We investigate three amine-based polymers, polyethylenimine and two amino-functionalized polyfluorenes, as electron injection layers (EILs) in organic light-emitting diodes (OLEDs) and find correlations between the molecular structure of the polymers, the electronic alignment at the emitter/EIL interface, and the resulting device performance. X-ray photoelectron spectroscopy measurements of the emitter/EIL interface indicate that all three EIL polymers induce an upward shift of the Fermi level in the emitting layer close to the interface similar to n-type doping. The absolute value of this Fermi level shift, which can be explained by an electron transfer from the EIL polymers into the emitting layer, correlates with the number of nitrogen-containing groups in the side chains of the polymers. Whereas polyethylenimine (PEI) and one of the investigated polyfluorenes (PFCON-C) have six such groups per monomer unit, the second investigated polyfluorene (PFN) only possesses two. Consequently, we measure Fermi level shifts of 0.5-0.7 eV for PEI and PFCON-C and only 0.2 eV for PFN. As a result of these Fermi level shifts, the energetic barrier for electron injection is significantly lowered and OLEDs which comprise PEI or PFCON-C as an EIL exhibit a more than twofold higher luminous efficacy than OLEDs with PFN.
Keywords: OLEDs; amino-functionalized polyfluorenes; electron injection layers; polyethylenimine; solution processing.