High dielectric constant insulators deposited at low temperatures rapidly absorb water during exposure to the atmosphere, and the resulting OH leads to detrimental interface reactions. We report the effect of atmospheric exposure on ultrathin yttrium oxide, and details of silicon substrate reactions during postdeposition anneals. Infrared absorption analysis indicates significant absorption of water vapor during atmospheric exposure, even for very short times (<15 min). X-ray photoelectron spectroscopy demonstrates that after OH absorption, a thermally activated interface reaction proceeds with an activation energy of 0.33 eV, consistent with substrate reaction with OH present in the film. The OH absorption rate is reduced for annealed films or when capping layers are deposited in situ. Similar oxidation processes are expected to occur in other high-k materials of interest, where the rate of OH absorption will depend on the deposition process and material thermal history. © 2002 American Institute of Physics.