The inelastic electron tunnelling spectroscopy (IETS) technique is performed to provide information concerning the vibrational and excitational modes present in MOS tunnelling junctions (molecular species present in silicon dioxide and phonon modes of both silicon Substrate and silicon dioxide). The first relevant structures of silicon substrate phonons are investigated in both (1 1 1) and (1 0 0) orientations for the first time. The separated peaks obtained after deconvolution are identified and compared with literature data for both silicon orientations. The IET spectrum of ultra-thin silicon dioxide is also obtained though this spectrum is more difficult to detect. Finally, two different technologies of manufacturing MOS tunnelling junctions are compared. (C) 2003 Elsevier Ltd. All rights reserved.