Molecular electrical doping is of central technological relevance for organic (opto-) electronics since it allows control of charge carrier density and Fermi level position in organic semiconductors (OSCs). Here, we chose to investigate the doping capability of the n-dopant 1,2,3,4,1′,2′,3′,4′-octaphenylrhodocene (OPR). Using the bulky, strongly reducing metallocene to dope the electron-transport polymer poly{[N,N-bis(2-octyldodecyl)naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5’-(2,2’-bithiophene)} [P(NDI2OD-T2)] leads to an increased bulk conductivity and decreased contact resistance. While the former is due to low-level n-doping of the polymer, trap filling and concomitant charge carrier mobility increase, the latter is caused by an accumulation of OPR at an indium tin oxide (ITO) substrate.
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