Electron configurations at 3d orbital of metal ion determining charge transition process in memory devices  

存储器件中由金属离子3d轨道电子排布控制的电荷转移过程

作　　者：Jiacong Guo Yankun Zhang Guofeng Tian Deyang Ji Shengli Qi Dezhen Wu Wenping Hu 郭家聪;张焱坤;田国峰;纪德洋;齐胜利;武德珍;胡文平(State Key Laboratory of Chemical Resource Engineering,Beijing University of Chemical Technology,Beijing 100029,China;Tianjin Key Laboratory of Molecular Optoelectronic Science,Department of Chemistry,Institute of Molecular Aggregation Science,Tianjin University,Tianjin 300072,China;Beijing National Laboratory for Molecular Sciences,Beijing 100190,China;Changzhou Institute of Advanced Materials,Beijing University of Chemical Technology,Changzhou 213164,China;Tianjin Key Laboratory of Molecular Optoelectronic Science,Department of Chemistry,School of Science,Tianjin University&Collaborative Innovation Center of Chemical Science and Engineering,Tianjin 300072,China)

机构地区：[1]State Key Laboratory of Chemical Resource Engineering,Beijing University of Chemical Technology,Beijing 100029,China [2]Tianjin Key Laboratory of Molecular Optoelectronic Science,Department of Chemistry,Institute of Molecular Aggregation Science,Tianjin University,Tianjin 300072,China [3]Beijing National Laboratory for Molecular Sciences,Beijing 100190,China [4]Changzhou Institute of Advanced Materials,Beijing University of Chemical Technology,Changzhou 213164,China [5]Tianjin Key Laboratory of Molecular Optoelectronic Science,Department of Chemistry,School of Science,Tianjin University&Collaborative Innovation Center of Chemical Science and Engineering,Tianjin 300072,China

出　　处：《Science China Materials》2021年第7期1713-1722,共10页中国科学（材料科学（英文版）

基　　金：sincerely appreciate the financial support from the National Natural Science Foundation of China(51673017 and 62004138);Beijing National Laboratory for Molecular Sciences(BNLMS202006);the Fundamental Research Funds for the Central Universities(XK1802-2);the National Key Basic Research Program of China(973 program,2014CB643604);the Natural Science Foundation for Distinguished Young Scholars of Jiangsu Province(BK20140006)。

摘　　要：Functional polymeric materials with electrical bi-stable states possess significant potential for high-density data storage due to their nanoscale memory site,threedimensional-stacking ability and intrinsic flexibility.Aromatic polyimides bearing donor-acceptor(D-A)skeleton could form the charge transfer complex(CTC)under an electrical field,leading to their feasibility as memory materials.Three novel porphyrinated polyimides DATPP-DSDA,Zn-DATPP-DSDA and Mn-DATPP-DSDA were designed and synthesized for information memory applications.Metal ions with different electron configurations at 3 d orbital have a determining influence on memory behaviors of polyimides:nonvolatile write-once-read-many-times memory(WORM)for DATPP-DSDA,volatile static random access memory(SRAM)for Zn-DATPP-DSDA,but no memory performance for Mn-DATPP-DSDA.By comparing the contribution of orbital transition and hole-electron distribution of chargetransfer excited states,roles of metal ions in regulating memory types were discussed.Molecular simulation results indicate that the Zn ion could play a bridge role in paving the route for excited electrons from a D to an A,while a trap role for the Mn ion in hindering this process.This study proves the feasibility of the strategy for modulating the memory behaviors of porphyrinated polyimides by varying the central metal ion and provides the exact effects of various metal ions on regulating charge transfer processes.具有电双稳态的功能性聚合物材料因其纳米尺寸的存储位点、3D可堆叠性和固有柔性等优点,在高密度数据存储领域展现出巨大的应用潜力.具有电子给体-受体结构的聚酰亚胺在电场下可以形成电荷转移络合物,使其可以作为存储材料.本文合成了三种卟啉基聚酰亚胺DATPP-DSDA、Zn-DATPP-DSDA和MnDATPP-DSDA用于信息存储.研究发现金属离子的不同3d轨道电子排布对于聚酰亚胺的存储行为有决定性的影响.其中,DATPPDSDA展现出非易失性WORM存储行为,Zn-DATPP-DSDA展现出易失性SRAM存储行为,而Mn-DATPP-DSDA不具有存储性能.通过分析轨道跃迁贡献和电荷转移激发态的空穴-电子分布,研究了不同金属离子调节存储行为类型的作用.分子模拟结果表明锌离子起到一个"桥"的作用,可以促使电子从电子给体转移到电子受体部分,而锰离子起到一个"阱"的作用来阻止这一过程.对于卟啉基聚酰亚胺,这一研究证明了通过改变中心金属离子来调节存储行为的策略是可行的,并且提出了不同金属离子调节电荷转移过程的不同作用.

关 键 词：memory POLYIMIDE PORPHYRIN charge transfer 

分 类 号：TQ323.7[化学工程—合成树脂塑料工业] TP333[自动化与计算机技术—计算机系统结构]