METALLIC SURFACE ENHANCEMENT

• US 20080261025A1
• Filed: 04/18/2007
• Published: 10/23/2008
• Est. Priority Date: 04/18/2007
• Status: Active Grant

• Current Assignee: MacDermid Enthone Inc. (Element Solutions Inc)
• Original Assignee: Enthone Incorporated (Element Solutions Inc)
• Inventors: Abys, Joseph A., Fan, Chonglun, Sun, Shenliang, Kudrak, Edward J.
• Granted Patent: US 7,883,738 B2
• Time in Patent Office: Days
• US Class Current: 428/332
• CPC Class Codes: C23C 22/03 containing phosphorus compounds
• CPC Class Codes: C23F 11/10 using organic inhibitors
• CPC Class Codes: C23F 11/149 Heterocyclic compounds containing nitrogen as hetero atom
• CPC Class Codes: H05K 2203/124 Heterocyclic organic compounds, e.g. azole, furan
• CPC Class Codes: H05K 3/282 for inhibiting the corrosion of the circuit, e.g. for preserving the solderability
• CPC Class Codes: Y10T 428/12611 Oxide-containing component
• CPC Class Codes: Y10T 428/12903 Cu-base component
• CPC Class Codes: Y10T 428/26 Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
• CPC Class Codes: Y10T 428/31678 Of metal

Abstract

A method and composition for enhancing corrosion resistance, wear resistance, and contact resistance of a device comprising a copper or copper alloy substrate and at least one metal-based layer on a surface of the substrate. The composition comprises a phosphorus oxide compound selected from the group consisting of a phosphonic acid, a phosphonate salt, a phosphonate ester, a phosphoric acid, a phosphate salt, a phosphate ester, and mixtures thereof; an aromatic heterocycle comprising nitrogen; and a solvent having a surface tension less than about 50 dynes/cm as measured at 25° C.

Claims

1. A composition for enhancing corrosion resistance, wear resistance, and contact resistance of a device comprising a copper or copper alloy substrate and at least one metal-based layer on a surface of the substrate, the composition comprising:

a phosphorus oxide compound selected from the group consisting of a phosphonic acid, a phosphonate salt, a phosphonate ester, a phosphoric acid, a phosphate salt, a phosphate ester, and mixtures thereof;

an aromatic heterocycle comprising nitrogen; and

a solvent having a surface tension less than about 50 dynes/cm as measured at 25°

C.

2. The composition of claim 1 wherein the phosphorus oxide compound has the structure (I):

3. The composition of claim 2 wherein the phosphorus oxide compound is selected from the group consisting of n-decyl phosphonic acid, n-dodecyl phosphonic acid, n-tetradecyl phosphonic acid, n-hexadecyl phosphonic acid, n-octadecyl phosphonic acid, their salts, and their esters.

4. The composition of claim 1 wherein the phosphorus oxide compound has the structure (II):

5. The composition of claim 4 wherein the phosphorus oxide compound is selected from the group consisting of n-decyl phosphoric acid, n-dodecyl phosphoric acid, n-tetradecyl phosphoric acid, n-hexadecyl phosphoric acid, n-octadecyl phosphoric acid, their salts, and their esters.

6. The composition of claim 1 wherein the aromatic heterocycle comprising nitrogen has the following structure (III):

7. The composition of claim 6 wherein any one or more of R₁₁, R₂₂, R₃₃, R₄₄, and R₅₅ is carbon, and the carbon is part of an aliphatic group having between one carbon atom and 24 carbon atoms or part of an aryl group having between two carbon atoms and fourteen carbon atoms.

8. The composition of claim 6 wherein any two consecutive R₁₁, R₂₂, R₃₃, R₄₄, and R₅₅ form together with the carbon or nitrogen atoms to which they are bonded a six-membered aromatic ring.

9. The composition of claim 6 wherein the aromatic heterocycle comprising nitrogen is selected from the group consisting of pyrrole (1H-azole);

imidazole (1,3-diazole);

pyrazole (1,2-diazole);

1,2,3-triazole;

1,2,4-triazole;

tetrazole;

isoindole;

benzimidazole (1,3-benzodiazole);

indazole (1,2-benzodiazole);

1H-benzotriazole;

2H-benzotriazole;

imidazo[4,5-b]pyridine;

indole (1H-Benzo[b]pyrrole);

purine (7H-Imidazo(4,5-d)pyrimidine);

pyrazolo[3,4-d]pyrimidine;

Triazolo[4,5-d]pyrimidine; and

combinations thereof.

10. The composition of claim 6 wherein the aromatic heterocycle comprising nitrogen is selected from the group consisting of imidazole (1,3-diazole), benzimidazole (1,3-benzodiazole), 1H-benzotriazole, and 2H-benzotriazole.

11. The composition of claim 1 wherein a concentration of the phosphorus oxide compound is between about 0.1% by weight and about 5% by weight and a concentration of the aromatic heterocycle comprising nitrogen is between about 0.1% by weight and about 1.0% by weight.

12. The composition of claim 1 wherein the solvent has a surface tension less than about 40 dynes/cm as measured at 25°

C.

13. The composition of claim 1 wherein the solvent is a paraffinic mineral oil solvent or an isoparaffinic mineral oil solvent.

14. The composition of claim 1 wherein the solvent is a naphthenic oil solvent.

15. The composition of claim 1 wherein the solvent is an alcohol having a boiling point of at least about 90°

C.

16. The composition of claim 1 further comprising a thiol having the following structure (IV):

R₁—

S—

H  

 

Structure (IV)

wherein R₁ is a hydrocarbyl having between one carbon atom and about 24 carbon atoms.

17. The composition of claim 16 wherein the thiol is selected from the group consisting of ethyl mercaptan, n-propyl mercaptan, isopropyl mercaptan, n-butyl mercaptan, sec-butyl mercaptan, isobutyl mercaptan, tert-butyl mercaptan, n-pentyl mercaptan, n-hexyl mercaptan, n-heptyl mercaptan, n-octyl mercaptan, n-nonyl mercaptan, n-decyl mercaptan, n-dodecyl mercaptan, n-tetradecyl mercaptan, n-hexadecyl mercaptan, and n-octadecyl mercaptan.

18. The composition of claim 1 further comprising a disulfide having the following structure (V):

R₁—

S—

S—

R₂  

 

Structure (V)

wherein R₁ and R₂ are hydrocarbyls having between one carbon atom and about 24 carbon atoms.

19. The composition of claim 18 wherein the disulfide is selected from the group consisting of diethyl disulfide, di-n-propyl disulfide, diisopropyl disulfide, di-n-butyl disulfide, di-sec-butyl disulfide, diisobutyl disulfide, di-tert-butyl disulfide, di-n-pentyl disulfide, di-n-hexyl disulfide, di-n-heptyl disulfide, di-n-octyl disulfide, di-n-nonyl disulfide, di-n-decyl disulfide, di-n-dodecyl disulfide, di-n-tetradecyl disulfide, di-n-hexadecyl disulfide, and di-n-octadecyl disulfide.

20. A method for enhancing the corrosion resistance, wear resistance, and contact resistance of a device comprising a copper or copper alloy substrate and at least one metal-based layer on a surface of the substrate, the method comprising:

exposing the device to a composition comprising a phosphorus oxide compound selected from the group consisting of a phosphonic acid, a phosphonate salt, a phosphonate ester, a phosphoric acid, a phosphate salt, a phosphate ester, and mixtures thereof;

an aromatic heterocycle comprising nitrogen; and

a solvent having a surface tension less than about 50 dynes/cm as measured at 25°

C.

21. The method of claim 20 wherein the at least one metal-based layer comprises a base metal layer.

22. The method of claim 21 wherein the base metal layer comprises a base metal selected from the group consisting of nickel, tin, zinc, chromium, titanium, aluminum, tantalum, zirconium, hafnium, molybdenum, tungsten, and alloys thereof.

23. The method of claim 20 wherein the phosphorus oxide compound has the structure (I):

24. The method of claim 23 wherein the phosphorus oxide compound is selected from the group consisting of n-decyl phosphonic acid, n-dodecyl phosphonic acid, n-tetradecyl phosphonic acid, n-hexadecyl phosphonic acid, n-octadecyl phosphonic acid, their salts, and their esters.

25. The method of claim 20 wherein the phosphorus oxide compound has the structure (II):

26. The method of claim 25 wherein the phosphorus oxide compound is selected from the group consisting of n-decyl phosphoric acid, n-dodecyl phosphoric acid, n-tetradecyl phosphoric acid, n-hexadecyl phosphoric acid, n-octadecyl phosphoric acid, their salts, and their esters.

27. The method of claim 20 wherein the aromatic heterocycle comprising nitrogen has the following structure (III):

28. The method of claim 27 wherein any one or more of R₁₁, R₂₂, R₃₃, R₄₄, and R₅₅ is carbon, and the carbon is part of an aliphatic group having between one carbon atom and 24 carbon atoms or part of an aryl group having between two carbon atoms and fourteen carbon atoms.

29. The method of claim 27 wherein any two consecutive R₁₁, R₂₂, R₃₃, R₄₄, and R₅₅ together with the carbon or nitrogen atoms to which they are bonded form a six-membered aromatic ring.

30. The method of claim 27 wherein the aromatic heterocycle comprising nitrogen is selected from the group consisting of pyrrole (1H-azole);

imidazole (1,3-diazole);

pyrazole (1,2-diazole);

1,2,3-triazole;

1,2,4-triazole;

tetrazole;

isoindole;

benzimidazole (1,3-benzodiazole);

indazole (1,2-benzodiazole);

1H-benzotriazole;

2H-benzotriazole;

imidazo[4,5-b]pyridine;

indole (1H-Benzo[b]pyrrole);

purine (7H-Imidazo(4,5-d)pyrimidine);

pyrazolo[3,4-d]pyrimidine;

Triazolo[4,5-d]pyrimidine; and

combinations thereof.

31. The method of claim 27 wherein the aromatic heterocycle comprising nitrogen is selected from the group consisting of imidazole (1,3-diazole), benzimidazole (1,3-benzodiazole), 1H-benzotriazole, and 2H-benzotriazole.

32. The method of claim 20 wherein a concentration of the phosphorus oxide compound is between about 0.1% by weight and about 5% by weight and a concentration of the aromatic heterocycle comprising nitrogen is between about 0.1% by weight and about 1.0% by weight.

33. The method of claim 20 wherein the solvent has a surface tension less than about 40 dynes/cm as measured at 25°

C.

34. The method of claim 20 wherein the solvent is a paraffinic mineral oil solvent or an isoparaffinic mineral oil solvent.

35. The method of claim 20 wherein the solvent is a naphthenic oil solvent.

36. The method of claim 20 wherein the solvent is an alcohol having a boiling point of at least about 90°

C.

37. The method of claim 22 wherein the device further comprises a precious metal layer deposited on a surface of the base metal layer.

38. The method of claim 37 wherein the precious metal layer comprises a precious metal selected from the group consisting of gold, silver, platinum, palladium, and alloys thereof.

39. The method of claim 37 wherein the composition further comprises a thiol having the following structure (IV):

R₁—

S—

H  

 

Structure (IV)

wherein R₁ is a hydrocarbyl having between one carbon atom and about 24 carbon atoms.

40. The method of claim 39 wherein the thiol is selected from the group consisting of ethyl mercaptan, n-propyl mercaptan, isopropyl mercaptan, n-butyl mercaptan, sec-butyl mercaptan, isobutyl mercaptan, tert-butyl mercaptan, n-pentyl mercaptan, n-hexyl mercaptan, n-heptyl mercaptan, n-octyl mercaptan, n-nonyl mercaptan, n-decyl mercaptan, n-dodecyl mercaptan, n-tetradecyl mercaptan, n-hexadecyl mercaptan, and n-octadecyl mercaptan.

41. The method of claim 37 wherein the composition further comprises a disulfide having the following structure (V):

R₁—

S—

S—

R₂  

 

Structure (V)

wherein R₁ and R₂ are hydrocarbyls having between one carbon atom and about 24 carbon atoms.

42. The method of claim 41 wherein the disulfide is selected from the group consisting of diethyl disulfide, di-n-propyl disulfide, diisopropyl disulfide, di-n-butyl disulfide, di-sec-butyl disulfide, diisobutyl disulfide, di-tert-butyl disulfide, di-n-pentyl disulfide, di-n-hexyl disulfide, di-n-heptyl disulfide, di-n-octyl disulfide, di-n-nonyl disulfide, di-n-decyl disulfide, di-n-dodecyl disulfide, di-n-tetradecyl disulfide, di-n-hexadecyl disulfide, and di-n-octadecyl disulfide.

43. An electronic device comprising:

a copper substrate having a surface; and

a base metal underlayer having a surface deposited on the surface of the copper substrate; and

wherein the surface of the copper substrate comprises a first protective organic film comprising an aromatic heterocycle comprising nitrogen; and

wherein the surface of the base metal underlayer comprises a second protective organic film comprising a phosphorus oxide compound selected from the group consisting of a phosphonic acid, a phosphonate salt, a phosphonate ester, a phosphoric acid, a phosphate salt, a phosphate ester, and mixtures thereof.

44. The electronic device of claim 43 wherein the precious metal overlayer has a thickness of less than about 1.0 μ

m.

45. The electronic device of claim 43 wherein the precious metal overlayer has a thickness of less than about 0.5 μ

m.

46. The electronic device of claim 43 wherein the precious metal overlayer has a thickness of less than about 0.25 μ

m.

47. The electronic device of claim 43 wherein the base metal underlayer has a thickness of about 2.5 μ

m.

48. The electronic device of claim 43 further comprising a precious metal overlayer having a surface deposited on the surface of the base metal underlayer and the surface of the precious metal overlayer comprises a third protective organic film comprising a sulfur containing compound.