Towards understanding the doping mechanism of organic semiconductors by Lewis acids
Towards understanding the doping mechanism of organic semiconductors by Lewis acids
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DOI：
10.1038/s41563-019-0479-0
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发表时间：
2019-12-01
期刊：
影响因子：
41.2
通讯作者：
Thuc-Quyen Nguyen
中科院分区：
文献类型：
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作者：
Yurash, Brett;Cao, David Xi;Thuc-Quyen Nguyen
有机半导体的精确掺杂允许控制这些材料的导电性，这是电子应用中的一个重要参数。虽然刘易斯酸最近显示出作为溶液加工聚合物的掺杂剂的前景，但它们的掺杂机理尚未完全理解。在这项研究中，我们发现，B（C6 F5）（3）是一个上级掺杂剂比其他刘易斯酸研究（BF 3，BBr 3和AlCl 3）。实验表明，与聚合物形成的刘易斯酸碱加合物抑制了掺杂过程。电子-核双共振和核磁共振实验，连同密度泛函理论，表明p型掺杂发生通过生成水-路易斯酸络合物与大量的布朗斯台德酸度，然后由质子化的聚合物主链和电子转移从中性链段带正电的，质子化的。这项研究为质子酸掺杂提供了一条潜在的途径，并显示了微量的水如何将刘易斯酸转化为强大的布朗斯台德酸。
Precise doping of organic semiconductors allows control over the conductivity of these materials, an essential parameter in electronic applications. Although Lewis acids have recently shown promise as dopants for solution-processed polymers, their doping mechanism is not yet fully understood. In this study, we found that B(C6F5)(3) is a superior dopant to the other Lewis acids investigated (BF3, BBr3 and AlCl3). Experiments indicate that Lewis acid-base adduct formation with polymers inhibits the doping process. Electron-nuclear double-resonance and nuclear magnetic resonance experiments, together with density functional theory, show that p-type doping occurs by generation of a water-Lewis acid complex with substantial Bronsted acidity, followed by protonation of the polymer backbone and electron transfer from a neutral chain segment to a positively charged, protonated one. This study provides insight into a potential path for protonic acid doping and shows how trace levels of water can transform Lewis acids into powerful Bronsted acids.