The investigation of the molecular layering (ML)-ALE synthesis of the SiO ₂ nanolayers on the Si substrate was performed by use of IR multiple transmission spectroscopy, ellipsometry and contact angle measurements. SiCl ₄ and H ₂ O were used as precursors. The correlation between structure of the native oxide on the Si surface, contact angle and the coverage of the surface by the SiO _4\2 tetrahedrons was established. The affect of the composition and the thickness of the SiO ₂ layer, as well as its hydroxylation, on the kinetics of the SiO ₂ layers growth was found.