Method and composition for electrodeposition of copper in microelectronics with dipyridyl-based levelers

1. A method for metalizing a via feature in a semiconductor integrated circuit device substrate, wherein the semiconductor integrated circuit device substrate comprises a front surface, a back surface, and the via feature and wherein the via feature comprises an opening in the front surface of the substrate, a sidewall extending from the front surface of the substrate inward, and a bottom, the method comprising:

contacting the semiconductor integrated circuit device substrate with an electrolytic copper deposition chemistry comprising (a) a source of copper ions and (b) a leveler compound, wherein the leveler compound comprises a reaction product of a dipyridyl compound and an alkylating agent and the alkylating agent comprises the following structure (IIIb):

Y—(CH 2 ) p —B—(CH 2 ) q —Z  Structure (IIIb)

wherein

B is selected from among:

a single bond, an oxygen atom (—O—), a methenyl hydroxide

a carbonyl

an amino

an imino

a sulfur atom (—S—), a sulfoxide a

phenylene

and a glycol

and

p and q may be the same or different, are integers between 0 and 6, wherein at least one of p and q is at least 1;

X is an integer from one to about four;

Y and Z are leaving groups selected from among chloride, bromide, iodide, tosyl, triflate, sulfonate, mesylate, methosulfate, fluorosulfonate, methyl tosylate, brosylate, or nosylate; and

R 1 through R 14 are each independently hydrogen, substituted or unsubstituted alkyl having from one to six carbon atoms, substituted or unsubstituted alkylene having from one to six carbon atoms, or substituted or unsubstituted aryl; and

supplying electrical current to the electrolytic deposition chemistry to deposit copper metal onto the bottom and sidewall of the via feature, thereby yielding a copper filled via feature.

2. The method of claim 1 wherein the dipyridyl compound comprises the following structure (I):

wherein R 1 is a moiety that connects the pyridine rings.

3. The method of claim 1 wherein the dipyridyl compound comprises the following structure (Ia):

wherein h is an integer from 0 to 6, and R 2 and R 3 are each independently selected from among hydrogen or a short alkyl chain having from 1 to about 3 carbon atoms.

4. The method of claim 3 wherein R 2 and R 3 are each hydrogen, and the dipyridyl compound comprises the general structure (IIa):

wherein m is an integer from 0 to 6.

5. The method of claim 1 wherein the dipyridyl compound comprises any of the following structures (IIb) through (IId):

wherein m is an integer from 0 to 6.

6. The method of claim 1 wherein the dipyridyl compound comprises structure (IIe) or (IIf):

7. The method of claim 1 wherein the dipyridyl compound comprises structure (IIf):

8. The method of claim 1 wherein the dipyridyl compound comprises the following structure (Ib):

wherein i and j are integers from 0 to 6, and R 4 , R 5 , R 6 , and R 6 are each independently selected from among hydrogen or a short alkyl chain having from 1 to about 3 carbon atoms.

9. The method of claim 8 wherein i and j are both 0, and the dipyridyl compound comprises one of the following structures:

10. The method of claim 1 wherein the dipyridyl compound comprises the following structure (Ic):

wherein k and l are integers from 0 to 6, and R 8 , R 9 , R 10 , R 11 , and R 12 are each independently selected from among hydrogen or a short alkyl chain having from 1 to about 3 carbon atoms.

11. The method of claim 1 wherein the dipyridyl compound comprises the following structure (Id):

12. The method of claim 1 wherein:

p and q are both one or are both two; and

B is selected from among:

an oxygen atom (—O—),

a methenyl hydroxide

a carbonyl

a phenylene group

an ethylene glycol group

and

a propylene glycol group

13. The method of claim 1 wherein:

p and q are both one or are both two; and

B is selected from among:

an oxygen atom (—O—),

a methenyl hydroxide

a carbonyl

a phenylene group

and

an ethylene glycol group

14. The method of claim 1 wherein the alkylating agent is selected from the group consisting of 1-chloro-2-(2-chloroethoxy)ethane, 1,2-bis(2-chloroethoxy)ethane, 1,3-dichloropropan-2-one, 1,3-dichloropropan-2-ol, 1,2-dichloroethane, 1,3-dichloropropane, 1,4-dichlorobutane, 1,5-dichloropentane, 1,6-dichlorohexane, 1,7-dichloroheptane, 1,8-dichlorooctane, 1,2-di(2-chloroethyl)ether, 1,4-bis(chloromethyl)benzene, m-di(chloromethyl)benzene, and o-di(chloromethyl)benzene.

15. The method of claim 1 wherein the leveler compound comprises a polymer comprising the following general structure (IV):

wherein B, p, q, Y, and Z are as defined with regard to (IIIb); m is an integer between one and six; and n is an integer that is at least 2.

16. The method of claim 1 wherein the leveler compound comprises a polymer comprising the following general structure (V):

wherein B, p, q, Y, and Z are as defined with regard to structure (IIIb) and n is an integer of at least 2.

17. The method of claim 1 wherein the leveler compound comprises a polymer comprising the following structure (VI):

wherein n is an integer of at least 2.

18. The method of claim 1 wherein the leveler compound comprises a polymer comprising the following general structure (VII):

wherein B, p, q, Y, and Z are as defined with regard to structure (IIIb) and n is an integer of at least 2.

19. The method of claim 1 wherein the leveler compound comprises a polymer comprising the following structure (VIII):

wherein n is an integer of at least 2.

20. The method of claim 1 wherein the leveler compound comprises a polymer comprising the following structure (IX):

wherein n is an integer of at least 2.

21. The method of claim 1 wherein the leveler compound comprises a polymer comprising the following structure (X):

wherein n is an integer of at least 2.

22. The method of claim 1 wherein the leveler compound comprises a polymer comprising the following structure (XI):

wherein n is an integer of at least 2.

23. The method of claim 1 wherein the leveler compound comprises a polymer comprising the following structure (XII):

wherein n is an integer of at least 2.

24. The method of claim 1 wherein the leveler compound comprises the following general structure (XIII):

wherein B, p, q, Y, and Z are as defined with regard to structure (IIIb); and m is an integer between one and six.

25. The method of claim 1 wherein the leveler compound comprises the following general structure (XIV):

wherein B, p, q, Y, and Z are as defined with regard to Structure (IIIb).

26. The method of claim 1 wherein the leveler compound comprises the following structure (XV):

27. The method of claim 1 wherein the leveler compound comprises the following general structure (XVI):

wherein B, p, q, Y, and Z are as defined with regard to structure (IIIb).

28. The method of claim 1 wherein the leveler compound comprises the following structure (XVII):

29. The method of claim 1 wherein the leveler compound comprises the following structure (XVIII):

30. A method for metalizing a via feature in a semiconductor integrated circuit device substrate, wherein the semiconductor integrated circuit device substrate comprises a front surface, a back surface, and the via feature and wherein the via feature comprises an opening in the front surface of the substrate, a sidewall extending from the front surface of the substrate inward, and a bottom, the method comprising:

contacting the semiconductor integrated circuit device substrate with an electrolytic copper deposition composition comprising (a) a source of copper ions and (b) a leveler compound, wherein the leveler compound comprises a polymer comprising the following general structure (IV):

wherein B is selected from among:

a single bond, an oxygen atom (—O—), a methenyl hydroxide

a carbonyl

an amino

an imino

a sulfur atom (—S—), a sulfoxide

a phenylene

and a glycol

and

p and q may be the same or different, are integers between 0 and 6, wherein at least one of p and q is at least 1;

X is an integer from one to about four;

Y and Z are leaving groups selected from among chloride, bromide, iodide, tosyl, triflate, sulfonate, mesylate, methosulfate, fluorosulfonate, methyl tosylate, brosylate, or nosylate; m is an integer between one and six; and n is an integer that is at least 2; and

supplying electrical current to the electrolytic deposition composition to deposit copper metal onto the bottom and sidewall of the via feature, thereby yielding a copper filled via feature.

31. The method of claim 30 wherein the dipyridyl moiety of structure IV comprises a residue of the structure (IIf):

32. The method of claim 30 wherein the leveler compound comprises a polymer having the following general structure (V):

33. The method as set forth in claim 30 wherein the leveler comprises a polymer selected from the group consisting of:

(a) a polymer comprising the following structure (VI):

wherein n is an integer of at least 2;

(b) a polymer comprising the following structure (IX):

wherein n is an integer of at least 2;

(c) a polymer comprising the following structure (X):

wherein n is an integer of at least 2;

(d) a polymer comprising the following structure (XI):

wherein n is an integer of at least 2; and

(e) a polymer comprising the following structure (XII):

wherein n is an integer of at least 2.

34. The method of claim 30 wherein the leveler compound comprises a polymer comprising the following general structure (VII):

35. The method of claim 34 wherein the leveler compound comprises a polymer comprising the following structure (VIII):

wherein n is an integer of at least 2.

36. A method for metalizing a via feature in a semiconductor integrated circuit device substrate, wherein the semiconductor integrated circuit device substrate comprises a front surface, a back surface, and the via feature and wherein the via feature comprises an opening in the front surface of the substrate, a sidewall extending from the front surface of the substrate inward, and a bottom, the method comprising:

contacting the semiconductor integrated circuit device substrate with an electrolytic copper deposition composition comprising (a) a source of copper ions and (b) a leveler compound, wherein the leveler compound comprises the following general structure (XIII):

wherein B is selected from among:

a single bond, an oxygen atom (—O—), a methenyl hydroxide

a carbonyl

an amino

an imino

a sulfur atom (—S—), a sulfoxide

a phenylene

and a glycol

and

p and q may be the same or different, are integers between 0 and 6, wherein at least one of p and q is at least 1;

X is an integer from one to about four;

Y and Z are leaving groups selected from among chloride, bromide, iodide, tosyl, triflate, sulfonate, mesylate, methosulfate, fluorosulfonate, methyl tosylate, brosylate, or nosylate; m is an integer between one and six; and m is an integer between one and six; and

supplying electrical current to the electrolytic deposition composition to deposit copper metal onto the bottom and sidewall of the via feature, thereby yielding a copper filled via feature.

37. The method of claim 36 wherein the leveler compound comprises the following general structure (XVI):

38. The method of claim 36 wherein the leveler compound comprises the following structure (XVII):

39. The method of claim 36 wherein the leveler compound comprises the following structure (XVIII):

; and

supplying electrical current to the electrolytic deposition composition to deposit copper metal onto the bottom and sidewall of the via feature, thereby yielding a copper filled via feature.

40. A composition for metalizing a via feature in a semiconductor integrated circuit device substrate comprising:

(a) a source of copper ions;

(b) a leveler compound, wherein the leveler compound comprises a polymer comprising the following general structure (IV):

wherein B is selected from among:

a single bond, an oxygen atom (—O—), a methenyl hydroxide

a carbonyl

an amino

an imino

a sulfur atom (—S—), a sulfoxide

a phenylene

and a glycol

and

p and q may be the same or different, are integers between 0 and 6, wherein at least one of p and q is at least 1;

X is an integer from one to about four;

Y and Z are leaving groups selected from among chloride, bromide, iodide, tosyl, triflate, sulfonate, mesylate, methosulfate, fluorosulfonate, methyl tosylate, brosylate, or nosylate; m is an integer between one and six; and n is an integer that is at least 2;

(c) an accelerator; and

(d) a suppressor.

41. A composition as set forth in claim 40 wherein the leveler compound comprises a polymer having the following general structure (V):

42. A composition as set forth in claim 40 wherein the leveler compound is selected from the group consisting of:

(i) a polymer comprising the following structure (VI):

wherein n is an integer of at least 2;

(ii) a polymer comprising the following structure (IX):

wherein n is an integer of at least 2;

(iii) a polymer comprising the following structure (X):

wherein n is an integer of at least 2;

(iv) a polymer comprising the following structure (XI):

wherein n is an integer of at least 2; and

(v) a polymer comprising the following structure (XII):

wherein n is an integer of at least 2.

43. A composition as set forth in claim 40 wherein the leveler compound comprises a polymer comprising the following general structure (VII):

44. A composition as set forth in claim 40 wherein the leveler compound comprises a polymer comprising the following structure (VIII):

wherein n is an integer of at least 2.

45. A composition for metalizing a via feature in a semiconductor integrated circuit device substrate comprising:

(a) a source of copper ions;

(b) a leveler compound, the leveler compound comprises the following general structure (XIII):

wherein B is selected from among:

a single bond, an oxygen atom (—O—), a methenyl hydroxide

a carbonyl

an amino

an imino

a sulfur atom (—S—), a sulfoxide

a phenylene

and a glycol

and

p and q may be the same or different, are integers between 0 and 6, wherein at least one of p and q is at least 1;

X is an integer from one to about four;

Y and Z are leaving groups selected from among chloride, bromide, iodide, tosyl, triflate, sulfonate, mesylate, methosulfate, fluorosulfonate, methyl tosylate, brosylate, or nosylate; m is an integer between one and six; and m is an integer between one and six;

(c) an accelerator; and

(d) a suppressor.

46. A composition as set forth in claim 45 wherein the leveler compound comprises the following general structure (XVI):

47. A composition as set forth in claim 45 wherein the leveler compound comprises the following structure (XVII):

48. A composition as set forth in claim 45 wherein the leveler compound comprises the following structure (XVIII):

49. A method for metalizing a via feature in a semiconductor integrated circuit device substrate, wherein the semiconductor integrated circuit device substrate comprises a front surface, a back surface, and the via feature and wherein the via feature comprises an opening in the front surface of the substrate, a sidewall extending from the front surface of the substrate inward, and a bottom, the method comprising:

contacting the semiconductor integrated circuit device substrate with an electrolytic copper deposition composition comprising (a) a source of copper ions and (b) a leveler compound, wherein the leveler compound comprises a polymer comprising repeating units that comprise dipyridyl moieties; and

supplying electrical current to the electrolytic deposition composition to deposit copper metal onto the bottom and sidewall of the via feature, thereby yielding a copper filled via feature.

50. A method as set forth in claim 49 wherein said polymer comprises repeating units that comprise quaternized dipyridyl moieties.