The impact of hydrogen desorption on the electrical properties of TiOx on crystalline silicon (c-Si) with SiOy interlayers is studied for the development of high-performance TiOx carrier-selective contacts. Compared with the TiOx/c-Si heterocontacts, a lower surface recombination velocity of 9.6 cm/s and lower contact resistivity of 7.1 m Omega cm(2) are obtained by using SiOy interlayers formed by mixture (often called SC2). The hydrogen desorption peaks arising from silicon dihydride (alpha 1) and silicon monohydride (alpha 2) on the c-Si surface of the as deposited samples are observed. The alpha 1 peak pressure of as-deposited heterocontacts with SiOx interlayers is lower than that of heterocontacts without a SiOy interlayer. Furthermore, the hydrogen desorption energies are found to be 1.76 and 2.13 eV for the TiOx/c-Si and TiOx/SC2-SiOy/c-Si heterocontacts, respectively. Therefore, the excellent passivation of the TiOx/SC2-SiOy/c-Si heterocontacts is ascribed to the relatively high rupture energy of bonding between Si and H atoms.