Several conductive structures which appeared to be usable as base electrodes in VLSI capacitors based on high dielectric materials have been annealed in oxygen at 650 °C. The studied structures were Pt/TiN, Pt/Ta, Au/TiN, Ru, and RuO2/Ru, prepared under a variety of conditions. The structures have been studied by Rutherford backscattering (RBS) and Auger Electron Spectroscopy (AES). It was found that none of the pure metals, Pt, Au, or Ru, can prevent the diffusion of oxygen to the underlying layer and its oxidation, thus causing a possible break in the electrical conduction path to the silicon substrate. Of the investigated materials, in the thickness range ≤ 110 nm only the RuO2/Ru couple preserved its electrical connectivity to the Si substrate and prevented diffusion of silicon to the surface of the electrode.