The microstructural and electrical properties of Ge-based metal–oxide–semiconductor capacitors containing high-k gate dielectric layers were investigated with and without the presence of a GeOxNy interface layer. The effect of this nitrided layer on thermal stability of the metal oxide/Ge structures was probed by medium energy ion energy spectroscopy (MEIS). Atomic-layer deposited HfO2 on a chemical oxide-terminated Ge (100) surface exhibited poor capacitance–voltage behavior; however, direct substrate surface nitridation at 600 °C in NH3 ambient before HfO2 deposition improved the carrier trapping characteristics. Diffusion of metal impurities (including Hf) into the interfacial oxide/Ge-substrate may be an important source of the measured degradation of electrical properties. MEIS results suggested that the GeOxNy interface layer may inhibit Hf diffusion into the underlying semiconductor at the temperatures investigated.