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In vacuo high-sensitivity low energy ion scattering (HS-LEIS) has been used to investigate the initial growth stages of DC sputtered Ru on top of Si, SiN and SiO2. The high surface sensitivity of this technique allowed an accurate determination of surface coverages and thicknesses required for closing the Ru layer on all three substrates. The Ru layer closes (100% Ru surface signal) at about 2.0, 3.2 and 4.7 nm on top of SiO2, SiN and Si, respectively. In-depth Ru concentration profiles can be reconstructed from the Ru surface coverages when considering an error function like model. The large intermixing (4.7 nm) for the Ru-on-Si system is compared to the reverse system (Si-on-Ru), where only 0.9 nm intermixing occurs. The difference is predominantly explained by the strong Si surface segregation that is observed for Ru-on-Si. This surface segregation effect is also observed for Ru-on-SiN, but is absent for Ruon-SiO2. For this last system, in vacuo HS-LEIS analysis revealed surface oxygen directly after deposition, which suggests an oxygen surface segregation effect for Ru-on-SiO2. In vacuo XPS measurements confirmed this hypothesis based on the reaction of Ru with oxygen from the SiO2, followed by oxygen surface segregation.

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The initial growth of DC sputtered ZrO2 on top of a-Si, SiN, and SiO2 layers has been studied by in vacuo high-sensitivity low energy ion scattering for two gas deposition conditions with different oxygen contents (high-O and low-O conditions). This unique surface sensitive technique allowed the determination of surface composition and thicknesses required to close the ZrO2 layer on all three substrates for both conditions. The ZrO2 layer closes similarly on all substrates due to more favorable enthalpies of formation for ZrO2 and ZrSiO4, resulting in passivation of the Si from the substrate. However, this layer closes at about half of the thickness (∼1.7 nm) for low-O conditions due to less oxidative conditions and less energetic particles arriving at the sample, which leads to less intermixing via silicate formation. In contrast, for high-O conditions, there is more ZrSiO4 and/or SiOx formation, giving more intermixing (∼3.4 nm). In vacuo X-ray photoelectron spectroscopy (XPS) measurements revealed similar stoichiometric ZrO2 layers deposited by both conditions and a higher interaction of the ZrO2 layer with the underlying a-Si for high-O conditions. In addition, oxygen diffusion through low-O ZrO2 films on a-Si has been investigated by ex situ angular-resolved XPS of samples annealed in atmospheric oxygen. For temperatures below 400 °C, no additional oxidation of the underlying a-Si was observed. This, together with the amorphous nature and smoothness of these samples, makes ZrO2 a good candidate as an oxidation protective layer on top of a-Si.