Leveling composition and method for electrodeposition of metals in microelectronics
The present disclosure relates to a leveling composition for electrodepositing metals. The composition comprises a compound of formula (I):
1. A composition for electrodeposition of metals, comprising a leveling compound of formula (I):
wherein X is Cl − , or Br − ;
R 1 is O, S or N;
R 2 , R 3 and R 4 are independently selected from the group consisting of hydrogen, unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted alkynyl, unsubstituted or substituted C 3-12 cycloalkyl, unsubstituted or substituted C 6-12 aryl, unsubstituted or substituted 3-12 membered heterocyclic, and unsubstituted or substituted 5-12 membered heteroaryl; or R 2 and R 3 may combine with an atom or atoms to which they are attached to form unsubstituted or substituted C 3-12 cycloalkyl, unsubstituted or substituted 3- to 12-membered heterocyclic, unsubstituted or substituted C 6-12 aryl, or unsubstituted or substituted 5- to 12-membered heteroaryl;
Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Y 7 , and Y 8 are independently selected from the group consisting of hydrogen, halogen, unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted alkynyl, unsubstituted or substituted C 3-12 cycloalkyl, unsubstituted or substituted C 6-12 aryl, unsubstituted or substituted 3-12 membered heterocyclic, and unsubstituted or substituted 5-12 membered heteroaryl; and
L is selected from the group consisting of unsubstituted or substituted alkyl, unsubstituted or substituted C 6-12 aryl, and unsubstituted or substituted 3- to 12-membered heterocyclyl; and
at least one source of metal ions.
2. The composition of claim 1 , wherein R 1 is O.
3. The composition of claim 1 , wherein Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Y 7 and Y 8 are hydrogen.
4. The composition of claim 1 , wherein R 2 , R 3 and R 4 are each independently C 1-6 alkyl.
5. The composition of claim 1 , wherein R 2 is methyl, and R 3 and R 4 are isopropyl.
6. The composition of claim 1 , wherein R 2 and R 3 are ethyl, and R 4 is benzyl.
7. The composition of claim 1 , further comprising an accelerator, and a suppressor.
8. The composition of claim 7 , wherein the accelerator is of formula (IV):
wherein X is O or S;
n is 1 to 6;
M is hydrogen, alkali metal, or ammonium;
R 1 is an alkylene, cyclic alkylene group of 1 to 8 carbon atoms; or an aromatic hydrocarbon of 6 to 12 carbon atoms; and
R 2 is MO 3 SR 1 .
9. The composition of claim 8 , wherein X in formula (IV) is S.
10. The composition of claim 7 , wherein the suppressor is of formula (VIII):
wherein n is between 1 and about 200 and m is between 1 and about 200.
11. The composition of claim 1 , wherein the leveling compound of formula (I) is of structure:
12. The composition of claim 1 , wherein the source of metal ions comprises copper ion.
13. The composition of claim 1 , wherein the source of metal ions comprises copper sulfate.
14. The composition of claim 13 , further comprising sulfuric acid.
15. The composition of claim 1 , wherein the source of metal ions comprises copper methanesulfonate.
16. The composition of claim 15 , further comprising methanesulfonic acid.
17. The composition of claim 1 , wherein X is Br − .
18. The composition of claim 1 , wherein R 3 and R 4 are isopropyl.
19. The composition of claim 1 , wherein R 4 is benzyl.
20. The composition of claim 1 , wherein the leveling compound of formula (I) is of structure:
21. A composition for electrodeposition of metals, comprising a compound of formula (II):
wherein X is Cl − or Br − ;
R 1 is O, S or N; and
R 2 , R 3 and R 4 are independently selected from the group consisting of hydrogen, unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted alkynyl, unsubstituted or substituted C 3-12 cycloalkyl, unsubstituted or substituted C 6-12 aryl, unsubstituted or substituted 3-12 membered heterocyclic, and unsubstituted or substituted 5-12 membered heteroaryl; or R 2 and R 3 may combine with an atom or atoms to which they are attached to form unsubstituted or substituted C 3-12 cycloalkyl, unsubstituted or substituted 3- to 12-membered heterocyclic, unsubstituted or substituted C 6-12 aryl, or unsubstituted or substituted 5- to 12-membered heteroaryl; and
at least one source of metal ions.
22. The composition of claim 21 , wherein R 1 is O.
23. The composition of claim 21 , wherein R 2 , R 3 and R 4 are each independently C 1-6 alkyl.
24. The composition of claim 21 , wherein R 3 and R 4 are isopropyl.
25. The composition of claim 21 , wherein R 2 and R 3 are ethyl.
26. The composition of claim 21 , wherein R 4 is benzyl.
27. A composition for electrodeposition of metals, comprising a leveling compound of formula (III):
wherein R 1 is O, S or N;
R 2 , R 3 and R 4 are independently selected from the group consisting of hydrogen, unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted alkynyl, unsubstituted or substituted C 3-12 cycloalkyl, unsubstituted or substituted C 6-12 aryl, unsubstituted or substituted 3-12 membered heterocyclic, and unsubstituted or substituted 5-12 membered heteroaryl; or R 2 and R 3 may combine with an atom or atoms to which they are attached to form unsubstituted or substituted C 3-12 cycloalkyl, unsubstituted or substituted 3- to 12-membered heterocyclic, unsubstituted or substituted C 6-12 aryl, or unsubstituted or substituted 5- to 12-membered heteroaryl; and
at least one source of metal ions.
28. The composition of claim 27 , wherein R 1 is O.
29. A method for a metal depositing onto a substrate, comprising:
contacting a substrate with an electrolytic metal deposition composition comprising a source of metal ions, and a leveler composition, wherein the leveler composition comprises the compound of formula (I):
wherein X is Cl − , or Br − ;
R 1 is O, S or N;
R 2 , R 3 and R 4 are independently selected from the group consisting of hydrogen, unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted alkynyl, unsubstituted or substituted C 3-12 cycloalkyl, unsubstituted or substituted C 6-12 aryl, unsubstituted or substituted 3-12 membered heterocyclic, and unsubstituted or substituted 5-12 membered heteroaryl; or R 2 and R 3 may combine with an atom or atoms to which they are attached to form unsubstituted or substituted C 3-12 cycloalkyl, unsubstituted or substituted 3- to 12-membered heterocyclic, unsubstituted or substituted C 6-12 aryl, or unsubstituted or substituted 5- to 12-membered heteroaryl;
Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Y 7 , and Y 8 are independently selected from the group consisting of hydrogen, halogen, unsubstituted or substituted alkyl, unsubstituted or substituted alkenyl, unsubstituted or substituted alkynyl, unsubstituted or substituted C 3-12 cycloalkyl, unsubstituted or substituted C 6-12 aryl, unsubstituted or substituted 3-12 membered heterocyclic, and unsubstituted or substituted 5-12 membered heteroaryl; and
L is selected from the group consisting of unsubstituted or substituted alkyl, unsubstituted or substituted C 6-12 aryl, and unsubstituted or substituted 3- to 12-membered heterocyclyl; and
applying an electrical current to the electrolytic deposition composition to deposit a metal onto the substrate.
30. The method of claim 29 , wherein the electrolytic metal deposition composition further comprises a suppressor compound of formula (VIII):
wherein n is an integer between 1 and about 200; and m is an integer between 1 and about 200.
31. The method of claim 29 , wherein the electrolytic metal deposition composition further comprises an accelerator of formula (IV):
wherein X is O or S;
n is an integer between 1 to 6;
M is hydrogen, alkali metal, or ammonium;
R 1 is an alkylene, cyclic alkylene group of 1 to 8 carbon atoms; or an aromatic hydrocarbon of 6 to 12 carbon atoms; and
R 2 is MO 3 SR 1 .
32. The method of claim 29 , wherein the source of metal ions comprises a copper ion source, and further comprises a transition metal ion source.
33. The method of claim 29 , wherein the source of metal ions comprises a copper ion source and further comprises a metal ion source selected from the group consisting of a source of tin ions, a source of silver ions, a source of zinc ions, a source of manganese ions, a source of zirconium ions, and a source of bismuth ions.
34. The method of claim 29 , wherein copper sulfate is used as the metal ion source.
35. The method of claim 34 , wherein the electrolytic metal deposition composition further comprises sulfuric acid.
36. The method of claim 29 , wherein the electrolytic metal deposition composition comprises copper methanesulfonate as the metal ion source, and further comprises methanesulfonic acid.