Towards understanding the doping mechanism of organic semiconductors by Lewis acids

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 Brønsted 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 Brønsted acids.