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A comparative investigation is performed on the effects of vacancies induced by rapid thermal processing on oxygen precipitation behavior in heavily arsenic- and antimony-doped Czochralski silicon wafers. It is experimentally found that vacancy-assisted oxide precipitate nucleation occurs at 800, 900, and 1000 °C in the Sb-doped wafers, while it only occurs at 800 °C in the As-doped ones. Density functional theory calculations indicate that it is energetically favorable to form AsVO and SbVO complexes in As- and Sb-doped silicon crystals, respectively. These complexes might act as precursors for oxide precipitate nucleation under appropriate conditions. The difference between the effects of rapid thermal processing -induced vacancies on oxide precipitate nucleation in the heavily As- and Sb-doped Cz silicon crystals is tentatively elucidated based on density functional theory calculations revealing the difference in binding energies of AsVO and SbVO complexes.