The authors have investigated ultrashallow p+∕n-junction formation by solid-phase epitaxy, by using x-ray absorption near-edge spectroscopy measurements on the B K edge. A clear fingerprint of B–B clusters is detected in the spectra. The authors demonstrate that B clustering occurs during the very early stages of annealing-induced Si recrystallization, i.e., when B is still in an amorphous matrix. After complete regrowth the local structure around B remains the same as in the amorphous phase, implying that B clusters are transferred to the crystalline structure.