CMP method utilizing amphiphilic nonionic surfactants
View Patent ↗The invention provides methods of polishing a substrate comprising (i) contacting a substrate comprising at least one metal layer comprising copper with a chemical-mechanical polishing (CMP) system and (ii) abrading at least a portion of the metal layer comprising copper to polish the substrate. The CMP system comprises (a) an abrasive, (b) an amphiphilic nonionic surfactant, (c) a means for oxidizing the metal layer, (d) an organic acid, (e) a corrosion inhibitor, and (f) a liquid carrier. The invention further provides a two-step method of polishing a substrate comprising a first metal layer and a second, different metal layer. The first metal layer is polishing with a first CMP system comprising an abrasive and a liquid carrier, and the second metal layer is polished with a second CMP system comprising (a) an abrasive, (b) an amphiphilic nonionic surfactant, and (c) a liquid carrier.
1. A method of polishing a substrate comprising:
(i) contacting a substrate comprising at least one metal layer comprising copper with a chemical-mechanical polishing system comprising:
(a) an abrasive having a mean primary particle size of about 100 nm or greater,
(b) an amphiphilic nonionic surfactant comprising a head group and a tail group, and having an HLB value of greater than 6,
(c) a means for oxidizing the metal layer comprising copper,
(d) an organic acid,
(e) a corrosion inhibitor, and
(f) a liquid carrier; and
(ii) abrading at least a portion of the metal layer comprising copper to polish the substrate,
wherein the amphiphilic nonionic surfactant is a block or graft copolymer comprising polyoxyethylene and polydimethylsiloxane, polyoxyethylene and polyoxypropylene, or polyoxyethylene and polyethylene.
2. The method of claim 1 , wherein the amiphiphilic nonionic surfactant has an HLB of about 7 or greater.
3. The method of claim 1 , wherein the amiphiphilic nonionic surfactant has an HLB of about 6 to about 18.
4. The method of claim 1 , wherein the abrasive has a mean particle size of about 105 nm to about 180 nm.
5. The method of claim 1 , wherein the abrasive comprises silica or polyelectrolyte-coated alumina.
6. The method of claim 1 , wherein the means for oxidizing the metal layer comprising copper comprises a chemical oxidizing agent.
7. The method of claim 1 , wherein the organic acid is selected from the group consisting of acetic acid, oxalic acid, tartaric acid, lactic acid, phthalic acid, propionic acid, and combinations thereof.
8. The method of claim 1 , wherein the corrosion inhibitor is selected from the group consisting of benzotriazole, 6-tolyltriazole, 1,2,3-triazole, 1,2,4-triazole, and combinations thereof.
9. The method of claim 1 , wherein the system has a pH of about 3 or greater.
10. The method of claim 1 , wherein the polishing system comprises about 0.005 wt. % or more amphiphilic nonionic surfactant, based on the weight of the liquid carrier and any compounds dissolved or suspended therein.
11. A method of polishing a substrate comprising:
(i) contacting a substrate comprising at least one metal layer comprising copper with a chemical-mechanical polishing system comprising:
(a) an abrasive selected from the group consisting of silica, ceria, titania, zirconia, co-formed particles thereof, polymer particles, polymer-coated particles thereof, polymer-coated alumina, and combinations thereof,
(b) an amphiphilic nonionic surfactant comprising a head group and a tail group, and having an HLB value of greater than 6,
(c) a means for oxidizing the metal layer comprising copper,
(d) an organic acid,
(e) a corrosion inhibitor, and
(f) a liquid carrier; and
(ii) abrading at least a portion of the metal layer comprising copper to polish the substrate,
wherein the amphiphilic nonionic surfactant is a block or graft copolymer comprising polyoxyethylene and polydimethylsiloxane, polyoxyethylene and polyoxypropylene, or polyoxyethylene and polyethylene.
12. The method of claim 11 , wherein the amphiphilic nonionic surfactant has an HLB of about 18 or less.
13. The method of claim 11 , wherein the abrasive has a mean particle size of about 100 nm or greater.
14. The method of claim 11 , wherein the abrasive comprises silica or polymer-coated alumina.
15. The method of claim 11 , wherein the means for oxidizing the metal layer comprising copper comprises a chemical oxidizing agent.
16. The method of claim 11 , wherein the organic acid is selected from the group consisting of acetic acid, oxalic acid, tartaric acid, lactic acid, phthalic acid, propionic acid, and combinations thereof.
17. The method of claim 11 , wherein the corrosion inhibitor is selected from the group consisting of benzotriazole, 6-tolyltriazole, 1,2,3-triazole, 1,2,4-triazole, and combinations thereof.
18. The method of claim 11 , wherein the system has a pH of about 3 or greater.
19. The method of claim 11 , wherein the polishing system comprises about 0.005 wt. % or more amphiphilic nonionic surfactant, based on the weight of the liquid carrier and any compounds dissolved or suspended therein.
20. A method of polishing a substrate comprising:
(i) contacting a substrate comprising at least a first metal layer and a second, different metal layer, with a first chemical-mechanical polishing system suitable for removal of the first metal layer and abrading at least a portion of the first metal layer to polish the substrate, wherein the first chemical-mechanical polishing system comprises an abrasive and a liquid carrier, and subsequently,
(ii) contacting the substrate with a second chemical-mechanical polishing system suitable for removal of the second metal layer, and abrading at least a portion of the second metal layer to polish the substrate, wherein the second chemical-mechanical polishing system comprises:
(a) an abrasive,
(b) an amphiphilic nonionic surfactant comprising a head group and a tail group, and having an HLB value of greater than 6, and
(c) a liquid carrier, and
wherein the first and second chemical-mechanical polishing systems are different.
21. The method of claim 20 , wherein the amphiphilic nonionic surfactant has an HLB of about 6 to about 18.
22. The method of claim 20 , wherein the first metal layer comprises copper, tungsten, an alloy thereof, or combination thereof.
23. The method of claim 20 , wherein the second metal layer comprises tantalum, titanium, an alloy thereof, or combination thereof.
24. The method of claim 20 , wherein the second chemical-mechanical polishing system further comprises a means of oxidizing the second metal layer, an organic acid, or a corrosion inhibitor.
25. The method of claim 20 , wherein the tail group comprises a polyoxyethylene having about 4 or more ethylene oxide repeating units, a sorbitan, or a mixture thereof.
26. The method of claim 20 , wherein the head group comprises a polysiloxane, a tetra-C 1-4 -alkyldecyne, a saturated or partially unsaturated C 6-12 alkyl, a polyoxypropylene, a C 6-12 alkyl phenyl, a C 6-30 alkyl cyclohexyl, a polyethylene, or mixture thereof.
27. The method of claim 20 , wherein the amphiphilic nonionic surfactant is selected from the group consisting of polyoxyethylene alkyl ethers and polyoxyethylene alkyl acid esters, wherein the alkyl is a C 6-30 alkyl, which can be saturated or partially unsaturated, and is optionally branched.
28. The method of claim 20 , wherein the amphiphilic nonionic surfactant is a polyoxyethylene alkylphenyl ether or a polyoxyethylene alkylcyclohexyl ether, wherein the alkyl is a C 6-30 alkyl, can be saturated or partially unsaturated, and can be optionally branched.
29. The method of claim 20 , wherein the amphiphilic nonionic surfactant is a block or graft copolymer comprising polyoxyethylene and polydimethylsiloxane, polyoxyethylene and polyoxypropylene, or polyoxyethylene and polyethylene.
30. The method of claim 20 , wherein the abrasive comprises silica or polymer-coated alumina.