The authors have investigated ultrashallow p+∕n-junction formation by solid-phase epitaxy, by using x-ray absorption near-edge spectroscopy (XANES) measurements at the B K edge. The authors demonstrate that B clustering occurs during the very early stages of annealing-induced Si recrystallization, i.e., when B is still in the 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. The XANES structure are assigned to B–B sp2 bonds that are present in B clusters with two or more B atoms. Boron clustering and diffusion are further investigated by means of concentration profile analysis of ad hoc amorphous on insulator structures that evidences a clear concentration threshold for clustering and a concentration dependent B diffusion.