Ultra-thin magnesium oxide layers were elaborated by atomic layer deposition and oxidation process on silicon (100) starting from (2 x 1) thermally-reconstructed or hydrogen-terminated Si surfaces. Low-energy electron diffraction experiments show (2 x 3) and (3 x 3) reconstructions while depositing a magnesium monolayer on Si clean surfaces, and a 3-dimentional growth of the oxide as confirmed by ex-situ atomic force microscopy. For hydrogen-terminated or clean surfaces previously physisorbed by oxygen, uniform cobalt/magnesium-oxide/silicon stacks of layers are observed by transmission electron microscopy. Annealing above 150 degrees C leads to MgO dissolution and formation of an interfacial complex compound by inter-diffusion of Si and Co. (C) 2011 Elsevier B.V. All rights reserved.