Since the pivotal discovery that alkylsilane can covalently bond and induce doping phenomena in organic semiconductors, subsequent studies have clearly demonstrated its strengths and potential applicability in organic electronics. However, the underlying reactions and doping mechanisms remain elusive, limiting their widespread application. In this study, poly(benzodifurandione) (PBFDO) was used to elucidate these two mechanisms. The findings revealed that hydrolyzed alkylsilane deforms carbonyl groups by nucleophilic addition, leading to electrostatic doping driven by the dipole moment. This study provides clear evidence of the exact reaction site where covalent bonding occurs and further accentuates the strengths and potential applications of the alkylsilane doping strategy. Remarkably, aminoalkylsilanes enable further doping of the highly doped pristine PBFDO, achieving an unprecedentedly high doping efficiency of up to 1.79 electrons per repeating unit.
Kang et al. (Mon,) studied this question.