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Abstract The combination of inorganic and organic semiconductors in a heterojunction is considered a promising approach to overcome limitations of each individual material class. However, to date only few examples of improved (opto‐)electronic functionality have been realized with such hybrid heterojunctions. The key to unraveling the full potential offered by inorganic/organic semiconductor heterojunctions is the ability to deliberately control the interfacial electronic energy levels. Here, a universal approach to adjust the offset between the energy levels at inorganic/organic semiconductor interfaces is demonstrated: the interlayer method. A monolayer‐thick interlayer comprising strong electron donor or acceptor molecules is inserted between the two semiconductors and alters the energy level alignment due to charge transfer with the inorganic semiconductor. The general applicability of this method by tuning the energy levels of hydrogenated silicon relative to those of vacuum‐processed films of a molecular semiconductor as well as solution‐processed films of a polymer semiconductor is exemplified, and is shown that the energy level offset can be changed by up to 1.8 eV. This approach can be used to adjust the energy levels at the junction of a desired material pair at will, and thus paves the way for novel functionalities of optoelectronic devices. 

Abstract Doping 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)] with the bulky, strongly reducing metallocene 1,2,3,4,1′,2′,3′,4′‐octaphenylrhodocene (OPR) leads to an increased bulk conductivity and a decreased contact resistance. While the former arises from low‐level n‐doping of the intrinsic polymer and increased carrier mobility due to trap‐filling, the latter arises from a pronounced accumulation of dopant molecules at an indium tin oxide (ITO) substrate. Electron transfer from OPR to ITO leads to a work function reduction, which pins the Fermi level at the P(NDI2OD‐T₂) conduction band and thus minimizes the electron injection barrier and the contact resistance. The results demonstrate that disentangling the effects of electrode modification by the dopant and bulk doping is essential to comprehensively understand doped organic semiconductors.