10的3方数量级，且具有典型的WORM型记忆存储性能。