Positron annihilation spectroscopy (PAS) in Doppler broadening mode was used to study the vacancy profile of crystalline Si after He and B implantation and subsequent annealing. In the He-implanted samples two different void layers were observed, one consisting of large voids at the projected range of He and another containing “nanovoids” slightly larger than divacancies at roughly halfway between Rp of He and the surface. The nanovoid layer was shown to be absent from samples co-implanted with B, implying that interstitials created during B implantation get trapped in the nanovoids and fill them, thus hindering interstitial-mediated B diffusion.