Method of depositing a metal on a surface

• US 4,100,037 A
• Filed: 03/08/1976
• Issued: 07/11/1978
• Est. Priority Date: 03/08/1976
• Status: Expired due to Term

• Current Assignee: AT&T Technologies Inc (Nokia Corporation)
• Original Assignee: Western Electric Co., Inc. (Nokia Corporation)
• Inventors: Kenney, John Thomas, Baron, William James
• Primary Examiner(s): Kendall, Ralph S.
• Application Number:
  US05/664,610
• Time in Patent Office: 855 Days
• Field of Search: 427/98, 427/304-306, 427/259, 106/1, 204/38 B, 204/20, 204/15
• US Class Current: 205/118
• CPC Class Codes: C23C 18/1608 from pretreatment step, i.e. selective pre-treatment
• CPC Class Codes: C23C 18/2086 with use of organic or inorganic compounds other than metals, first
• CPC Class Codes: H05K 2203/1173 Differences in wettability, e.g. hydrophilic or hydrophobic areas
• CPC Class Codes: H05K 2203/1415 Applying catalyst after applying plating resist
• CPC Class Codes: H05K 3/184 using masks

Abstract

A method of depositing a metal on a surface of a substrate is disclosed. The method comprises selectively coating portions of the surface with a colloidophobic material to render the portions colloidophobic and to delineate an exposed surface pattern which is capable of retaining a colloidal species thereon. The selectively coated surface is treated with a sol comprising a colloidal species selected from the group comprising (1) a species capable of reducing an activating metal ion to an activating metal, and (2) a colloidal activating metal species capable of participating in an electroless metal deposition to deposit the colloidal species on the exposed surface pattern.

Claims

1. A method of depositing a metal on a surface capable of retaining a colloidal species thereon which comprises:

(a) selectively coating a portion of the surface with a colloidophobic material selected from the group of colloidophobic materials consisting of (1) a composition comprising dimethoxy polysiloxane having a viscosity ranging from 20 to 100,000 centipoise, (2) a composition comprising a polyfluoroalkyl ester, (3) a composition comprising a perfluoro epoxy resin, and (4) a composition comprising a colloidal silica having chemically bonded to the surface thereof amounts of from about 0.01 to about 30 percent by weight based on the weight of the silica of a disilizane compound having the general formula ##STR9## wherein R₁, R₂, R₃, R₄, R₅ and R₆ are like or unlike radicals selected from the group consisting of alkyl having one to five carbon atoms to render said portion collodiophobic and to delineate an exposed surface pattern capable of retaining a colloidal species thereon; and

(b) treating said selectively coated surface with a sol comprising a colloidal species selected from the group consisting of (a¹) a colloidal species capable of reducing an activating metal ion to an activating metal, and (b¹) a colloidal activating metal species capable of participating in an electroless metal deposition to deposit said colloidal species on said exposed surface pattern.

2. The method as defined in claim 1 which further comprises forming an electroless metal deposition catalyst pattern by:

exposing said deposited pattern to an activating metal ion, when said deposited colloidal species comprises (a¹), to deposit an activating metal thereon;

or

exposing said deposited pattern to a suitable reducing species, when said deposited species comprises (b¹), and where said colloidal activating metal species is capable of being reduced to a reduction catalyst in an electroless process, to reduce said activating metal species to deposit an activating metal thereon.

3. The method as defined in claim 2 which further comprises exposing said catalyst pattern to an electroless metal deposition solution to deposit an electroless metal thereon.

4. The method as defined in claim 3 which further comprises electroplating said deposited electroless metal pattern to electrodeposit a metal thereon.

5. The method as defined in claim 1 which further comprises treating said sol treated surface with an inert rinsing agent to remove excess portions of said sol from said sol treated surface.

6. The method as defined in claim 5 wherein said inert reagent comprises an aqueous solution.

7. The method as defined in claim 1 wherein said colloidophobic material comprises said composition comprising said colloidal silica.

8. The method as defined in claim 1 wherein said polyfluoroalkyl ester is selected from the group consisting of polyperfluoro octyl methacrylate and polyperfluoro lauryl methacrylate.

9. The method as defined in claim 1 wherein said perfluoro epoxy resin is selected from the group consisting of (a) the reaction product of a reaction mixture comprising the diglycidyl ether of 1,3 bis [2-hydroxy-hexafluoro-2-propyl]-5-heptafluoro-propyl benzene and 1,4 bis (aminomethyl) cyclohexane and (b) the reaction product of a reaction mixture comprising the diglycidyl ether of 1,3 bis [2-hydroxyhexafluoro-2-propyl]-5-pentadecafluoro-heptylbenzene, 1,4 bis (aminomethyl) cyclohexane and perfluorotetradecane.

10. The method as defined in claim 1 wherein in step (b) said selectively coated surface is treated with a stable aqueous sol comprising colloidal particles of a hydrous oxide of an element selected from the group consisting of Ti, V, Cr, Fe, Sn, Pb, Bi and mixtures thereof.

11. The method as defined in claim 1 wherein in step (b) said selectively coated surface is treated with a stable aqueous sol comprising colloidal particles of hydrous oxide of Pd, Pt, Ag and Au.

12. The method as defined in claim 1 wherein said deposited species comprises (b¹) which is initially capable of catalyzing an electroless metal deposition and which further comprises treating said deposited surface with an electroless metal deposition solution to deposit an electroless metal thereon.

13. A method of depositing a metal pattern on a surface, capable of retaining a colloidal species thereon, which comprises:

(a) coating a portion of the surface with a colloidophobic material selected from the group of colloidophobic materials consisting of (1) a composition comprising dimethoxy polysiloxane having a viscosity ranging from 20 to 100,000 centipoise, (2) a composition comprising a polyfluoroalkyl ester, (3) a composition comprising a perfluoro epoxy resin, and (4) a composition comprising a colloidal silica having chemically bonded to the surface thereof amounts of from about 0.01 to about 30 percent by weight based on the weight of the silica of a disilizane compound having the general formula ##STR10## wherein R₁, R₂, R₃, R₄, R₅ and R₆ are like or unlike radicals selected from the group consisting of alkyl having one to five carbon atoms to render the surface energy of said portion lower relative to untreated portions to render said treated portion colloidophobic and to delineate an untreated surface pattern corresponding to the metal pattern; and

(b) treating said coated surface with a sol having a higher surface energy relative to the colloidophobic surface to adherently deposit and retain on said delineated surface pattern colloidal particles selected from the group consisting of (a¹) colloidal particles comprising a species capable of reducing an activating metal ion to an activating metal, and (b¹) colloidal particles comprising an activating metal species capable of participating in an electroless metal deposition.

14. The method as defined in claim 13 wherein said colloidophobic material comprises said composition comprising said colloidal silica.

15. The method as defined in claim 13 wherein said polyfluoroalkyl ester is selected from the group consisting of polyperfluoro octyl methacrylate and polyperfluoro lauryl methacrylate.

16. The method as defined in claim 13 wherein said perfluoro epoxy resin is selected from the group consisting of (a) the reaction product of a reaction mixture comprising the diglycidyl ether of 1,3 bis [2-hydroxy-hexafluoro-2-propyl]-5-heptafluoro-propyl benzene and 1,4 bis (aminomethyl) cyclohexane and (b) the reaction product of a reaction mixture comprising the diglycidyl ether of 1,3 bis [2-hydroxyhexafluoro-2-propyl]-5-pentadecafluoro-heptyl benzene, 1,4 bis (aminomethyl) cyclohexane and perfluorotetradecane.

17. The method as defined in claim 13 wherein in step (b) said selectively coated surface is treated with a stable aqueous sol comprising colloidal particles of hydrous oxide of an element selected from the group consisting of Ti, V, Cr, Fe, Sn, Pb, Bi and mixtures thereof.

18. The method as defined in claim 13 wherein in step (b) said selectively coated surface is treated with a stable aqueous sol comprising colloidal particles of a hydrous oxide of Pd, Pt, Ag and Au.

19. The method as defined in claim 13 which further comprises rinsing said sol-treated surface with an inert agent to remove excess portions of said sol from said sol-treated surface.

20. The method as defined in claim 19 which further comprises:

when said deposited colloidal particles comprise (a¹), exposing said deposited pattern to an activating metal ion to deposit an activating metal thereon to form an activating metal pattern.

21. The method as defined in claim 20 which further comprises exposing said activating metalpattern to an electroless metal deposition solution to deposit an electroless metal thereon.

22. The method as defined in claim 21 which further comprises elctroplating said deposited electroless metal pattern to electrodeposit a metal thereon.

23. The method as defined in claim 19 wherein:

said selected species (b¹) comprises an activating metal species capable of being reduced to a reduction catalyst in a elctroless metal deposition process; and

which further comprises threating said deposited pattern with a suitable reducing species to reduce said activating metal species to said catalyst to form a catalyst pattern.

24. The method as defined in claim 23 which further comprises exposing said atalyst pattern to an electroless metal deposition solutionto deposit an electroless metal thereon.

25. The method as defined in claim 19 wherein:

said selected species (b¹) comprises an activating metal species initially capable of functioning as a reduction catalyst in an electroless metal-deposition process, and

which further comprises exposing said deposited pattern to an electroless metal deposition solution to deposit an electroless metal thereon.

26. A method of rendering an article, capable of retaining thereon a collodial species, selectively capable of reducing thereon a precious metal from a precious metal salt, which comprises:

selectively coating a portion of the article with a colloidophobic material selected from the group of colloidophobic materials consisting of (1) a composition comprising a dimethoxy polysiloxane having a viscosity ranging from 20 to 100,000 centipoise, (2) a composition comprising a polyfluoroalkyl ester, (3) a composition comprising a perfluoro epoxy resin, and (4) a composition comprising a colloidal silica having chemically bonded to the surface thereof amounts of from about 0.01 to about 30 percent by weight based on the weight of the silica of a disilizane compound having the general formula ##STR11## wherein R₁, R₂, R₃, R₄, R₅ and R₆ are like or unlike radicals selected from the group consisting of alkyl having one to five carbon atoms to delineate a colloidophobic surface pattern and a colloidophilic surface pattern;

treating said selectively coated article with a sol comprising a colloidal species capable of reducing a precious metal ion to a precious metal to deposit said colloidal species thereon;

treating said deposited article with an inert rinsing agent to remove excess portions of said sol from at least said colloidophobic pattern; and

exposing said deposited colloidophilic pattern to a precious metal ion to reduce and deposit a precious metal thereon.

27. The method as defined in claim 26 wherein said colloidophobic material comprises said composition comprising said colloidal silica.

28. The method as defined in claim 26 wherein said polyfluoroalkyl ester is selected from the group consisting of polyperfluoro octyl methacrylate and polyperfluoro lauryl methacrylate.

29. The method as defined in claim 26 wherein said perfluoro epoxy resin is selected from the group consisting of (a) the reaction product of a reaction mixture comprising the diglycidyl ether of 1,3 bis [2-hydroxy-hexafluoro-2-propyl]-5-heptafluoro-propyl benzene and 1,4 bis (aminomethyl) cyclohexane and (b) the reaction product of a reaction mixture comprising the diglycidyl ether of 1,3 bis [2-hydroxyhexafluoro-2-propyl]-5-penta decafluoro-heptyl benzene, 1,4 bis (aminomethyl) cyclohexane and perfluorotetradecane.

30. The method as defined in claim 26 where in step (b) said selectively coated surface is treated with a stable aqueous sol comprising colloidal particles of a hydrous oxide of an element selected from the group consisting of Ti, V, Cr, Fe, Sn, Pb, Bi and mixtures thereof.

31. The method as defined in claim 26 wherein said inert rinsing agent comprises an aqueous solution.

32. A process for the preparation of an electrically non-conductive surface capable of retaining thereon a colloidal species to receive a metal coating over a selected area thereof, which comprises:

selectively coating a portion of the surface with a colloidophobic material selected from the group of colloidophobic materials consisting of (1) a composition comprising a dimethoxy polysiloxane having a viscosity ranging from 20 to 100,000 centipoise, (2) a composition comprising a polyfluoroalkyl ester, (3) a composition comprising a perfluoro epoxy resin, and (4) a composition comprising a colloidal silica having chemically bonded to the surface thereof amounts of from about 0.01 to about 30 percent by weight based on the weight of the silica of a disilizane compound having the general formula ##STR12## wherein R₁, R₂, R₃, R₄, R₅ and R₆ are like or unlike radicals selected from the group consisting of alkyl having one to five carbon atoms to delineate a relatively colloidophilic area corresponding to the selected area;

depositing on said selectively coated surface a sol comprising a colloidal activating metal species selected from the group consisting of (a¹) a species capable of initially functioning as a reduction catalyst in an electroless metal deposition, and (b¹) a species capable of being reduced to a species capable of functioning as a reduction catalyst in an electroless metal deposition; and

rinsing said deposited surface with an inert agent to remove said sol from said coated portion.

33. The method as defined in claim 32 which further comprises:

when said activating metal species comprises (b¹), treating said rinsed surface with a suitable reducing agent to form a catalytic pattern corresponding to the selected area; and

exposing said catalytic pattern to an electroless plating solution to deposit an electroless metal thereon.

34. The method as defined in claim 32 which further comprises when said activating metal species comprises (a¹), exposing said rinsed surface to an electroless plating solution to deposit an electroless metal thereon.

35. The method as defined in claim 32 wherein said colloidophobic material comprises said composition comprising said colloidal silica.

36. The method as defined in claim 32 wherein said polyfluoroalkyl ester is selected from the group consisting of polyperfluoro octyl methacrylate and polyperfluoro lauryl methacrylate.

37. The method as defined in claim 32 wherein said perfluoro epoxy resin is selected from the group consisting of (a) the reaction product of a reaction mixture comprising the diglycidyl ether of 1,3 bis [2-hydroxy-hexafluoro-2-propyl]-5-heptafluoro-propyl benzene and 1,4 bis (aminomethyl) cyclohexane and (b) the reaction product of a reaction mixture comprising the diglycidyl ether of 1,3 bis [2-hydroxyhexafluoro-2-propyl]-5-penta decafluoro-heptyl benzene, 1,4 bis (aminomethyl) cyclohexane and perfluorotetradecane.

38. The method as defined in claim 32 wherein said inert agent comprises an aqueous solution.

39. A method of selectively rendering a hydrophobic surface hydrophilic, said surface being capable of retaining thereon a colloidal species, which comprises:

(a) selectively coating a portion of the surface with a colloidophobic material, selected from the group of colloidophobic materials consisting of (1) a composition comprising a dimethoxy polysiloxane having a viscosity ranging from 20 to 100,000 centipoise, (2) a composition comprising a polyfluoroalkyl ester, (3) a composition comprising a perfluoro epoxy resin, and (4) a composition comprising a colloidal silica having chemically bonded to the surface thereof amounts of from about 0.01 to about 30 percent by weight based on the weight of the silica of a disilizane compound having the general formula ##STR13## wherein R₁, R₂, R₃, R₄, R₅ and R₆ are like or unlike radicals selected from the group consisting of alkyl having one to five carbon atoms, to render said portion colloidophobic and to delineate an exposed surface pattern capable of retaining a colloidal species thereon; and

(b) treating said selectively coated surface with a stable aqueous sol comprising colloidal particles of a hydrous oxide of an element selected from the group consisting of Be, Mg, Ti, Zr, V, Cr, Mo, W, Mn, Fe, Co, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, In, Tl, Si, Ge, Sn, Pb, Bi, La, Ce, Th, U and mixtures thereof to deposit said colloidal particles on said exposed surface pattern to render said pattern hydrophilic.

40. The method as defined in claim 39 which further comprises treating said sol treated surface with an inert rinsing agent to remove excess portions of said sol from said sol treated surface.

41. The method as defined in claim 40 wherein said inert reagent comprises an aqueous solution.

42. The method as defined in claim 39 wherein said colloidophobic material comprises said composition comprising said colloidal silica.

43. The method as defined in claim 39 wherein said polyfluoroalkyl ester is selected from the group consisting of polyperfluoro octyl methacrylate and polyperfluoro lauryl methacrylate.

44. The method as defined in claim 39 wherein said perfluoro epoxy resin is selected from the group consisting of (a) the reaction product of a reaction mixture comprising the diglycidyl ether of 1,3 bis [2-hydroxy-hexafluoro-2-propyl]-5-heptafluoro-propyl benzene and 1,4 bis (aminomethyl) cyclohexane and (b) the reaction product of a reaction mixture comprising the diglycidyl ether of 1,3 bis [2-hydroxyhexafluoro-2-propyl]-5-penta decafluoro-heptyl benzene, 1,4 bis (aminomethyl) cyclohexane and perfluorotetradecane.

45. A method of depositing a metal on a surface, capable of retaining thereon a colloidal species, which comprises:

(a) selectively coating a portion of the surface with a colloidophobic material selected from the group consisting of (1) a composition comprising a dimethoxy polysiloxane having a viscosity ranging from 20 to 100,000 centipoises, (2) a composition comprising a polyfluoroalkyl ester, (3) a composition comprising a perfluoro epoxy resin, and (4) a composition comprising a colloidal silica having chemically bonded to the surface thereof amounts of from about 0.01 to about 30 percent by weight based on the weight of silica of a disilizane compound having the general formula ##STR14## wherein R₁, R₂, R₃, R₄, R₅ and R₆ are like or unlike radicals selected from the group consisting of alkyl having having one to five carbon atoms, to render said portion colloidophobic and to delineate an exposed surface pattern capable of retaining a colloidal species thereon;

(b) treating said selectively coated surface with a sol comprising a colloidal species selected from the group consisting of (a¹) a colloidal species capable of reducing an activating metal ion to an activating metal, and (b¹) a colloidal activating metal species capable of participating in an electroless metal deposition to deposit said colloidal species on said exposed surface pattern; and

(c) treating said sol treated surface with an inert rinsing agent to remove excess portions of said sol from said sol treated surface to form retained, deposited colloidal species on said pattern.