Highly air-stable, n-doped conjugated polymers achieved by dimeric organometallic dopants
Highly air-stable, n-doped conjugated polymers achieved by dimeric organometallic dopants
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DOI：
10.1039/d0tc05931e
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发表时间：
2021-04
影响因子：
6.4
通讯作者：
Yu Yamashita;Samik Jhulki;D. Bhardwaj;E. Longhi;S. Kumagai;S. Watanabe;S. Barlow;S. Marder;J. Takeya
中科院分区：
文献类型：
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作者：
Yu Yamashita;Samik Jhulki;D. Bhardwaj;E. Longhi;S. Kumagai;S. Watanabe;S. Barlow;S. Marder;J. Takeya
化学掺杂是控制分子半导体电导率和功函数等电子性能的关键过程。n掺杂聚合物的一个共同限制是它们在环境条件下的不稳定性，这对n掺杂聚合物的表征和器件应用施加了限制。在本研究中，在以萘二亚胺和苝二亚胺为骨架的聚合物半导体薄膜上进行了有序的n掺杂有机金属掺杂。（RuCp*Mes）2, {Cp* =五甲基环戊二烯基；Mes = 1,3,5-三甲基苯}，这与用钴二烯（一种简单的单电子还原剂）获得的不稳定的n掺杂状态形成鲜明对比。与二茂铁相比，（RuCp*Mes）2的高阴极、有效氧化还原电位约为- 2.0 V，抑制了反向电子转移反应和随后在空气中的掺杂物损失，从而产生了观察到的空气稳定性。它还允许苝二酰亚胺基聚合物被还原到重复单元大部分是重阴离子的状态。光电子测量表明，重掺杂聚合物的电离电位约为3.9 eV。研究结果表明，化学掺杂（RuCp*Mes）2是制备高稳定性n掺杂共轭聚合物的有效方法。
Chemical doping is a key process for controlling the electronic properties of molecular semiconductors, including their conductivity and work function. A common limitation of n-doped polymers is their instability under ambient conditions, which has imposed restrictions on the characterisation and device application of n-doped polymers. In this study, sequential n-doping with organometallic dopants was performed on thin films of polymeric semiconductors with naphthalene diimide and perylene diimide-based backbones. Moderate ambient stability was achieved with (RuCp*Mes)2, {Cp* = pentamethylcyclopentadienyl; Mes = 1,3,5-trimethylbenzene}, which is in striking contrast to the unstable, n-doped state obtained with cobaltocene, a simple one-electron reductant. The highly cathodic, effective redox potential of (RuCp*Mes)2, ca. −2.0 V vs. ferrocene, suppresses the back electron transfer reaction and the subsequent dopant loss in air, which gives rise to the observed air stability. It also allows a perylene diimide-based polymer to be reduced to a state in which the repeat units are largely dianionic. Photoelectron measurements show that the ionization potential of the heavily doped polymer is ca. 3.9 eV. Our findings show that chemical doping with (RuCp*Mes)2 is an effective method to produce highly stable, n-doped conjugated polymers.