The silicon electrodeposition from the KF-KCl-(10 mol%) K₂SiF₆ melt at 943–1103 K has been studied. The polycrystalline continuous single-phase silicon coatings (∼99.9 wt% Si) have been obtained on the graphite, glassy carbon, silver, and tungsten substrates. The Raman spectroscopic study of the Si/C and Si/Ag interfaces has proved an absence of the intermediate phases. Two phases (Si and Ni₂Si) were formed during the silicon electrodeposition on nickel.

The regularities of silicon electrodeposition from the KF-KCl (2:1)—75 mol% KI melt containing 0.075 or 0.5 mol% of K ₂ SiF ₆ on glassy carbon and tungsten at 998 K were studied by the cyclic voltammetry, chronoamperometry and scanning electron microscopy methods. The silicon nucleation/growth processes on glassy carbon were analyzed in the framework of two theoretical models that imply diffusion controlled growth or kinetic (charge transfer) controlled growth. Continuous silicon nanofilms with good adhesion to the substrate were obtained by the electrodeposition under galvanostatic conditions. The reasons for the formation of Si films during electrodeposition from melts with potassium iodide were discussed.