The use of polyethylenimine (PEI) as a thin interlayer between cathodes and organic semiconductors in order to reduce interfacial Ohmic losses has become an important approach in organic electronics. It has also been shown that such interlayers can form spontaneously because of vertical phase separation when spin-coating a blended solution of PEI and the semiconductor. Furthermore, bulk doping of semiconducting polymers by PEI has been claimed. However, to our knowledge, a clear delineation of interfacial from bulk effects has not been published. Here, we report a study on thin films formed by spin-coating blended solutions of PEI and 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)] on indium tin oxide. We observed the vertical phase separation in such films, where PEI accumulates at the bottom and the top, sandwiching the semiconductor layer. The PEI interlayer on ITO reduces the electron injection barrier to the minimum value determined by Fermi level pinning, which, in turn, reduces the contact resistance by 5 orders of magnitude. Although we find no evidence for doping-induced polarons in P(NDI2OD-T2) upon mixing with PEI from optical absorption, more sensitive electron paramagnetic resonance measurements provide evidence for doping and an increased carrier density, at a very low level. This, in conjunction with an increased charge carrier mobility due to trap filling, results in an increase in the mixed polymer conductivity by 4 orders of magnitude relative to pure P(NDI2OD-T2). Consequently, both interfacial and bulk effects occur with notable magnitude in thin films formed from blended semiconductor polymer/PEI solution. Thus, this facile one-step procedure to form PEI interlayers must be applied with attention, as modification of the bulk semiconductor polymer (here doping) may occur simultaneously and might go un-noticed if not examined carefully.
