Enhancing the Backbone Coplanarity of n-Type Copolymers for Higher Electron Mobility and Stability in Organic Electrochemical Transistors.
Enhancing the Backbone Coplanarity of n-Type Copolymers for Higher Electron Mobility and Stability in Organic Electrochemical Transistors.
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DOI：
10.1021/acs.chemmater.2c01552
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发表时间：
2022-10-11
影响因子：
8.6
通讯作者：
McCulloch, Iain
中科院分区：
文献类型：
--
作者：
Maria, Iuliana P.;Griggs, Sophie;Rashid, Reem B.;Paulsen, Bryan D.;Surgailis, Jokubas;Thorley, Karl;Le, Vianna N.;Harrison, George T.;Combe, Craig;Hallani, Rawad;Giovannitti, Alexander;Paterson, Alexandra F.;Inal, Sahika;Rivnay, Jonathan;McCulloch, Iain
电子传输（n型）共轭聚合物最近已应用于众多需要离子和电子传输的电化学应用中。尽管人们不断努力提高其性能和稳定性，但具有混合传导的n型共轭聚合物仍然落后于其空穴传输（p型）同类材料，这限制了电化学装置的功能。在这项工作中，我们研究了增强主链共平面性对n型聚合物在水介质中运行时的电化学活性和混合离子 - 电子传导性能的影响。通过用广泛使用的缺电子萘二酰亚胺（NDI）单元替换核心扩展的萘并二噻吩二酰亚胺（NDTI）单元，所得聚合物显示出更平面的主链且堆积更紧密，使得有机电化学晶体管（OECTs）中的电子迁移率提高了两个数量级以上。基于NDTI的聚合物具有较低的最低未占分子轨道能级，使得OECT能够在相对于Ag/AgCl更接近0 V的电压下工作，此时与分子氧发生的寄生反应更少。增强主链共平面性还导致在循环过程中对吸水的亲和力降低，从而相对于NDI衍生物在连续电化学充电和开 - 关切换过程中稳定性得到提高。此外，基于NDTI的聚合物在长达一个月的测试中还表现出近乎完美的储存稳定性，最大导通电流和跨导的降低都可忽略不计。我们的结果强调了聚合物主链设计对于开发在水介质中具有混合离子 - 电子传导的稳定、高性能n型材料的重要性。
Electron-transporting (n-type) conjugated polymers have recently been applied in numerous electrochemical applications, where both ion and electron transport are required. Despite continuous efforts to improve their performance and stability, n-type conjugated polymers with mixed conduction still lag behind their hole-transporting (p-type) counterparts, limiting the functions of electrochemical devices. In this work, we investigate the effect of enhanced backbone coplanarity on the electrochemical activity and mixed ionic-electronic conduction properties of n-type polymers during operation in aqueous media. Through substitution of the widely employed electron-deficient naphthalene diimide (NDI) unit for the core-extended naphthodithiophene diimide (NDTI) units, the resulting polymer shows a more planar backbone with closer packing, leading to an increase in the electron mobility in organic electrochemical transistors (OECTs) by more than two orders of magnitude. The NDTI-based polymer shows a deep-lying lowest unoccupied molecular orbital level, enabling operation of the OECT closer to 0 V vs Ag/AgCl, where fewer parasitic reactions with molecular oxygen occur. Enhancing the backbone coplanarity also leads to a lower affinity toward water uptake during cycling, resulting in improved stability during continuous electrochemical charging and ON–OFF switching relative to the NDI derivative. Furthermore, the NDTI-based polymer also demonstrates near-perfect shelf-life stability over a month-long test, exhibiting a negligible decrease in both the maximum on-current and transconductance. Our results highlight the importance of polymer backbone design for developing stable, high-performing n-type materials with mixed ionic-electronic conduction in aqueous media.
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