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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

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Abstract

Functional polymeric materials with electrical bi-stable states possess significant potential for high-density data storage due to their nanoscale memory site, three-dimensional-stacking ability and intrinsic flexibility. Aromatic polyimides bearing donor-acceptor (D-A) skeleton could form charge transfer complex (CTC) under 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 3d 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 charge-transfer 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.

摘要

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Mn-DATPP-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, DATPP-DSDA 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.

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Acknowledgements

The authors 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), and the Natural Science Foundation for Distinguished Young Scholars of Jiangsu Province (BK20140006).

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Authors and Affiliations

  1. State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing, 100029, China

    Jiacong Guo  (郭家聪), Yankun Zhang  (张焱坤), Guofeng Tian  (田国峰), Shengli Qi  (齐胜利) & Dezhen Wu  (武德珍)

  2. Tianjin Key Laboratory of Molecular Optoelectronic Science, Department of Chemistry, Institute of Molecular Aggregation Science, Tianjin University, Tianjin, 300072, China

    Deyang Ji  (纪德洋)

  3. Beijing National Laboratory for Molecular Sciences, Beijing, 100190, China

    Deyang Ji  (纪德洋)

  4. Changzhou Institute of Advanced Materials, Beijing University of Chemical Technology, Changzhou, 213164, China

    Shengli Qi  (齐胜利) & Dezhen Wu  (武德珍)

  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

    Wenping Hu  (胡文平)

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  1. Jiacong Guo  (郭家聪)
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Contributions

Guo J, Zhang Y, Ji D and Qi S conceived and designed the experiments. Guo J and Zhang Y performed the experiments and molecular simulations. Guo J, Zhang Y, Wu D, Ji D, Qi S and Hu W discussed the results and co-wrote the manuscript.

Corresponding authors

Correspondence to Deyang Ji  (纪德洋) or Shengli Qi  (齐胜利).

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Conflict of interest

The authors declare no conflict of interest.

Jiacong Guo received his BEng degree from Nanjing Tech University in 2016. He is now a PhD student at Beijing University of Chemical Technology. His research interests are polyimide memory materials.

Deyang Ji is currently a Professor at the Institute of Molecular Aggregation Science, Tianjin University. He received his BSc degree from Ocean University of China in 2009. He received his PhD degree from the Institute of Chemistry, Chinese Academy of Sciences, in 2014 under the supervision of Prof. Wenping Hu. Then, he joined the University of Münster, Germany, as a postdoc fellow in the group of Prof. Harald Fuchs. His research interest focuses on organic optoelectronics.

Shengli Qi is currently a Professor at the School of Materials Science and Engineering, Beijing University of Chemical Technology, China. He received his PhD degree from Beijing University of Chemical Technology in 2008. Then he worked in Nagoya University as a postdoctoral fellow of Japan Society for the Promotion of Sciences in 2009–2011. His research focuses on high-performance and functional polyimide and its applications in flexible display, information storage and secondary energy systems.

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Guo, J., Zhang, Y., Tian, G. et al. Electron configurations at 3d orbital of metal ion determining charge transition process in memory devices. Sci. China Mater. 64, 1713–1722 (2021). https://doi.org/10.1007/s40843-020-1560-1

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  • DOI: https://doi.org/10.1007/s40843-020-1560-1

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