Continued reduction in resistance-capacitance (RC) delays in nano-electronic Cu interconnect structures will require new materials with increasingly lower dielectric constants (i.e. low-k). Significant reductions in RC delay can be achieved by reducing the dielectric constant of the relatively high dielectric constant Cu capping/etch stop layer. However, this risks comprising the required barrier performance of this material to the diffusion of Cu, H 2 O, and other species. In this regard, critical thresholds for the diffusion of water and solvents through low-k a-SiO x C y N z :H dielectrics of varying composition were investigated using a combination of X-ray reflectivity mass density and positronium annihilation lifetime spectroscopy pore size metrologies. It was observed that hermetic low-k a-SiO x C y N z :H dielectrics were achieved only at mass densities >2.0 g/cm 3 and when the pore diameter was less than twice the molecular diameter of water. The implications of these critical nano-porosity thresholds on continued scaling of low-k diffusion barrier and ILD materials are discussed as well as methods for overcoming these limitations.