Shallow fluorine-vacancy ͑FV͒ complexes in Si have been directly observed using variable-energy positron annihilation spectroscopy and secondary ion mass spectrometry. The FV complexes, introduced to combat the deactivation and transient-enhanced diffusion of ultrashallow boron, were observed in preamorphized Si wafers implanted with 0.5 keV B and 10 keV F ions at a dose of 10 15 cm −2 , and then annealed isothermally at 800°C for times ranging from 1 to 2700 s. The results are in agreement with a model which predicts that the complexes are of the form F 3n V n , with n most probably being 1 and/or 2. © 2006 American Institute of Physics. ͓DOI: 10.1063/1.2335594͔Interest in the beneficial consequences of implanting F ions in Si has grown in recent years as defect engineering has been developed to meet the continuing challenges of device miniaturization. The application of particular interest here concerns ultrashallow B implantation into preamorphized Si regrown via solid-phase epitaxy ͑SPE͒; efficient activation of the B while limiting its diffusion is the key to the formation of ultrashallow junctions. Recent work by Cowern et al. 1 showed that F in B-implanted Si can form clusters that trap interstitals ͑I͒ released from the band of end-of-range ͑EOR͒ defects, which in turn both retard the transient enhanced diffusion of B implants and significantly decrease their deactivation. Kham et al. 2 linked F found at half the projected ion range to the formation of clusters of F with vacancies ͑V͒ in this region. Other studies conclude that FV or FI complexes suppress B diffusion by reducing I emission from extended I defects generated by implantation. 3,4 Variable-energy positron annihilation spectroscopy ͑VE-PAS͒ is used here to probe the nature of the complexes formed by the implanted F ions. The technique has been used to identify FV complexes in thermally treated F-implanted Si. 5,6 VEPAS measures the Doppler broadening of the 511 keV ␥-ray annihilation line, whose extent is determined by the average momentum of the electrons at the annihilation site. The broadening is characterized by the line-shape parameter S, defined as the central fraction of the 511 keV line. S for a chosen experimental setup has a characteristic value for each annihilation site, for example, for pure bulk Si or for each specific vacancy-type defect, the latter being strong positron traps. The mean depth z of positrons implanted with energy E ͑keV͒ is determined from the relation z = 17.2 E 1.6 nm. Secondary ion mass spectrometry ͑SIMS͒ measurements were performed to determine atomic profiles.Samples used in this study were n-type ͗100͘ Cz Si wafers with a resistivity of 10-20 ⍀ cm. All wafers were first preamorphized with 30 keV, 10 15 cm −2 Ge ions, and implanted with 0.5 keV B ions at 10 15 cm −2 . Half of the samples were additionally implanted with F ions at 10 keV and 10 15 cm −2 , placing the F ions between the B implants and the amorphous-crystalline interface. After restoring the amorphous layer to crystallinity via SPE regrowth ...