Method for activating a copper surface for electroless plating
View Patent ↗The present invention relates to method for activating a copper or copper alloy surface for depositing a metal or metal alloy layer by electroless (autocatalytic) plating thereon wherein the formation of undesired voids is suppressed. The copper or copper alloy surface is contacted with palladium ions, at least one phosphonate compound and halide ions followed by electroless (autocatalytic) deposition of a metal such as palladium or a metal alloy such as a Ni—P alloy.
1. A method for activating a copper or copper alloy surface for depositing a metal or metal alloy layer by electroless (autocatalytic) plating thereon comprising, in this order, the steps of
i. providing a substrate comprising a copper or copper alloy surface,
ii. contacting said substrate directly with the following components
a. an aqueous solution containing a source of palladium ions,
b. an aqueous solution containing a phosphonate compound
c. an aqueous solution containing a source of halide ions and
iii. depositing a metal or metal alloy layer onto the activated copper or copper alloy surface obtained in step ii. by electroless plating wherein no organic acid or salt thereof comprising a carboxylic group without phosphonate group is used in step ii.
2. The method for activating a copper or copper alloy surface for depositing a metal or metal alloy layer thereon according to claim 1 wherein the substrate is contacted in step ii. with one aqueous solution comprising a source of palladium ions palladium ions, at least one phosphonate compound and halide ions.
3. The method for activating a copper or copper alloy surface for depositing a metal or metal alloy layer thereon according to claim 2 wherein the concentration of palladium ions ranges from 0.01 to 1 g/l.
4. The method for activating a copper or copper alloy surface for depositing a metal or metal alloy layer thereon according to claim 2 wherein the concentration of the at least one phosphonate compound ranges from 0.3 to 20 mmol/l.
5. The method for activating a copper or copper alloy surface for depositing a metal or metal alloy layer thereon according to claim 2 wherein the concentration of halide ions ranges from 0.1 to 100 mg/l.
6. The method for activating a copper or copper alloy surface for depositing a metal or metal alloy layer thereon according to claim 2 wherein the halide ions are chloride ions.
7. The method for activating a copper or copper alloy surface for depositing a metal or metal alloy layer thereon according to claim 1 wherein the substrate is contacted in step ii. with a first aqueous solution comprising a source of palladium ions and at least one phosphonate compound which is free of halide ions and thereafter with a second aqueous solution comprising halide ions.
8. The method for activating a copper or copper alloy surface for depositing a metal or metal alloy layer thereon according to claim 7 wherein the concentration of palladium ions in the first aqueous solution ranges from 0.01 to 1 g/l.
9. The method for activating a copper or copper alloy surface for depositing a metal or metal alloy layer thereon according to claim 7 wherein the concentration of the at least one phosphonate in the first aqueous solution ranges from 0.3 to 20 mmol/l.
10. The method for activating a copper or copper alloy surface for depositing a metal or metal alloy layer thereon according to claim 7 wherein the halide ions in the second aqueous solution are chloride ions.
11. The method for activating a copper or copper alloy surface for depositing a metal or metal alloy layer thereon according to claim 1 wherein the source of palladium ions is a water soluble palladium salt.
12. The method for activating a copper or copper alloy surface for depositing a metal or metal alloy layer thereon according to claim 1 wherein the at least one phosphonate compound is selected from the group comprising 1- hydroxyethane-1,1,-diphosphonic acid, hydroxyethyl-amino-di(methylene phosphonic acid), carboxymethyl-amino-di (methylene-phosphonic-acid), amino-tris(methylene phosphonic-acid), ethylendiamine-tetra(methylene phosphonic acid), hexamethylendiamino-tetra(methylene phosphonic acid), diethylen-triamine-penta (methylene phosphonic acid) and 2-phosphonobutane-1,2,4-tricarboxylic acid.
13. The method for activating a copper or copper alloy surface for depositing a metal or metal alloy layer thereon according to claim 1 wherein the metal or metal alloy deposited in step iii. is selected from the group comprising palladium, palladium alloys, nickel alloys and cobalt alloys.
14. The method for activating a copper or copper alloy surface for depositing a metal or metal alloy layer thereon according to claim 3 wherein the concentration of the at least one phosphonate compound ranges from 0.3to 20 mmol/l.
15. The method for activating a copper or copper alloy surface for depositing a metal or metal alloy layer thereon according to claim 3 wherein the concentration of halide ions ranges from 0.1 to 100 mg/l.
16. The method for activating a copper or copper alloy surface for depositing a metal or metal alloy layer thereon according to claim 4 wherein the concentration of halide ions ranges from 0.1 to 100 mg/l.
17. The method for activating a copper or copper alloy surface for depositing a metal or metal alloy layer thereon according to claim 8 wherein the concentration of the at least one phosphonate in the first aqueous solution ranges from 0.3 to 20 mmol/l.
18. The method for activating a copper or copper alloy surface for depositing a metal or metal alloy layer thereon according to claim 7 wherein the source of palladium ions is a water soluble palladium salt.
19. The method for activating a copper or copper alloy surface for depositing a metal or metal alloy layer thereon according to claim 7 wherein the at least one phosphonate compound is selected from the group comprising 1-hydroxyethane-1,1,-diphosphonic acid, hydroxyethyl-amino-di (methylene phosphonic acid), carboxymethyl-amino-di(methylene-phosphonic-acid), amino-tris(methylene phosphonic-acid), ethylendiamine-tetra (methylene phosphonic acid), hexamethylendiamino-tetra(methylene phosphonic acid), diethylen-triamine-penta(methylene phosphonic acid) and 2-phosphonobutane-1,2,4-tricarboxylic acid.
20. The method for activating a copper or copper alloy surface for depositing a metal or metal alloy layer thereon according to claim 7 wherein the metal or metal alloy deposited in step iii. is selected from the group comprising palladium, palladium alloys, nickel alloys and cobalt alloys.