For acid copper plating baths containing a brightener used to produce smooth copper coatings of high brilliancy, it has been found that the "break-in" period normally needed after a brightener is added to the plating bath, has been virtually eliminated by use of the brightener of this invention. This brightener consists essentially of a peroxide oxidation product of a dialkylamino-thioxomethyl-thioalkanesulfonic acid wherein each alkyl and alkane group individually contains 1 to 6 carbon atoms and wherein the peroxide oxidation of the dialkylamino-thioxomethyl-thioalkane-sulfonic acid is carried out in an acid, aqueous medium having a pH of not more than about 1. In an added embodiment of this invention the acid copper plating bath also contains hydrolysis products of the peroxide oxidation product of a dialkylamino-thioxomethyl-thioalkanesulfonic acid.
A method for electrolytic copper plating using an electrolytic copper plating solution including a compound containing a structure of --X--S--Y--, wherein X and Y are independently chosen from hydrogen atom, carbon atom, sulfur atom, nitrogen atom, and oxygen atom, and X and Y may be the same only when they are a carbon atom, and by contacting the electrolytic copper plating solution with ozone is disclosed.
The present invention relates to a copper electroplating bath composition and method of using it for microelectronic device fabrication. In particular, the present invention relates to copper electroplating in the fabrication of interconnect structures in semiconductor devices. By use of the inventive copper electroplating bath composition, the incidence of voids in the interconnect structures is reduced.
The present invention provides an aqueous electroplating solution. The aqueous electroplating solution includes a copper salt comprising a weight by weight percent of the electroplating solution between about 0.1% to about 2.5%. The electroplating solution also includes an inorganic acid having a dissociation constant of less than about 2.0, and comprising a weight by weight percent of the electroplating solution between about 0.1% to about 10%. The electroplating solution further includes a hydrogenated halide and a modulator, each that comprises a weight by weight percent of the electroplating solution between about 0.0001% to about 1%.
The present invention provides methods for the use of copper electroplating compositions. Electroplating compositions of the invention contain an increased brightener concentration that can provide effective copper plate on difficult-to-plate aperture walls, including high aspect ratio, small diameter microvias.
Disclosed are an electrolytic copper plating solution containing a specific sulfur-containing compound and a thiol-reactive compound, and an electrolytic copper plating process using such an electrolytic copper plating solution. The present invention can prevent the copper layer on the resulting composite material from forming aggregation and, when the plating is intended to fill vias, make it possible to achieve the via-filling without voids. The present invention also relates to a method for controlling the electrolytic copper plating solution by using an amount of a specific decomposition product of the sulfur-containing compound as an index.
