AbstractBy analyzing internal photoemission of electrons from Si/SiOx‐passivated Ge into insulating HfO2 we found that insertion of additional La interlayer between SiOx and HfO2 leads to dramatic increase (more than by factor of 20) of the barrier transparency. However, no measurable variation of the interface barrier height is observed suggesting that La induces intermixing of near‐interface oxide stack resulting in development of additional density of states corresponding to conduction band of LaOx and HfOx sub‐networks. At the same time, photoemission results indicate the presence of discrete positive charges in the near‐interface oxide layer which may explain the observed ∼1 V shift of capacitance‐voltage curves. (© 2016 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)