Using ultraviolet photoemission spectroscopy, we investigated the energy level alignment at the interfaces of typical anodes used in organic electronics, indium tin oxide (ITO) and poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS), with the oligomeric hole transport material N,N,N,N-tetrakis(4-methoxyphenyl)-benzidine (MeO-TPD), and studied the influence of electrical interface doping by the strong electron acceptor tetrafluoro tetracyanoquinodimethane (F4-TCNQ). The fundamentally different anode materials with work functions of 4.40eV (ITO) and 4.85eV (PEDOT:PSS) show different hole injection barriers, which also depend on the thickness of the F4-TCNQ interface dopant layer. PEDOT:PSS anodes exhibit a consistently lower hole injection barrier to MeO-TPD compared to ITO by 0.1eV. We attribute this low hole injection barrier to additional charge transfer reactions at the PEDOT:PSS/MeO-TPD interface. In contrast, the deposition of the electron acceptor at the interface helps significantly to lower the hole injection barrier for ITO anodes.

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