The present article evaluates, in qualitative and quantitative manners, the characteristics (i.e., thickness of layers, crystal structures, growth orientation, elemental diffusion depths, edge, and screw dislocation densities), within two GaN/AlN/Si heterostructures, that alter their efficiencies as positron moderators. The structure of the GaN film, AlN buffer layer, substrate, and their growth relationships were determined through high-resolution transmission electron microscopy (HR-TEM). Data resulting from high-resolution X-ray diffraction (HR-XRD) was mathematically modeled to extract dislocation densities and correlation lengths in the GaN film. Positron depth profiling was evaluated through an experimental Doppler broadening spectroscopy (DBS) study, in order to quantify the effective positron diffusion length. The differences in values for both edge ( ρ d e ) and screw ( ρ d s ) dislocation densities, and correlation lengths (Le, Ls) found in the 690 nm GaN film, were associated with the better effective positron diffusion length (Leff) of L eff GaN 2 = 43 ± 6 nm.