Polymeric inhibitors for enhanced planarization
View Patent ↗The invention provides a chemical-mechanical polishing system comprising a polishing component, a surfactant, and a liquid carrier. The invention further provides a method of chemically-mechanically polishing a substrate with the polishing system.
1. A chemical-mechanical polishing system comprising:
(a) a polishing component selected from the group consisting of a polishing pad, an abrasive, and a combination thereof,
(b) a surfactant comprising at least one azole group having a polymer chain attached thereto, wherein the surfactant is not polyvinylimidazole and wherein the surfactant does not comprise cyclic imide groups or both pendant amide and ester groups, and
(c) a liquid carrier.
2. The polishing system of claim 1 , wherein the at least one azole group is selected from the group consisting of 1,2,3-triazole, 1,2,4-triazole, pyrazole, imidazole, indazole, tetrazole, benzimidazole, benzotriazole, alkylated derivatives thereof, and combinations thereof.
3. The polishing system of claim 1 , wherein the surfactant comprises at least one azole group having a polyether chain attached thereto.
4. The polishing system of claim 1 , wherein the surfactant comprises at least one azole group having a polyacrylate chain attached thereto.
5. The polishing system of claim 3 , wherein the surfactant comprises a compound of the formula Het-X—(CH 2 CH 2 O) m (CH 2 CHR 1 O) n R 2 , wherein
Het is a heterocycle selected from the group consisting of 1,2,3-triazole, 1,2,4-triazole, pyrazole, imidazole, indazole, tetrazole, benzimidazole, and benzotriazole chemically bonded to X via a carbon atom of the heterocycle or a nitrogen atom which is part of the heterocycle;
X is (CH 2 ) p wherein p is an integer of 1-5, O, C(═O)O, CH 2 O, CH 2 CH 2 O, or a direct link;
m and n are integers from 0-20 with the proviso that m and n are not both 0;
R 1 is selected from the group consisting of H and C 1 -C 10 branched and straight chain alkyl and alkenyl; and
R 2 is selected from the group consisting of H, C 1 -C 10 branched and straight chain alkyl and alkenyl, and C 3 -C 10 cycloalkyl.
6. The polishing system of claim 1 , wherein the surfactant comprises at least one azole group having a polyamine chain attached thereto.
7. The polishing system of claim 6 , wherein the surfactant comprises a compound of the formula Het-X—(CH 2 CH 2 NR 3 ) n R 4 , wherein
Het is a heterocycle selected from the group consisting of 1,2,3-triazole, 1,2,4-triazole, pyrazole, imidazole, indazole, tetrazole, benzimidazole, and benzotriazole chemically bonded to X via a carbon atom of the heterocycle or a nitrogen atom which is part of the heterocycle;
X is selected from the group consisting of (CH 2 ) m wherein m is an integer of 1-5, NH, C(═O)NH, CH 2 NH, CH 2 CH 2 NH, and a direct link;
n is an integer from 1-20;
R 3 is H or (CH 2 CH 2 NHR 5 2 ) p wherein R 5 is a C 1 -C 5 branched and straight chain alkyl and p is an integer of 1-5; and
R 4 is selected from the group consisting of H, C 1 -C 10 branched and straight chain alkyl and alkenyl, and C 3 -C 10 cycloalkyl.
8. The polishing system of claim 1 , wherein the surfactant comprises a compound of the formula Het 1 -X—(CH 2 CHR 6 Z) n —Y-Het 2 , wherein
Het 1 and Het 2 are independently selected from the group consisting of 1,2,3-triazole, 1,2,4-triazole, pyrazole, imidazole, indazole, tetrazole, benzimidazole, and benzotriazole wherein Het 1 is chemically bonded to X, and wherein Het 2 is chemically bonded to Y via a carbon atom of the heterocycle or a nitrogen atom which is part of the heterocycle;
X is (CH 2 ) m wherein m is an integer of 1-5, Z, C(═O)Z, CH 2 Z, or a direct link;
n is an integer from 1-20;
R 6 is selected from the group consisting of H, C 1 -C 10 branched and straight chain alkyl and, when Z is N, (CH 2 CH 2 NR 7 2 ) m wherein R 7 is a C 1 -C 5 branched and straight chain alkyl and m is an integer of 1-5;
Y is (CH 2 ) m wherein m is as defined above, C(═O), or a direct link; and
Z is O or NR 1 , wherein R 1 is selected from the group consisting of H and C 1 -C 10 branched and straight chain alkyl and alkenyl.
9. The polishing system of claim 1 , wherein the surfactant comprises a polymer comprising three or more azole groups.
10. The polishing system of claim 9 , wherein the polymer comprises a polyester comprising monomers comprising at least one dicarboxylic acid and at least one diol, wherein the at least one dicarboxylic acid and/or diol comprises azole groups.
11. The polishing system of claim 9 , wherein the surfactant comprises about 20% or less of monomers comprising azole groups.
12. The polishing system of claim 10 , wherein the polyester comprises 1,2,3-triazole-4,5-dicarboxylic acid repeating groups.
13. The polishing system of claim 9 , wherein the polymer comprises a polyamide comprising monomers comprising at least one dicarboxylic acid and at least one diamine, wherein the at least one dicarboxylic acid and/or diamine comprises azole groups.
14. The polishing system of claim 13 , wherein the polyamide comprises 1,2,3-triazole-4,5-dicarboxylic acid repeating groups.
15. The polishing system of claim 9 , wherein the polymer comprises a polyamine comprising three or more azole groups.
16. The polishing system of claim 9 , wherein the polymer comprises chemical components A, B, and C; wherein
A is selected from the group consisting of one or more end groups selected from initiator fragments, chain transfer fragments, solvent fragments, and combinations thereof;
B is absent or is at least one ethylenically unsaturated monomer of the formula Het-W—CR 8 ═C(R 9 )(R 10 ), wherein Het is a heterocycle selected from the group consisting of 1,2,3-triazole, 1,2,4-triazole, pyrazole, imidazole, indazole, tetrazole, benzimidazole, and benzotriazole chemically bonded to W via a carbon atom of the heterocycle or a nitrogen atom which is part of the heterocycle;
W is (CH 2 ) n wherein n is an integer of 1-10 or a direct link;
R 8 is H or C 1 -C 10 branched and straight chain alkyl and alkenyl;
R 9 and R 10 are independently selected from the group consisting of H, C 1 -C 10 branched and straight chain alkyl and alkenyl, C 3 -C 10 cycloalkyl, and C 6 -C 10 aryl; with the proviso that if C is absent then R 8 , R 9 , and R 10 are not H, and
C is absent or includes an ethylenically unsaturated group of the formula CH(R 11 )═C(R 12 )(R 13 ),
wherein R 11 is selected from the group consisting of H, C 1 -C 10 branched and straight chain alkyl and alkenyl, C 3 -C 10 cycloalkyl, and Het-W wherein Het and W are as defined above;
R 12 and R 13 are independently selected from the group consisting of H, C 1 -C 5 branched and straight-chain alkyl and alkenyl, phenyl, substituted phenyl, COR 14 , and Het-W wherein Het and W are as defined above,
wherein R 14 is H, alkyl, OR 15 , or NR 16 R 17 ,
wherein R 15 is H or C 1 -C 5 branched and straight chain alkyl,
wherein R 16 and R 17 are independently H, C 1 -C 10 branched and straight chain alkyl, CN, or taken together form a 5-membered or 6-membered ring structure,
with the proviso that at least one of B and C comprises a heterocycle as defined herein.
17. The polishing system of claim 16 , wherein C comprises an ethylenically unsaturated group of the formula CH(R 11 )═C(R 12 )(R 13 ),
wherein R 11 is selected from the group consisting of H, C 1 -C 10 branched and straight chain alkyl and alkenyl, and C 3 -C 10 cycloalkyl,
wherein R 12 is COOR 15 wherein R 15 is as defined herein, and
wherein R 13 is selected from the group consisting of H, C 1 -C 5 branched and straight chain alkyl, phenyl, and substituted phenyl.
18. The polishing system of claim 1 , wherein the polymer comprises a hydrophilic polymer or copolymer functionalized with azole groups.
19. The polishing system of claim 18 , wherein the polymer comprises polyvinyl alcohol functionalized with azole groups.
20. The polishing system of claim 1 , wherein the azole group comprises at least a part of the polymer backbone.
21. The polishing system of claim 1 , wherein the polishing system further comprises an abrasive suspended in the liquid carrier.
22. The polishing system of claim 21 , wherein the abrasive is selected from the group consisting of alumina, ceria, germania, magnesia, silica, titania, zirconia, co-formed products thereof, and combinations thereof.
23. The polishing system of claim 1 , wherein the polishing system comprises an abrasive fixed on a polishing pad.
24. The polishing system of claim 1 , wherein the polishing system further comprises one or both of an oxidizing agent and a chelating agent.
25. A method of chemically-mechanically polishing a substrate, comprising:
(i) contacting a substrate with a polishing system comprising:
(a) a polishing component selected from the group consisting of a polishing pad, an abrasive, and a combination thereof,
(b) a surfactant comprising at least one azole group having a polymer chain attached thereto, wherein the surfactant is not polyvinylimidazole and wherein the surfactant does not comprise cyclic imide groups or both of pendant amide and ester groups, and
(c) a liquid carrier,
(ii) moving the polishing pad relative to the substrate, and
(iii) abrading at least a portion of the substrate to polish the substrate.
26. The method of claim 25 , wherein the at least one azole group is selected from the group consisting of 1,2,3-triazole, 1,2,4-triazole, pyrazole, imidazole, indazole, tetrazole, benzimidazole, benzotriazole, alkylated derivatives thereof, and combinations thereof.
27. The method of claim 25 , wherein the surfactant comprises at least one azole group having a polyether chain attached thereto.
28. The method of claim 25 , wherein the surfactant comprises at least one azole group having a polyacrylate chain attached thereto.
29. The method of claim 27 , wherein the surfactant comprises a compound of the formula Het-X—(CH 2 CH 2 O) m (CH 2 CHR 1 O) n R 2 , wherein
Het is a heterocycle selected from the group consisting of 1,2,3-triazole, 1,2,4-triazole, pyrazole, imidazole, indazole, tetrazole, benzimidazole, and benzotriazole chemically bonded to X via a carbon atom of the heterocycle or a nitrogen atom which is part of the heterocycle;
X is (CH 2 ) p wherein p is an integer of 1-5, O, C(═O)O, CH 2 O, CH 2 CH 2 O, or a direct link;
m and n are integers from 0-20 with the proviso that m and n are not both 0;
R 1 is selected from the group consisting of H and C 1 -C 10 branched and straight chain alkyl and alkenyl; and
R 2 is selected from the group consisting of H, C 1 -C 10 branched and straight chain alkyl and alkenyl, and C 3 -C 10 cycloalkyl.
30. The method of claim 25 , wherein the surfactant comprises at least one azole group having a polyamine chain attached thereto.
31. The method of claim 30 , wherein the surfactant comprises a compound of the formula Het-X—(CH 2 CH 2 NR 3 ) n R 4 , wherein
Het is a heterocycle selected from the group consisting of 1,2,3-triazole, 1,2,4-triazole, pyrazole, imidazole, indazole, tetrazole, benzimidazole, and benzotriazole chemically bonded to X via a carbon atom of the heterocycle or a nitrogen atom which is part of the heterocycle;
X is selected from the group consisting of (CH 2 ) m wherein m is an integer of 1-5, NH, C(═O)NH, CH 2 NH, CH 2 CH 2 NH, and a direct link;
n is an integer from 1-20;
R 3 is H or (CH 2 CH 2 NHR 5 2 ) p wherein R 5 is a C 1 -C 5 branched and straight chain alkyl and p is an integer of 1-5; and
R 4 is selected from the group consisting of H, C 1 -C 10 branched and straight chain alkyl and alkenyl, and C 3 -C 10 cycloalkyl.
32. The method of claim 25 , wherein the surfactant comprises a compound of the formula Het 1 -X—(CH 2 CHR 6 Z) n —Y-Het 2 , wherein
Het 1 and Het 2 are independently selected from the group consisting of 1,2,3-triazole, 1,2,4-triazole, pyrazole, imidazole, indazole, tetrazole, benzimidazole, and benzotriazole wherein Het 1 is chemically bonded to X, and wherein Het 2 is chemically bonded to Y via a carbon atom of the heterocycle or a nitrogen atom which is part of the heterocycle;
X is (CH 2 ) m wherein m is an integer of 1-5, Z, C(═O)Z, CH 2 Z, or a direct link;
n is an integer from 1-20;
R 6 is selected from the group consisting of H, C 1 -C 10 branched and straight chain alkyl and, when Z is N, (CH 2 CH 2 NR 7 2 ) m wherein R 7 is a C 1 -C 5 branched and straight chain alkyl and m is an integer of 1-5;
Y is (CH 2 ) m wherein m is as defined above, C(═O), or a direct link; and
Z is O or NR 1 , wherein R 1 is selected from the group consisting of H and C 1 -C 10 branched and straight chain alkyl and alkenyl.
33. The method of claim 25 , wherein the surfactant comprises a polymer comprising three or more azole groups.
34. The method of claim 33 , wherein the polymer comprises a polyester comprising monomers comprising at least one dicarboxylic acid and at least one diol, wherein the at least one dicarboxylic acid and/or diol comprises azole groups.
35. The method of claim 33 , wherein the surfactant comprises about 20% or less of monomers comprising azole groups.
36. The method of claim 34 , wherein the polyester comprises 1,2,3-triazole-4,5-dicarboxylic acid repeating groups.
37. The method of claim 33 , wherein the polymer comprises a polyamide comprising monomers comprising at least one dicarboxylic acid and at least one diamine, wherein the at least one dicarboxylic acid and/or diamine comprises azole groups.
38. The method of claim 37 , wherein the polyamide comprises 1,2,3-triazole-4,5-dicarboxylic acid repeating groups.
39. The method of claim 33 , wherein the polymer comprises a polyamine comprising three or more azole groups.
40. The method of claim 33 , wherein the polymer comprises chemical components A, B, and C; wherein
A is selected from the group consisting of one or more end groups selected from initiator fragments, chain transfer fragments, solvent fragments, and combinations thereof;
B is absent or is at least one ethylenically unsaturated monomer of the formula Het-W—CR 8 ═C(R 9 )(R 10 ), wherein Het is a heterocycle selected from the group consisting of 1,2,3-triazole, 1,2,4-triazole, pyrazole, imidazole, indazole, tetrazole, benzimidazole, and benzotriazole chemically bonded to W via a carbon atom of the heterocycle or a nitrogen atom which is part of the heterocycle;
W is (CH 2 ) n wherein n is an integer of 1-10 or a direct link;
R 8 is H or C 1 -C 10 branched and straight chain alkyl and alkenyl;
R 9 and R 10 are independently selected from the group consisting of H, C 1 -C 10 branched and straight chain alkyl and alkenyl, C 3 -C 10 cycloalkyl, and C 6 -C 10 aryl; with the proviso that if C is absent then R 8 , R 9 , and R 10 are not H, and
C is absent or includes an ethylenically unsaturated group of the formula CH(R 11 )═C(R 12 )(R 13 ),
wherein R 11 is selected from the group consisting of H, C 1 -C 10 branched and straight chain alkyl and alkenyl, C 3 -C 10 cycloalkyl, and Het-W wherein Het and W are as defined above;
R 12 and R 13 are independently selected from the group consisting of H, C 1 -C 5 branched and straight-chain alkyl and alkenyl, phenyl, substituted phenyl, COR 14 , and Het-W wherein Het and W are as defined above,
wherein R 14 is H, alkyl, OR 15 , or NR 16 R 17 ,
wherein R 15 is H or C 1 -C 5 branched and straight chain alkyl,
wherein R 16 and R 17 are independently H, C 1 -C 10 branched and straight chain alkyl, CN, or taken together form a 5-membered or 6-membered ring structure, with the proviso that at least one of B and C comprises a heterocycle as defined herein.
41. The method of claim 40 , wherein C comprises an ethylenically unsaturated group of the formula CH(R 11 )═C(R 12 )(R 13 ),
wherein R 11 is selected from the group consisting of H, C 1 -C 10 branched and straight chain alkyl and alkenyl, and C 3 -C 10 cycloalkyl,
wherein R 12 is COOR 15 wherein R 15 is as defined herein, and
wherein R 13 is selected from the group consisting of H, C 1 -C 5 branched and straight chain alkyl, phenyl, and substituted phenyl.
42. The method of claim 25 , wherein the polymer comprises a hydrophilic polymer or copolymer functionalized with azole groups.
43. The method of claim 42 , wherein the polymer comprises polyvinyl alcohol functionalized with azole groups.
44. The method of claim 25 , wherein the azole group comprises at least a part of the polymer backbone.
45. The method of claim 25 , wherein the polishing system further comprises an abrasive suspended in the liquid carrier.
46. The method of claim 45 , wherein the abrasive is selected from the group consisting of alumina, ceria, germania, magnesia, silica, titania, zirconia, co-formed products thereof, and combinations thereof.
47. The method of claim 25 , wherein the polishing system comprises an abrasive fixed on a polishing pad.
48. The method of claim 25 , wherein the polishing system further comprises one or both of an oxidizing agent and a chelating agent.
49. The method of claim 25 , wherein the substrate comprises one or both of a metallic layer and an insulating layer.
50. The method of claim 49 , wherein the metallic layer comprises copper.