Electroless palladium plating bath composition
View Patent ↗The present invention concerns an aqueous plating bath composition for electroless deposition of palladium and/or palladium alloys and a method which utilises such aqueous plating bath compositions. The aqueous plating bath comprises a source of palladium ions, a reducing agent, a nitrogenated complexing agent which is free of phosphorous and at least one organic stabilising agent comprising 1 to 5 phosphonate residues. The aqueous plating bath and the method are particularly useful if the aqueous plating bath comprises copper ions.
1. An aqueous plating bath for electroless deposition of palladium and/or palladium alloys onto a copper or copper alloy surface, the plating bath comprising
a. a source of palladium ions
b. at least one nitrogenated complexing agent which is free of phosphorous
c. a reducing agent selected from formic acid, formic acid derivatives, salts and mixtures of the aforementioned, hypophosphite compounds and amine-borane adducts and
d. at least one organic stabilising agent which comprises 1 to 5 phosphonate residues
wherein the concentration of the stabilising agent which comprises 1 to 5 phosphonate residues ranges from 0.1 to 100 mmol/l for stabilising agents comprising four and five phosphonate residues and from 50 to 500 mmol/l for stabilising agents comprising one, two and three phosphonate residues and wherein the at least one organic stabilising agent is selected from compounds according to formula (1)
wherein
R1 is selected from the group consisting of
hydrogen, methyl, ethyl, propyl and butyl;
R2 is selected from the group consisting of
hydrogen, methyl, ethyl, propyl and butyl;
R3 is selected from the group consisting of
hydrogen, methyl, ethyl, propyl and butyl;
R4 is selected from the group consisting of
hydrogen, methyl, ethyl, propyl and butyl;
n is an integer and ranges from 1 to 6; m is an integer and ranges from 1 to 6; o is an integer and ranges from 1 to 6; p is an integer and ranges from 1 to 6 and
X is selected from the group consisting of hydrogen and a suitable counter ion.
2. The aqueous plating bath according to claim 1 wherein X is selected from the group consisting of hydrogen, lithium, sodium, potassium and ammonium.
3. The aqueous plating bath according to claim 1 wherein n, m, o and p are independently selected from 1 and 2.
4. The aqueous plating bath according to claim 1 wherein n and m are 1 and o and p are 2.
5. The aqueous plating bath according to claim 1 wherein the stabilising agent is selected from compounds according to formula (1) with R1 and R3 selected from formula (2a), R2 selected from formula (2c) and R4 selected from formula (2d).
6. The aqueous plating bath according to claim 1 wherein the source of palladium ions is selected from palladium chloride, palladium nitrate, palladium acetate, palladium sulfate, palladium perchlorate and complex compounds comprising at least one palladium ion and at least one nitrogenated complexing agent which is free of phosphorous.
7. The aqueous plating bath according to claim 1 wherein the concentration of palladium ions ranges from 0.5 to 500 mmol/l.
8. The aqueous plating bath according to claim 1 wherein the nitrogenated complexing agent which is free of phosphorous is selected from primary amines, secondary amines and ternary amines.
9. The aqueous plating bath according to claim 1 wherein the mole ratio of nitrogenated complexing agent which is free of phosphorous and palladium ions ranges from 2:1 to 50:1.
10. The aqueous plating bath according to claim 1 wherein the concentration of the reducing agent ranges from 10 to 1000 mmol/l.
11. The aqueous plating bath according to claim 1 having a pH value in the range of 4 to 7.
12. The aqueous plating bath according to claim 3 wherein the stabilising agent is selected from compounds according to formula (1) with R1 and R3 selected from formula (2a), R2 selected from formula (2c) and R4 selected from formula (2d).
13. The aqueous plating bath according to claim 4 wherein the stabilising agent is selected from compounds according to formula (1) with R1 and R3 selected from formula (2a), R2 selected from formula (2c) and R4 selected from formula (2d).
14. The aqueous plating bath according to claim 1 wherein the hypophosphite compound is selected from sodium hypophosphite and potassium hypophosphite.
15. The aqueous plating bath according to claim 1 wherein the amine-borane adduct is dimethyl amine borane.
16. A method for electroless deposition of palladium or a palladium alloy onto a copper or copper alloy surface, the method comprising the steps of
a. providing a substrate having a metal surface,
b. providing an aqueous palladium or palladium alloy plating bath composition comprising a source of palladium ions, a reducing agent selected from formic acid, formic acid derivatives, salts and mixtures of the aforementioned, hypophosphite compounds and amine-borane adducts, a nitrogenated complexing agent which is free of phosphorous and at least one organic stabilising agent which comprises 1 to 5 phosphonate residues wherein the concentration of the stabilising agent which comprises 1 to 5 phosphonate residues ranges from 0.1 to 100 mmol/l for stabilising agents comprising four and five phosphonate residues and from 50 to 500 mmol/l for stabilising agents comprising one, two and three phosphonate residues and
c. depositing a layer of palladium or a palladium alloy onto the metal surface of the substrate from the palladium or palladium alloy plating bath from step b.
17. A method according to claim 16 wherein the method further comprises deposition of palladium by immersion-type plating onto the metal surface prior to step c.
18. The method according to claim 16 wherein the hypophosphite compound is selected from sodium hypophosphite and potassium hypophosphite.
19. The method according to claim 16 wherein the amine-borane adduct is dimethyl amine borane.