Reflectance difference spectroscopy (RDS) was applied to the characterization of SiO(2)/Si, GeO(2)/Ge, and high-k/III-V interface structures. We extended the spectral range of RDS to 8.4 eV in order to explore the optical transitions at the dielectrics-semiconductor interfaces as well as to have a high sensitivity to the interface anisotropy. Si surfaces with (110), (113), (331) and (120) orientations showed oxidation-induced RD changes in the vacuum-ultraviolet (VUV) range which were dependent on the surface orientation, oxidation method (dry or wet), and oxidation temperature. The Ge(110) surface also showed characteristic oxidation-induced changes in the VUV range, whereas Al(2)O(3) deposition on GaAs(001) and InP(001) surfaces induced only the RD amplitude changes. (C) 2010 Elsevier B.V. All rights reserved.