Al2O3 was deposited by pulsed DC reactive sputter on Ge(1 0 0) aiming at producing layers with reduced OH and H2O content in comparison with water-based atomic layer deposition. In this way, the intrinsic interaction of Al2O3 with Ge could be probed. Photoelectron spectroscopy showed evidence of a GeO2 interlayer in as-deposited samples. Thermal annealing in Ar or forming gas for 30 min at 350 degrees C reduced the amount of oxidized Ge, i.e. significant activity took place at the Al2O3/Ge interface irrespective of annealing ambient. The remaining transition layer consisted essentially of aluminum germanates. Analysis of Si companion samples indicates that in the absence of an oxidizing agent, Al2O3/Ge is more stable than Al2O3/Si. (C) 2012 Elsevier B.V. All rights reserved.