When considering the optical performance of thin films in the Extreme Ultraviolet (EUV), developing an accurate physical description of a thin film coating is necessary to be able to successfully model optical performance. With the short wavelengths of the EUV, film interfaces and sample roughness warrant special attention and care. The surfaces of thin film samples are routinely measured by Atomic Force Microscopy, from which roughness can be determined. However, characterizing the quality of interfaces below the surface is much more challenging. In a recent study of scandium oxide thin films, High Resolution Transmission Electron Microscopy and Annular Dark Field Scanning Transmission Electron Microscopy (ADF STEM) were used to study the cross section of the samples. ADF STEM data analyzed along the path into the volume of the sample (normal to the interfaces) reveals information of sample density versus depth. This density-depth profile reflects the presence of subsurface film interfaces in the volume of the sample. Additionally, information from the ADF STEM profile can be used to gauge the roughness of the subsurface interfaces, which is used to refine the sample description during modeling. We believe this is the first use of ADF STEM in this capacity. This characterization technique may provide key insight to subsurface interface quality, which is particularly important when optimizing the performance of multilayer coatings in the EUV.