High-energy Si implantation into silicon creates a net defect distribution that is characterized by an excess of interstitials near the projected range and a simultaneous excess of vacancies closer to the surface. This defect distribution is due to the spatial separation between the distributions of interstitials and vacancies created by the forward momentum transferred from the implanted ion to the lattice atom. This dissertation investigates the evolution of the near-surface vacancy excess in MeV Si-implanted silicon both during implantation and post-implant annealing. Although previous investigations have identified a vacancy excess in MeV-implanted silicon, the investigations presented in this dissertation are unique in that they are designed to correlate the free-vacancy supersaturation with the vacancies in clusters. Free-vacancy (and interstitial) supersaturations were measured with Sb (B) dopant diffusion markers. Vacancies in clusters were profiled by Au labeling; a new technique based on the observation that Au atoms trap in the presence of open-volume defects. The experiments described in this dissertation are also unique in that they were designed to isolate the deep interstitial excess from interacting with the much shallower vacancy excess during post-implant thermal processing.