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Spectroscopic ellipsometry was used to determine the density of oxides thermally grown on Si substrates as a function of the oxidation temperature, and the time and temperature of postoxidation anneals. All the oxides were found to be denser than fused silica. The density of the as-grown oxides was found to decrease as the growth temperature was increased. Postoxidation anneals were found to reduce the oxide density; high temperature or long-time anneals caused the greatest reduction in density. Holes alone, or holes and electrons, were injected into the oxides by irradiating with vacuum ultraviolet light or x rays under electric field bias. Using capacitance–voltage measurements, it was found that low-density oxides trap charge more efficiently than high-density oxides. Electron spin resonance measurements indicated that, for most of these oxides, the number of paramagnetic defects was substantially smaller than the number of trapped charges. It is hypothesized that the additional, nonparamagnetic, charge is in the form of protons trapped near network oxygen atoms that have large Si–O–Si bond angles. The number of these large-angle bonds in the near-interfacial oxide increases as the oxide density decreases, explaining the observed correlation between the charge trapping and the oxide density. © 1999 American Institute of Physics.