A study of resonant photo-absorption features in high-k dielectric film stacks using vacuum ultraviolet spectroscopic ellipsometry demonstrates that all optically observable dielectric-related defects are located in the interfacial SiO2 layer rather than in the bulk high-k film. The defects, located at 2.9 eV, 3.6 eV, 3.9 eV, and 4.75 eV within the bandgap of this bottom interface, are found to be strongly affected by processing conditions. These results are supported by both electrical and physical characterization measurements that identify a consistent trend in the evolution of charge trapping defects for samples subjected to identical processing conditions. In addition, evidence is provided correlating the optically active 2.9 eV defect to positively charged oxygen vacancies in the bottom interfacial layer that have recently been proposed as contributing to the flatband voltage roll-off phenomenon. The close connection between these results and both ab initio calculations and experimental findings substantiate the use of spectroscopic ellipsometry as a unique characterization method for identifying process-induced defects during development and fabrication of dielectric film stacks.