The use of a GeO2 interfacial layer (IL) between a high-k dielectric and a Ge substrate helps to reduce the interface state density in Ge MOS devices. We report that the presence of the GeO2 IL changes the effective work function (eWF) of the gate stack when annealed after high-k dielectric deposition. The eWF is reduced from 4.31 eV to 3.98 eV for TaN and from 5.00 eV to 4.44 eV for Ni. Consequently, the threshold voltage (V-th) decreases from 0.69 V to 0.21 V for Ni after post deposition annealing. Our investigation confirms that the generation of oxygen vacancies in the GeO2 IL near the Ge substrate is the main cause of the eWF modulation. In addition, the reliability of the GeO2 IL is investigated via the conductance method and a constant-current stress test. (C) 2017 Elsevier Ltd. All rights reserved.