Process for electrolytically plating copper
View Patent ↗An electrolytic copper plating process comprising two steps is proposed. The process is particularly suited to plating in very confined spaces. The first step comprises a pre-treatment solution comprising an anti-suppressor that comprises a sulfur containing organic compound, preferably incorporating an alkane sulfonate group or groups and/or an alkane sulfonic acid. The second step comprises an electrolytic copper plating solution based on an alkane sulfonic acid.
1. A process for electrolytically plating copper on a surface, said process comprising:
a) contacting the surface with a pre-treatment solution comprising an aqueous solution comprising a sulfur containing organic compound and from about 0.01 to about 5 g/l of copper ions; and then
b) contacting said surface as a cathode with an electrolytic copper plating solution comprising (i) copper ions, (ii) from about 40 to about 200 g/l of an alkane sulfonic acid; (iii) chloride ions, and (iv) an aldehyde or ketone compound; and applying a plating current such that copper is plated on the surface;
wherein the pH of the pre-treatment solution is in the range of 1 to 3.5.
2. A process according to claim 1 wherein the sulfur containing organic compound comprises a sulfonate group or a sulfonic acid group.
3. A process according to claim 1 wherein the plating solution also comprises at least one additive selected from the group consisting of brightener additives, leveler additives, surfactants and wetters.
4. A process according to claim 3 wherein the brightener additives comprise disodium bis(3-sulfopropyl) disulfide and the leveler additives comprise tetrapolypropoxy-ethoxy ethylenediamine sulfosuccinic ester sodium salt.
5. A process according to any one of claim 1 , 3 , or 4 , wherein the sulfur containing organic compound comprises disodium bis(3-sulfopropyl) disulfide.
6. A process according to claim 1 wherein the plating current is a constant direct current.
7. A process according to any one of claim 1 , 2 , 3 , or 4 , wherein the plating current varies over time.
8. A process according to claim 1 wherein the electrical polarity of the cathode is reversed periodically.
9. A process according to claim 1 wherein:
a) the pre-treatment solution comprises copper ions and disodium bis(3-sulfopropyl) disulfide; and
b) the plating solution comprises disodium bis(3-sulfopropyl) disulfide and tetrapolypropoxy ethoxy ethylene diamine sulfosuccinic ester sodium salt.