Silver nanoparticles having a mean height ranging from 2 to 20 nm have been electrodeposited on hydrogen-terminated n(2+)-Si(100) surfaces. The deposition of silver was carried out potentiostatically from dilute ([Ag+] = 1 mM) acetonitrile-based solutions using a large overpotential, E-appl -800 mV versus Ag+/Ag-0, and a voltage pulse duration ranging from 2 to 25 ms. Under these conditions, less than 0.20 of a silver monolayer was deposited, and this silver was present on the surface as silver nanoparticles which were similar in size. The metallic nature of these nanoparticles was confirmed using selected area electron diffraction. The evolution of the areal density of nanoparticles, and the nanoparticle height were both tracked as a function of the plating pulse duration ex situ using noncontact atomic force microscopy. As the pulse duration was increased from 2 to 25 ms, the mean nanoparticle height increased from 2 to 20 nm while the areal density of nanoparticles concurrently increased from 1 to 3 x 10(8) cm(-2) to 2-2.5 x 10(9) cm(-2). This result shows conclusively that the nucleation of silver on Si(100) is progressive in this time domain.