Abstract: This invention relates to a process for the preparation of polycrystalline silicon ingots by providing a first layer of coating on the inside walls of a mold with a slurry of silicon nitride powder in an organic binder dissolved in a solvent; charging the said coated mold with silicon pieces along with calcium chloride or/and calcium fluoride; heating the mold to a temperature in the range of 1420.degree.-1500.degree. C. so as to melt the silicon, by keeping the mold inside the furnace; bringing down the temperature of the mold to a temperature 5.degree.-10.degree. C. above the melting point of silicon; withdrawing the mold containing the melt downwardly and slowly from the hot zone of the furnace so that the solidification of the melt starts from the bottom of the mold and proceeds towards the top as the withdrawal continues till all the melt solidifies; cooling the mold to the room temperature under inert atmosphere and removing the polycrystalline silicon ingot from the mold.