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The transition regions of GdSiO/SiOx and HfO2/ SiOx interfaces have been studied with the high-k layers deposited on silicon substrates. The existence of transition regions was verified by medium energy ion scattering (MEIS) data and transmission electron microscopy (TEM). From measurements of thermally stimulated current (TSC), electron states were found in the transition region of the HfO2/SiOx structures, exhibiting instability attributed to the flexible structural molecular network expected to surround the trap volumes. The investigations were focused especially on whether the trap states belong to an agglomeration consisting of a single charge polarity or of a dipole constellation. We found that flat-band voltage shifts of MOS structures, that reach constant values for increasing oxide thickness, cannot be taken as unique evidence for the existence of dipole layers.