Semi-aqueous polymer removal compositions with enhanced compatibility to copper, tungsten, and porous low-K dielectrics
View Patent ↗A composition is provided that is effective for removing post etch treatment (PET) polymeric films and photoresist from semiconductor substrates. The composition exhibits excellent polymer film removal capability while maintaining compatibility with copper and low-κ dielectrics and contains water, ethylene glycol, a glycol ether solvent, morpholinopropylamine and a corrosion inhibiting compound and optionally one or more metal ion chelating agent, one or more other polar organic solvent, one or more tertiary amine, one or more aluminum corrosion inhibition agent, and one or more surfactant.
1. A removal composition for removing post etch treatment (PET) polymeric film from a microelectronic device, the composition consisting essentially of: (a) from about 5% to about 49% by weight of water; (b) from about 2% to about 20% by weight of ethylene glycol; (c) from about 30% to about 70% by weight of one or more glycol ether solvent; (d) from about 0.5% to about 20% by weight of morpholinopropylamine; (e) from about 0.1% to about 0.5% by weight of a corrosion inhibitor compound selected from the group consisting of methylbenzotriazole and tolyltriazole; and optionally one or more of the following components: (f) one or more metal ion chelating agent in an amount of from about 0.01% to about 1% by weight when present in the composition; (g) one or more other polar organic solvent in an amount of from about 0.5% to about 40% by weight when present in the composition; (h) one or more tertiary amine in an amount of from about 2% to about 12% by weight when present in the composition; (i) one or more of catechol or an alkyl catechol in an amount of from about 0.01% to 10% by weight when present in the composition; and (j) one or more surfactant in an amount of from about 0.01% to about 1% by weight when present in the composition.
2. A removal composition according to claim 1 wherein the composition contain 5-methylbenzotriazole and 3-morpholinopropylamine and ethylene glycol butyl ether.
3. A removal composition of claim 1 wherein the composition contains a tertiary amine.
4. A removal composition of claim 3 wherein said tertiary amine is triethanolamine.
5. A removal composition of claim 3 wherein the composition contains a metal ion chelating agent.
6. A removal composition of claim 5 wherein said is trans-1,2-cyclohexanediamine tetraacetic acid.
7. A removal composition of claim 5 wherein the composition contains another polar organic solvent.
8. A removal composition of claim 7 wherein said polar organic solvent is N-methyl pyrrolidone.
9. A removal composition of claim 1 wherein the composition contains catechol or an alkyl catechol.
10. A removal composition according to claim 9 wherein the composition contains 4-t-butylcatechol.
11. A removal composition of claim 1 comprising about 20.9% water, about 20% N-methyl pyrrolidone, about 46.5% ethylene glycol butyl ether, about 5% ethylene glycol, about 6% triethanolamine, about 1.5% morpholinopropylamine, and about 0.1% methylbenzotriazole.
12. A removal composition of claim 1 comprising about 20.75% water, about 20% N-methyl pyrrolidone, about 46.5% ethylene glycol butyl ether, about 5% ethylene glycol, about 6% triethanolamine, about 1.5% morpholinopropylamine, about 0.1% trans-1,2-cyclohexanediamine tetraacetic acid, about 0.05% dipolar pyrrolidone ring surfactant with n-dodecyl group and about 0.1% methylbenzotriazole.
13. A removal composition of claim 1 comprising about 19.95% water, about 60.7% ethylene glycol butyl ether, about 10% ethylene glycol, about 9% morpholinopropylamine, about 0.1% trans-1,2-cyclohexanediaminetetraacetic acid, about 0.05% dipolar pyrrolidone ring surfactant with n-dodecyl group and about 0.2% methylbenzotriazole.
14. A removal composition of claim 1 comprising about 20.0% water, about 19.2% n-methylpyrrolidinone, about 44.7% ethylene glycol butyl ether, about 4.8% ethylene glycol, about 1.4% morpholinopropylamine, about 0.1% methylbenzotriazole and about 4% of an aluminum corrosion inhibitor selected from catechol and an alkyl catechol.
15. A process for removing post etch treatment (PET) polymeric film from a microelectronic device, the process comprising contacting the microelectronic device with a composition of claim 1 for a time and at a temperature effective to remove the post etch treatment (PET) polymeric film from the microelectronic device.
16. A process for removing post etch treatment (PET) polymeric film from a microelectronic device, the process comprising contacting the microelectronic device with a composition of claim 2 for a time and at a temperature effective to remove the post etch treatment (PET) polymeric film from the microelectronic device.
17. A process for removing post etch treatment (PET) polymeric film from a microelectronic device, the process comprising contacting the microelectronic device with a composition of claim 3 for a time and at a temperature effective to remove the post etch treatment (PET) polymeric film from the microelectronic device.
18. A process for removing post etch treatment (PET) polymeric film from a microelectronic device, the process comprising contacting the microelectronic device with a composition of claim 4 for a time and at a temperature effective to remove the post etch treatment (PET) polymeric film from the microelectronic device.
19. A process for removing post etch treatment (PET) polymeric film from a microelectronic device, the process comprising contacting the microelectronic device with a composition of claim 5 for a time and at a temperature effective to remove the post etch treatment (PET) polymeric film from the microelectronic device.
20. A process for removing post etch treatment (PET) polymeric film from a microelectronic device, the process comprising contacting the microelectronic device with a composition of claim 6 for a time and at a temperature effective to remove the post etch treatment (PET) polymeric film from the microelectronic device.
21. A process for removing post etch treatment (PET) polymeric film from a microelectronic device, the process comprising contacting the microelectronic device with a composition of claim 7 for a time and at a temperature effective to remove the post etch treatment (PET) polymeric film from the microelectronic device.
22. A process for removing post etch treatment (PET) polymeric film from a microelectronic device, the process comprising contacting the microelectronic device with a composition of claim 8 for a time and at a temperature effective to remove the post etch treatment (PET) polymeric film from the microelectronic device.
23. A process for removing post etch treatment (PET) polymeric film from a microelectronic device, the process comprising contacting the microelectronic device with a composition of claim 9 for a time and at a temperature effective to remove the post etch treatment (PET) polymeric film from the microelectronic device.
24. A process for removing post etch treatment (PET) polymeric film from a microelectronic device, the process comprising contacting the microelectronic device with a composition of claim 10 for a time and at a temperature effective to remove the post etch treatment (PET) polymeric film from the microelectronic device.
25. A process for removing post etch treatment (PET) polymeric film from a microelectronic device, the process comprising contacting the microelectronic device with a composition of claim 11 for a time and at a temperature effective to remove the post etch treatment (PET) polymeric film from the microelectronic device.
26. A process for removing post etch treatment (PET) polymeric film from a microelectronic device, the process comprising contacting the microelectronic device with a composition of claim 12 for a time and at a temperature effective to remove the post etch treatment (PET) polymeric film from the microelectronic device.
27. A process for removing post etch treatment (PET) polymeric film from a microelectronic device, the process comprising contacting the microelectronic device with a composition of claim 13 for a time and at a temperature effective to remove the post etch treatment (PET) polymeric film from the microelectronic device.
28. A process for removing post etch treatment (PET) polymeric film from a microelectronic device, the process comprising contacting the microelectronic device with a composition of claim 14 for a time and at a temperature effective to remove the post etch treatment (PET) polymeric film from the microelectronic device.
29. A process according to claim 15 wherein the microelectronic device has a low-κ dielectric.