卟啉改性D-A型共轭高分子的合成及光电性能  

Synthesis and Optoelectronic Properties of Porphyrin-Modified D-A Type Conjugated Polymers

作　　者：孙赛 况挺 蒋建忠 高凯 张斌[2] 李真 董文芊 SUN Sai;KUANG Ting;JIANG Jianzhong;GAO Kai;ZHANG Bin;LI Zhen;DONG Wenqian(Sinopec(Shanghai)Petrochemical Research Institute Co.Ltd.,Shanghai 201208,China;Key Laboratory for Advanced Materials,School of Chemistry and Molecular Engineering,East China University of Science and Technology,Shanghai 200237,China)

机构地区：[1]中石化(上海)石油化工研究院有限公司,上海201208 [2]华东理工大学化学与分子工程学院,教育部结构可控先进功能材料及其制备重点实验室,上海200237

出　　处：《功能高分子学报》2025年第2期177-186,共10页Journal of Functional Polymers

基　　金：中国石化优秀青年科技创新基金。

摘　　要：随着智能化时代的到来,信息量激增,人们对更大容量、稳定性强、功能全的存储设备需求增加。在众多材料中,有机高分子材料因其可调节的电学性能而受到关注。通过Knoevenagel缩合合成了含卟啉的D-A型共轭高分子对苯二甲腈-锌卟啉(PCN-ZnPor),该材料具有良好的热稳定性且可溶于极性溶剂。以此高分子为活性层制备的Al/PCN-ZnPor/ITO器件具有非易失性可擦写阻变存储性能,开启电压为-3.04 V,电流开关比为7×10^(3),且稳定性较好。本研究表明,含卟啉的高分子材料在高密度存储领域具有巨大潜力。With the advent of the intelligent era,the explosive growth of the amount of information has led to a strong demand for the development of storage devices with larger capacity,greater stability and more comprehensive functions.Among many alternative materials,organic polymers can be designed with different structures to regulate the electrical properties,thus attracting the attention of researchers.We polymerized p-phenylene diacetonitrile and zinc porphyrin by Knoevenagel condensation reaction to obtain the D-A type conjugated polymer PCN-ZnPor,and then tested the material,which has good thermal stability and is soluble in polar solvents.The Al/PCN-ZnPor/ITO devices prepared with the polymer as the active layer film showed non-volatile erasable resistive variable storage performance with a turn-on voltage of -3.04 V,and the current switching ratio of 7×10^(3).After durability test,the ON state and OFF state of the Al/PCN-ZnPor/ITO device correspond to the current basically remain at a relatively stable value,which indicates that the device has good stability and reproducibility.Meanwhile,we performed in situ fluorescence tests on PCN-ZnPor films spin-coated on ITO substrates.When a voltage greater than the ON voltage(-3.04 V)was applied,no change in the shape of the fluorescence spectra was observed,while the overall fluorescence intensity was weakened.This fluorescence quenching behavior may be related to the charge transfer between the metal zinc porphyrin and the main chain of the polymer with a cyano group,which is consistent with the transition of the device from the OFF state to the ON state,suggesting that intramolecular charge transfer may have taken place in our prepared devices.This work demonstrates the great potential of porphyrin-containing polymers in the field of high-density storage.

关 键 词：有机高分子 D-A型 卟啉 非易失性存储 光电性能 

分 类 号：O69[理学—化学] TB34[一般工业技术—材料科学与工程] O633.5