Non-precious metal colloidal dispersions for electroless metal deposition

• US 4,136,216 A
• Filed: 10/12/1976
• Issued: 01/23/1979
• Est. Priority Date: 08/26/1975
• Status: Expired due to Term

• Current Assignee: Surface Technology Incorporated
• Original Assignee: Surface Technology Incorporated
• Inventors: Feldstein, Nathan
• Primary Examiner(s): Kendall, Ralph S.
• Application Number:
  US05/731,212
• Time in Patent Office: 833 Days
• Field of Search: 427/304, 427/305, 427/306, 252/317, 252/363.5, 106/1.11
• US Class Current: 427/306
• CPC Class Codes: C23C 18/28 Sensitising or activating
• CPC Class Codes: H05K 3/181 by electroless plating adhesives therefor H05K3/387

Abstract

Metallic surfaces are imparted to non-conductive or dielectric substrates by an electroless coating process comprising coating the surface of the substrate with a hydrous oxide colloid of non-precious metal ions preferably selected from the group consisting of cobalt, nickel and copper ions, reducing the selected metal ions to a reduced or zero valence state with a suitable reducing agent, and exposing the substrate to an electroless plating bath.

Claims

1. An improved process for the preparation of non-conductor substrates for electroless metal or alloy plating thereon comprising contacting said substrate with a catalytic non-precious metal colloidal composition wherein said catalytic non-precious metal is the admixture of copper and at least one metal selected from the group consisting of nickel, cobalt, and iron and wherein said colloidal composition is formed by interaction of the metal ions with a precipitating agent and wherein said precipitating agent is selected from the group of hypophosphorus acid and its derivatives and hydroxyl ions.

2. The process according to claim 1 wherein the colloidal composition further contains a colloidal stabilizer.

3. The process according to claim 1 wherein the catalytic non-precious metal is part of an alloy.

4. The process according to claim 1 wherein the catalytic non-precious metal is in an elemental state.

5. The process according to claim 1 further containing the step of activation thereby activating the catalytic sites towards electroless plating wherein said activation comprises a reducing composition.

6. The process according to claim 1 wherein said colloidal composition is derived by the dispersion of a powder in a suitable solvent medium.

7. The process according to claim 1 wherein said colloidal composition further containing a mild reducing agent.

8. An improved process for the metallization of non-conductor substrate by electroless plating thereon comprising

(a) contacting said substrate with a colloidal composition said composition comprised of a colloid of a catalytic non-precious metal wherein said metal is higher in the EMF series in comparison to said platable metal ion present in the electroless bath with said colloid reduced after the substrate has been treated to a lower or elemental state prior to the electroless plating build-up, and b) plating from an electroless bath comprising said platable metal ion.

9. The process according to claim 8 wherein said colloidal catalytic composition further contains a colloid stabilizer.

10. The process according to claim 8 wherein said colloidal catalytic composition further containing a mild reducing agent.

11. The process according to claim 8 wherein said colloidal catalytic composition is derived by the dispersion of a powder in a suitable medium.

12. An improved process of electroless metal deposition of dielectric substrates comprising the steps of,

(A) Coating the surface of the substrate with colloid of at least one non-precious elemental metal wherein said elemental metal is selected from the group consisting of copper, cobalt, iron and nickel and mixtures thereof, and

(B) Immersing the substrate in an electroless plating composition.

13. The process recited in claim 12 including the step of activating the substrate by reduction subsequent to coating.

14. The process according to claim 12 wherein said colloid further containing a mild reducing agent.

15. The process according to claim 12 wherein said colloid is derived by the dispersion of a powder in a suitable medium.

16. An improved process for electroless plating of a non-conductor substrate comprising

(a) contacting the non-conductor with a colloidal catalytic composition of non-noble elemental metal and/or alloy thereof wherein said metal is catalytic for electroless metal initiation and further wherein said composition was previously contacted with water and air;

and subsequently (b) contacting the treated non-conductor with a composition comprising a reducing agent capable of interacting with the treated non-conductor and thereby rendering said non-conductor active for electroless build-up.

17. The process according to claim 16 wherein said non-noble metal is selected from the group consisting of copper, cobalt, nickel and iron, mixtures and alloys thereof.

18. The process according to claim 16 wherein said reducing agent is part of the electroless plating bath.

19. The process according to claim 16 wherein said non-conductor substrate is ABS.

20. The process according to claim 16 wherein said electroless build-up is carried forth utilizing an electroless copper composition.

21. The process according to claim 16 wherein said colloidal composition further contains at least one colloid stabilizer.

22. The process according to claim 16 wherein said colloidal catalytic composition comprises negative colloids.

23. The process according to claim 16 wherein said colloidal catalytic composition comprises positive colloids.

24. The process according to claim 16 wherein said colloidal composition is prepared by a chemical precipitation method.

25. The process according to claim 16 wherein said colloidal composition was prepared by the admixing of a soluble metal compound comprising a catalytic metal along with a reducing agent capable of homogeneous reduction of the metal ions within said metal compound to a lower oxidation state.

26. The process according to claim 16 wherein said catalytic composition further containing a mild reducing agent.

27. The process according to claim 16 wherein said catalytic composition is derived by the dispersion of a powder in a suitable medium.

28. An improved process for the preparation of non-conductor substrates prior to electroless metal deposition comprising the steps of:

a. Coating the surface of the substrate with a colloidal composition comprising cuprous oxide, and

b. Contacting the coated surface with a composition comprising a reducing agent capable of reducing the cuprous oxidation state to the metallic state.

29. An improved process for the preparation of non-conductor substrates for electroless plating thereon comprising the contacting of said substrate with a colloidal catalytic composition, said composition comprised of a colloid of a catalytic non-precious metal compound wherein said metal is higher in the EMF series in comparison to said platable metal ion(s) present in the electroless bath, and wherein said non-precious metal compound of said colloid is reduced to a lower or elemental state prior to the electroless plating build-up and wherein said colloidal composition is derived by the dispersion of a powder in a suitable medium.

30. An improved process for electroless plating a non-conductor substrate comprising the steps of

(a) contacting the non-conductor with a stabilized colloidal composition of non-noble metal selected from the group comprising hydrous oxides, metals and alloys and mixtures thereof and wherein said metal is catalytic for electroless plating initiation and further wherein said composition is derived by the dispersion of a powder in a suitable medium and is further permitted to be contacted with water and air, and

(b) contacting the treated non-conductor with a composition comprising a reducing agent capable of interacting with the treated non-conductor and thereby rendering said non-conductor active for electroless build-up.

31. The process according to claim 30 wherein said colloidal composition comprises positive colloids.

32. The process according to claim 30 wherein said colloidal composition comprises negative colloids.

33. An improved process for preparing dielectric substrates for electroless plating comprising

a. coating the surface of a dielectric substrate to be plated with a hydrous oxide colloid of a non-precious metal selected from the group consisting of cobalt, iron, nickel and copper and alloys of said metals, and mixtures thereof, and at least one colloid stabilizer, and

b. reducing said metal to a lower or zero valence state with a chemical reducing agent to effect a catalytic surface receptive to electroless plating initiation.

34. The process of claim 33 wherein said reducing agent is selected from the group consisting of dimethylamine borane, diethylhydroxylamine, N-alkyl-borozones, N-alkyl-borozoles, borozenes, borozines, and mixtures thereof.

35. The process of claim 33 wherein said reducing agent is selected from the group consisting of the alkali metal and alkaline earth metal borohydrides.

36. The process of claim 33, wherein said dielectric substrate is coated by immersion in a bath of said hydrous oxide colloid.

37. The process of claim 33, wherein said metal is reduced by immersion of said dielectric substrate into aqueous bath of said reducing agent.

38. The process of claim 33, wherein said dielectric substrate is ABS.

39. The process of claim 33 wherein said dielectric substrate is etched prior to coating.

40. An improved process for the electroless plating of dielectric substrates comprising

a. coating the surface of a dielectric substrate with a hydrous oxide colloid of a non-precious metal selected from the group consisting of copper, nickel, iron and cobalt and alloys of said metals, and mixtures thereof and further containing at least one colloid stabilizer;

b. reducing the valence state of said metal to effect a catalytic surface receptive to electroless plating; and

c. contacting the catalytic surface with an electroless plating bath.

41. The process of claim 40, wherein said dielectric substrate is etched prior to coating.

42. The process of claim 40, wherein the valence state of said metal is reduced with a reducing agent selected from the group consisting of dimethylamine borane, diethylhydroxylomine, N-alkyl-borazones, N-alkyl-borazoles, borazenes, borazines, and mixtures thereof.

43. The process of claim 40, wherein the valence state of said metal is reduced with a reducing agent selected from the group consisting of the alkali metal and alkaline earth metal borohydrides.

44. The process of claim 40, wherein said dielectric substrate is ABS.

45. An improved process for preparing dielectric substrates for electroless plating comprising

a. coating the surface of a dielectric substrate to be plated with a hydrous oxide colloid of a non-precious metal selected from the group consisting of cobalt, iron, nickel and copper and alloys of said metals, and mixtures thereof and at least one colloid stabilizer;

b. rinsing said substrate to remove excess colloid; and

c. reducing said metal to a lower or zero valence state with a chemical reducing agent to render the surface catalytic for electroless plating.