USRE49202EExpiredUtilityPatentIndex 61

Copper electrodeposition in microelectronics

Assignee: MACDERMID ENTHONE INCPriority: Nov 12, 2004Filed: Jul 9, 2018Granted: Sep 6, 2022

Est. expiryNov 12, 2024(expired)· nominal 20-yr term from priority

Inventors:PANECCASIO JR VINCENT LIN XUAN FIGURA PAUL HURTUBISE RICHARD

H10W 20/056H10P 14/47H10D 64/011C25D 7/12C25D 3/38C25D 7/123H01L 21/2885H01L 21/76877

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Claims

Abstract

An electrolytic plating method and composition for electrolytically plating Cu onto a semiconductor integrated circuit substrate having submicron-sized interconnect features. The composition comprises a source of Cu ions and a suppressor compound comprising polyether groups. The method involves superfilling by rapid bottom-up deposition at a superfill speed by which Cu deposition in a vertical direction from the bottoms of the features to the top openings of the features is substantially greater than Cu deposition on the side walls.

Claims

exact text as granted — not AI-modified

What is claimed is:

1. An electrolytic plating composition for electrolytically plating Cu onto a semiconductor integrated circuit substrate having a planar plating surface and submicron-sized interconnect features by immersion of the semiconductor integrated circuit substrate into the electrolytic solution, the composition comprising:
a source of Cu ions in an amount sufficient to electrolytically deposit Cu onto the substrate and into the electrical interconnect features; and a suppressor comprising a compound selected from the group consisting of: (i) a first suppressor compound comprising a polyether group bonded to a nitrogen-containing species, wherein the polyether group comprises a combination of propylene oxide (PO) repeat units and ethylene oxide (EO) repeat units present in a PO:EO ratio between about 1:9 and about 9:1, and wherein the molecular weight of the first suppressor compound is between about 1000 and about 3600 g/mol; (ii) a second suppressor compound comprising a polyether group bonded to a nitrogen-containing species, wherein the polyether group comprises a combination of propylene oxide (PO) repeat units and ethylene oxide (EO) repeat units present in a PO:EO ratio between about 1:9 and about 9:1, wherein the molecular weight of the second suppressor compound is between about 1000 and about 30,000 g/mol, and wherein the second suppressor compound further comprises a capping moiety selected from the group consisting of an alkyl group or a block polymer comprising propylene oxide repeat units; (iii) a third suppressor compound comprising a polyether group bonded to a nitrogen-containing species, wherein the polyether group comprises a combination of propylene oxide (PO) repeat units and ethylene oxide (EO) repeat units present in a PO:EO ratio between about 1:9 and about 9:1, wherein the nitrogen-containing species is an alkylether amine, and wherein the molecular weight of the third suppressor compound is between about 1000 and about 30,000 g/mol; and (iv) a fourth suppressor compound comprising a polyether group bonded to a nitrogen-containing species, wherein the polyether group comprises a combination of propylene oxide (PO) repeat units and ethylene oxide (EO) repeat units present in a PO:EO ratio between about 1:9 and about 9:1, wherein the molecular weight of the fourth suppressor compound is between about 1000 and about 30,000 g/mol, and wherein a nitrogen in the nitrogen-containing species is a quaternary amine; (v) a fifth suppressor compound comprising a polyether group bonded to a nitrogen-containing species, wherein the polyether group comprises a combination of propylene oxide (PO) repeat units and ethylene oxide (EO) repeat units present in a PO:EO ratio between about 1:9 and about 9:1, wherein the molecular weight of the fifth suppressor compound is between about 1000 and about 30,000 g/mol, and wherein the composition comprises less than about 30 g/L acid when the fifth suppressor is selected; (vi) a sixth suppressor compound comprising a polyether group bonded to a nitrogen-containing species, wherein the polyether group comprises a combination of propylene oxide (PO) repeat units and ethylene oxide (EO) repeat units present in a PO:EO ratio between about 1:9 and about 9:1, wherein the molecular weight of the sixth suppressor compound is between about 1000 and about 30,000 g/mol, and wherein the composition comprises between about 4 g/L and about 30 g/L copper ion when the sixth suppressor is selected; and (vi) combinations thereof.

2. The electrolytic plating composition of claim 1 wherein the propylene oxide repeat units and ethylene oxide repeat units are present in a PO:EO ratio between about 2:3 and about 3:2.

3. The electrolytic plating composition of claim 1 wherein the EO and PO repeat units are arranged in a block co-polymer sequence.

4. The electrolytic plating composition of claim 2 wherein the EO and PO repeat units are arranged in a block co-polymer sequence.

5. The electrolytic plating composition of claim 1 wherein the nitrogen-containing species comprises at least one amine functional group.

6. The electrolytic plating composition of claim 5 wherein the polyether group is bonded to a nitrogen atom in the at least one amine functional group.

7. The electrolytic plating composition of claim 5 wherein the at least one amine functional group is a quaternary amine.

8. The electrolytic plating composition of claim 2 wherein the nitrogen-containing species comprises at least one amine functional group.

9. The electrolytic plating composition of claim 7 wherein the polyether group is bonded to a nitrogen atom in the at least one amine functional group.

10. The electrolytic plating composition of claim 8 wherein the at least one amine functional group is a quaternary amine.

11. The electrolytic plating composition of claim 1 wherein the nitrogen-containing species comprises between two and five amine functional groups.

12. The electrolytic plating composition of claim 2 wherein the nitrogen-containing species comprises between two and five amine functional groups.

13. The electrolytic plating composition of claim 2 wherein the nitrogen-containing species comprises a diamine.

14. The electrolytic plating composition of claim 2 wherein the nitrogen-containing species is selected from the group consisting of ethylene diamine and triethylene glycol diamine.

15. The electrolytic plating composition of claim 1 wherein the suppressor compound comprises a structure selected from the group consisting of:

and combinations thereof;
wherein
R 1 is a substituted or unsubstituted alkyl group;
R 2 is selected from the group consisting of hydrogen and alkyl group;
R 3 is a polyether comprising repeat units selected from the group consisting of ethylene oxide repeat units, propylene oxide repeat units, and a combination thereof;
and
R 4 is selected from the group consisting of hydrogen, substituted or unsubstituted alkyl group, aryl group, aralkyl, or heteroaryl group.

16. The electrolytic plating composition of claim 15 wherein the R 1 alkyl group has between 1 and 8 carbons, and R 1 is substituted with another amino group to which a polyether group is covalently bonded, the polyether comprising ethylene oxide repeat units, propylene oxide repeat units, or a combination thereof arranged in random, alternating, or block configurations.

17. The electrolytic plating composition of claim 2 wherein the polyether suppressor is present in a concentration between about 50 mg/L and about 200 mg/L.

18. The electrolytic plating composition of claim 1 wherein the polyether suppressor comprises the structure:

wherein n is between 1 and about 30 and m is between 1 and about 30.

19. The electrolytic plating composition of claim 1 wherein the polyether suppressor comprises the structure:

wherein n is between 1 and about 30 and m is between 1 and about 30.

20. An electrolytic plating composition for electrolytically plating Cu onto a semiconductor integrated circuit substrate having a planar plating surface and submicron-sized interconnect features by immersion of the semiconductor integrated circuit substrate into the electrolytic solution, the composition comprising:
a source of Cu ions in an amount sufficient to electrolytically deposit Cu onto the substrate and into the electrical interconnect features; and a suppressor compound comprising a polyether group bonded to a nitrogen-containing species comprising at least one amine functional group that is a quaternary amine, wherein the polyether group comprises a combination of propylene oxide (PO) repeat units and ethylene oxide (EO) repeat units present in a PO:EO ratio between about 1:9 and about 9:1, wherein the molecular weight of the suppressor compound is between about 1000 and about 30,000 g/mol.

21. The electrolytic plating composition of claim 20 wherein the concentration of said suppressor is between 10 and 1,000 mg/l.

22. The electrolytic plating composition of claim 20 further comprising a leveler.

23. The electrolytic plating composition of claim 22 wherein the leveler does not substantially interfere with superfilling.

24. The electrolytic plating composition of claim 22 wherein said leveler comprises a dipyridyl polymer.

25. The electrolytic plating composition of claim 20 wherein the EO repeat units and PO repeat units are in random or alternating configuration.

26. The electrolytic plating composition of claim 20 wherein said polyether comprises a PO repeat unit bonded to said nitrogen atom.

27. The electrolytic plating composition of claim 26 wherein said polyether comprises a block of PO repeat units bonded to said nitrogen atom.

28. The electrolytic plating composition of claim 20 comprising less than about 30 g/l acid.

29. The electrolytic plating composition of claim 20 wherein the polyether group is bonded to a nitrogen atom in the at least one amine functional group.

30. The electrolytic plating composition of claim 20 wherein the EO and PO repeat units are arranged in a block co-polymer sequence.

31. The electrolytic plating composition of claim 20 wherein the suppressor compound is present in a concentration between about 50 mg/L and about 200 mg/L.

32. The electrolytic plating composition of claim 20 further comprising an accelerator.

33. The electrolytic plating composition of claim 20 wherein the suppressor compound comprises a structure selected from the group consisting of:

and combinations thereof;
wherein
R 1 is substituted or unsubstituted alkyl;
R 2 is alkyl;
R 3 is a polyether comprising repeat units selected from the group consisting of ethylene oxide repeat units, propylene oxide repeat units, and a combination thereof; and
R 4 is selected from group consisting of hydrogen, substituted or unsubstituted alkyl, aryl, aralkyl, or heteroaryl.

34. The electrolytic plating composition of claim 33 wherein R 1 has between 1 and 8 carbons, and R 1 is substituted with another amino group to which a polyether group is covalently bonded, the polyether comprising ethylene oxide repeat units, propylene oxide repeat units, or a combination thereof arranged in random, alternating, or block configurations.

35. An electrolytic plating composition for electrolytically plating Cu onto a semiconductor integrated circuit substrate having a planar plating surface and submicron-sized interconnect features by immersion of the semiconductor integrated circuit substrate into the electrolytic solution, the composition comprising:
a source of Cu ions in an amount sufficient to electrolytically deposit Cu onto the substrate and into the electrical interconnect features; and a suppressor compound comprising a polyether group bonded to a nitrogen-containing species comprising at least one amine functional group that is a quaternary amine, wherein the polyether group comprises a combination of propylene oxide (PO) repeat units and ethylene oxide (EO) repeat units present in a PO:EO ratio between about 2:3 and about 3:2, wherein the molecular weight of the suppressor compound is between about 1000 and about 30,000 g/mol.

36. The electrolytic plating composition of claim 35 wherein the EO and PO repeat units are arranged in a block co-polymer sequence.

37. An electrolytic plating composition for electrolytically plating Cu onto a semiconductor integrated circuit substrate having a planar plating surface and submicron-sized interconnect features by immersion of the semiconductor integrated circuit substrate into the electrolytic solution, the composition comprising:
a source of Cu ions in an amount sufficient to electrolytically deposit Cu onto the substrate and into the electrical interconnect features; and a suppressor comprising a compound selected from the group consisting of: (i) a first suppressor compound comprising a polyether group bonded to a nitrogen atom of a nitrogen-containing species comprising at least three amine functional groups, wherein the polyether group comprises a combination of propylene oxide (PO) repeat units and ethylene oxide (EO) repeat units present in a PO:EO ratio between about 1:9 and about 9:1, and wherein the molecular weight of the first suppressor compound is between about 1000 and about 3600 g/mol; (ii) a second suppressor compound comprising a polyether group bonded to a nitrogen atom of a nitrogen-containing species comprising at least three amine functional groups, wherein the polyether group comprises a combination of propylene oxide (PO) repeat units and ethylene oxide (EO) repeat units present in a PO:EO ratio between about 1:9 and about 9:1, wherein the molecular weight of the second suppressor compound is between about 1000 and about 30,000 g/mol, and wherein the second suppressor compound further comprises a capping moiety selected from the group consisting of an alkyl group or a block polymer comprising propylene oxide repeat units; (iii) a third suppressor compound comprising a polyether group bonded to a nitrogen atom of a nitrogen-containing species comprising at least three amine functional groups, wherein the polyether group comprises a combination of propylene oxide (PO) repeat units and ethylene oxide (EO) repeat units present in a PO:EO ratio between about 1:9 and about 9:1, wherein the nitrogen-containing species is an alkylether amine, and wherein the molecular weight of the third suppressor compound is between about 1000 and about 30,000 g/mol; and (iv) a fourth suppressor compound comprising a polyether group bonded to a nitrogen atom of a nitrogen-containing species comprising at least three amine functional groups, wherein the polyether group comprises a combination of propylene oxide (PO) repeat units and ethylene oxide (EO) repeat units present in a PO:EO ratio between about 1:9 and about 9:1, wherein the molecular weight of the fourth suppressor compound is between about 1000 and about 30,000 g/mol, and wherein a nitrogen in the nitrogen-containing species is a quaternary amine; (v) a fifth suppressor compound comprising a polyether group bonded to a nitrogen atom of a nitrogen-containing species comprising at least three amine functional groups, wherein the polyether group comprises a combination of propylene oxide (PO) repeat units and ethylene oxide (EO) repeat units present in a PO:EO ratio between about 1:9 and about 9:1, wherein the molecular weight of the fifth suppressor compound is between about 1000 and about 30,000 g/mol, and wherein the composition comprises less than about 30 g/L acid when the fifth suppressor is selected; (vi) a sixth suppressor compound comprising a polyether group bonded to a nitrogen atom of a nitrogen-containing species comprising at least three amine functional groups, wherein the polyether group comprises a combination of propylene oxide (PO) repeat units and ethylene oxide (EO) repeat units present in a PO:EO ratio between about 1:9 and about 9:1, wherein the molecular weight of the sixth suppressor compound is between about 1000 and about 30,000 g/mol, and wherein the composition comprises between about 4 g/L and about 30 g/L copper ion when the sixth suppressor is selected; and (vii) combinations thereof.

38. The electrolytic plating composition of claim 37 wherein the propylene oxide repeat units and ethylene oxide repeat units are present in a PO:EO ratio between about 2:3 and about 3:2.

39. The electrolytic plating composition of claim 37 wherein said nitrogen-containing species comprises a triamine.

40. The electrolytic plating composition of claim 39 wherein said nitrogen-containing species comprises diethylene triamine.

41. The electrolytic plating composition of claim 37 wherein said nitrogen-containing species comprises a tetraamine or pentaamine.

42. The electrolytic plating composition of claim 41 wherein said nitrogen-containing species is selected from the group consisting of triethylene tetraamine and tetraethylene pentaamine.

43. The electrolytic plating composition of claim 37 wherein said nitrogen-containing species comprises more than five amine functional groups.

44. The electrolytic plating composition of claim 37 wherein the concentration of said suppressor is between 10 and 1,000 mg/l.

45. The electrolytic plating composition of claim 37, further comprising a leveler.

46. The electrolytic plating composition of claim 45 wherein the leveler does not substantially interfere with superfilling.

47. The electrolytic plating composition of claim 45 wherein said leveler comprises a dipyridyl polymer.

48. The electrolytic plating composition of claim 37 wherein the EO repeat units and PO repeat units are in random or alternating configuration.

49. The electrolytic plating composition of claim 37 wherein said polyether comprises a PO repeat unit bonded to said nitrogen atom.

50. The electrolytic plating composition of claim 37 comprising the fifth suppressor.

51. The electrolytic plating composition of claim 37 wherein the suppressor compound is present in a concentration between about 50 mg/L and about 200 mg/L.

52. The electrolytic plating composition of claim 37 further comprising an accelerator.

53. An electrolytic plating composition for electrolytically plating Cu onto a semiconductor integrated circuit substrate having a planar plating surface and submicron-sized interconnect features by immersion of the semiconductor integrated circuit substrate into the electrolytic solution, the composition comprising:
a source of Cu ions in an amount sufficient to electrolytically deposit Cu onto the substrate and into the electrical interconnect features; and a suppressor comprising a polyether group bonded to a nitrogen-containing species, wherein the polyether group comprises a combination of propylene oxide (PO) repeat units and ethylene oxide (EO) repeat units present in a PO:EO ratio between about 1:9 and about 9:1, wherein the nitrogen-containing species is an alkylether amine, and wherein the molecular weight of the suppressor compound is between about 1000 and about 30,000 g/mol.

54. The electrolytic plating composition of claim 53 wherein said suppressor comprises the structure:

wherein n is between 1 and about 30 and m is between 1 and about 30.

55. The electrolytic plating composition of claim 53 wherein the nitrogen containing species comprises a triethylene glycol diamine.

56. The electrolytic plating composition of claim 53 wherein the propylene oxide repeat units and ethylene oxide repeat units are present in a PO:EO ratio between about 2:3 and about 3:2.

57. The electrolytic plating composition of claim 56 wherein the EO and PO repeat units are arranged in a block co-polymer sequence.

58. The electrolytic plating composition of claim 53 wherein the EO and PO repeat units are arranged in a block co-polymer sequence.

59. The electrolytic plating composition of claim 53 wherein the polyether group is bonded to a nitrogen atom in the at least one amine functional group.

60. The electrolytic plating composition of claim 53 wherein the concentration of said suppressor is between 10 and 1,000 mg/l.

61. The electrolytic plating composition of claim 53 further comprising a leveler.

62. The electrolytic plating composition of claim 61 wherein the leveler does not substantially interfere with superfilling.

63. The electrolytic plating composition of claim 61 wherein said leveler comprises a dipyridyl polymer.

64. The electrolytic plating composition of claim 53 wherein the EO repeat units and PO repeat units are in random or alternating configuration.

65. The electrolytic plating composition of claim 53 wherein said polyether comprises a PO repeat unit bonded to said nitrogen atom.

66. The electrolytic plating composition of claim 53 wherein said polyether comprises a block of PO repeat units bonded to said nitrogen atom.

67. The electrolytic plating composition of claim 53 comprising less than about 30 g/L acid.

68. The electrolytic plating composition of claim 53 wherein the suppressor compound is present in a concentration between about 50 mg/L and about 200 mg/L.

69. The electrolytic plating composition of claim 53 further comprising an accelerator.

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