High work-function metal oxides are common for enhancing
hole injection
into organic semiconductors. However, the current understanding of
the electrostatic mechanism needs to be more consistent with materials’
electronic properties. Here, we study the electrostatic profile of
high work-function oxides by considering their dielectricity and energetic
disorder. Using MoO3 as an example, we first show that
the significant vacuum-level change at the electrode–oxide
interface originates from electrode doping rather than the conventionally
assumed interface dipole. Moreover, electrode doping is enough to
explain the Fermi-level shift, so MoO3’s characteristic
n-type property is not necessarily due to intrinsic donors. This conclusion
also applies to the n-type oxides with reduced work functions, like
WO3, V2O5, and p-type NiO. Finally,
the dielectricity of the oxide, either n-type or p-type, reduces the
surface p-doping of the further deposited organic layer. Increasing
the oxide’s metallicity and energetic disorder facilitates
the hole injection.