Nanometer-thick amorphous boron (a-B) layers were formed on (100) Si during exposure to diborane (B 2 H 6 ) in a chemical vapor deposition (CVD) system, either at atmospheric or reduced pressures, at temperatures down to 500°C. The dependence of the growth mechanism on processing parameters was investigated by analytical techniques, such as transmission electron microscopy (TEM) and secondary ion mass spectrometry (SIMS), in conjunction with extensive electrical characterization. In particular, devices fabricated by B deposition effectively demonstrated that p + doping of the silicon substrate can be achieved within 10 nm from the surface in a manner that is finely controlled by the B 2 H 6 exposure conditions. High-quality, extremely ultrashallow, p + n junctions were fabricated, and their saturation current was tuned from high Schottky-like values to low deep pn junction-like values by the increasing of the deposited B layer thickness. This junction formation exhibited high selectivity, isotropy, spatial homogeneity, and compatibility with standard Si device fabrication.