有机聚合物/无机二维纳米杂化多阶阻变存储材料与器件研究

Organic-inorganic hybrid memory technology is an important research direction in the current interdisciplinary of materials science and information storage. Based on recent advances and trends in organic-inorganic hybrid memories and flexible organic electronics, the proposal demonstrates that organic polymer semiconductor materials will be synthesized through the simple, effective and non-metal catalyst Friedel-Crafts polymerization of fluorenyl tertiary alcohols. Inorganic two-dimensional semiconductor nanomaterials will be produced by liquid exfoliation methods. Then, flexible memory devices with tunable memory performances and multilevel resistive switching properties will be prepared by using the organic-inorganic hybrid materials as the functional layers. After that, the impact of energy levels, microscopic structure of films and interfacial characterization on the multilever resistive switching performances of memory devices will be studied systematically. Material component-functional layer strucutre-memory property relationships are further explored. The flexible function of these devices will be studied. The charge injection and transfer processes of the functional layers in different resistance states will be discussed. Moreover, the model of operation mechanism of resistive switching in organic-inorganic hybrid based memory devices will be made. The design and fabrication of novel organic polymer semiconductor-inorganic two-dimensional hybrid and flexible memory devices with multilevel resistive switching properties has great significance for the development of mechanism study and application of memory technologies.

有机无机杂化电存储技术是材料科学与信息存储交叉领域的一个重要研究方向。本项目结合当前有机无机杂化电存储与柔性有机电子的研究现状与发展趋势，提出通过简单高效、非金属催化的芴基叔醇傅克聚合反应设计合成有机聚合物半导体材料；通过液相剥离法制备无机二维半导体纳米材料；将两类材料在分子尺寸进行杂化得到存储功能层，制造柔性有机无机杂化阻变存储器并实现阻变存储性能的调控和多阶阻变存储。系统研究能级结构、薄膜微观形貌与界面特性等因素对实现多阶阻变存储特性的影响，明确材料组分-功能层结构-存储性能三者之间的关系，考察器件的柔性功能，分析功能层在不同电阻态时的载流子注入与传输过程，进而建立适用于有机无机杂化阻变存储器实现电转化的作用机制模型。这种新型有机聚合物半导体/无机二维纳米杂化阻变材料的制备与器件的柔性加工对于推动电存储技术的机制研究和应用具有重要意义。

有机无机杂化电存储技术是材料科学与信息存储交叉领域的一个重要研究方向。本项目结合当前有机无机杂化电存储与柔性有机电子的研究现状与发展趋势，在电存储材料制备方面，提出通过表面限域氧化聚合的策略在任意衬底上成功制备了一系列大面积二维共轭微孔聚合物(2D CMP)；此外，将2D CMP生长在还原氧化石墨烯(rGO)薄膜上，构建了大面积2D CMP/rGO异质结。通过光掩模板辅助的固态光聚合制备了图案化的2D CMPs；通过调节聚合反应时间和掩膜板，能实现2D CMPs厚度和图案的可控化。结合层层生长策略和改变聚合单体，可控制备了多层异质结构的2D CMPs。此外，通过液-固界面的席夫碱反应，制备了一种卟啉基2D CMP。在电存储器件应用方面，制备了首例基于二维聚合物的电存储器件，器件具有非易失性电存储性能和高的开光比；依赖于2D CMP膜丰富的电子结构和出色的化学结构稳定性，通过溶液加工制备了基于2D CMP的多层整流阻变存储器件，该器件能有效减少电流串扰引起的误读问题，实现信息的准确读取；基于2D CMP良好的化学结构稳定性，通过在其表面旋涂共轭聚合物构筑了共轭聚合物异质结，进而获得了高开光比的聚合物电存储器件；在以部分还原氧化石墨烯(p-rGO)为功能层的电存储器件中，以2D CMP为电荷阻挡层，获得了一种基于二维混合异质结构的本征低电流存储器；以共轭聚合物为活性层，还原氧化石墨烯薄膜为器件电极，制备了一种聚合物基柔性电存储器，该器件具有高的稳定性。这些成果的获得极大促进了二维聚合物材料与电存储器件的发展与实用化进程，丰富了半导体材料与器件理论。