Water and oxygen molecules determine many of the properties of amorphous SiO2 used in several technologies, but the underlying atomic-scale processes remain unresolved. We report results of first-principles calculations showing that a wide range of behavior is possible in an amorphous environment, including diffusion of the molecule as a whole and various reactions with the network. Experimental data including oxygen exchange reaction and radiation sensitivity are accounted for. The possibility of H3O+ formation as a source of positive charge is discussed.

Redshifts of luminescence relative to optical absorption bands (Stokes shifts) of molecules and of defects in solids are universally attributed to slow atomic relaxations on the grounds that electronic transitions are fast (Franck-Condon principle). Here we report a novel phenomenon that can occur only in the solid state: Stokes shifts caused by slow electronic relaxations. We demonstrate that the phenomenon occurs in the nonbridging oxygen defect in amorphous SiO2. We predict that another defect (OH group), which can exist in either crystalline or amorphous SiO2, has a similar Stokes shift, but it arises from a mix of lattice and electronic relaxations with manifest differences in the two phases.

Interstitial water and oxygen molecules are ubiquitous impurities and participate in various defect formation processes in thermally grown SiO 2 films and synthetic silica glass. Using results of first-principles calculations we report the types of defects ͑including different possible charge states͒ that H 2 O and O 2 molecules may form in bulk amorphous SiO 2 . We calculate their formation energies and, in the most interesting cases, the energy barriers in order to map out the most likely defect formation scenarios. In particular, we show that water molecules may form double silanol groups ͑Si-OH͒ as well as H 3 O ϩ and OH Ϫ ions at a low energy cost with a barrier of about 1.5 eV. The formation energies of other defects emanating from H 2 O interstitials are, however, too high to be thermally activated. We found that O 2 molecules may form ozonyl ͑Si-O-O-O-Si͒ linkages with an energy barrier of ϳ2.4 eV. An explanation for the oxygen isotope exchange observed in thin SiO 2 films near the Si-SiO 2 and SiO 2 -vacuum interfaces is suggested based on the energy barrier for ozonyl formation being commensurate with the O 2 diffusion barrier close to the Si/SiO 2 interface and the O 2 incorporation energy from vacuum. We also explain the different creation rates of EЈ centers in wet and dry oxides by studying the annihilation mechanism of neutral and charged oxygen vacancies.

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