Barrier film material and pattern formation method using the same
View Patent ↗A resist film made of a chemically amplified resist is formed on a substrate. Subsequently, a barrier film for preventing a component of the resist film from eluting into an immersion liquid or preventing the immersion liquid from permeating into the resist film is formed on the resist film. Thereafter, with an immersion liquid provided on the barrier film, pattern exposure is carried out by selectively irradiating the resist film with exposing light through the barrier film. Then, after removing the barrier film, the resist film having been subjected to the pattern exposure is developed, so as to form a resist pattern made of the resist film.
1. A pattern formation method comprising the steps of:
forming a resist film made of a chemically amplified resist on a substrate;
forming a barrier film on said resist film;
performing pattern exposure by selectively irradiating said resist film with exposing light with a liquid provided on said barrier film;
removing said barrier film; and
forming a resist pattern made of said resist film by developing said resist film after removing said barrier film,
wherein said barrier film includes an alkali-soluble polymer and a fluorine-based surface active agent, and
said barrier film prevents a component of said resist film from eluting into said liquid or prevents said liquid from permeating into said resist film.
2. The pattern formation method of claim 1 , further comprising, before the step of performing pattern exposure, a step of annealing said barrier film.
3. The pattern formation method of claim 1 ,
wherein said barrier film has solubility different depending upon a value of hydrogen ion exponent (pH).
4. The pattern formation method of claim 3 ,
wherein said barrier film is soluble in a solution with a value of hydrogen ion exponent (pH) larger than 7.
5. The pattern formation method of claim 3 ,
wherein said barrier film includes a polymer having a sulfonamide structure.
6. The pattern formation method of claim 5 ,
wherein said polymer is polyvinyl sulfonamide or a polysulfonamide derivative.
7. The pattern formation method of claim 6 ,
wherein said polyvinyl sulfonamide derivative is polyvinylsulfone alkylamide, polyvinylsulfone alkylamide fluoride or polyvinylsulfone substituted alkylamide.
8. The pattern formation method of claim 7 ,
wherein a substituent group of said polyvinylsulfone substituted alkylamide is a hydroxyl group, an alkoxy group, an oxo group, an amino group or an alkylamino group.
9. The pattern formation method of claim 1 ,
wherein said alkali-soluble polymer is at least one of polyvinyl hexafluoroisopropyl alcohol, polyvinyl alcohol, polyacrylic acid, polystyrenesulfonic acid, hydroxyethyl cellulose, polyisoprenesulfonic acid, polyvinyl pyrrolidone and pullulan.
10. The pattern formation method of claim 1 ,
wherein said fluorine-based surface active agent has a group with a double bond.
11. The pattern formation method of claim 10 ,
wherein said group with a double bond is a perfluoroalkenyl group.
12. The pattern formation method of claim 11 ,
wherein said perfluoroalkenyl group is a 1,1-di(perfluoromethyl)-2-perfluoroethylethenyl group or a 1,1-di(perfluoroisopropyl)-2-perfluoromethylethenyl group.
13. The pattern formation method of claim 12 ,
wherein said fluorine-based surface active agent having said 1,1-di(perfluoromethyl)-2-perfluoroethylethenyl group is 1,1-di(perfluoromethyl)-2-perfluoroethylethenyloxybenzyltrimethylammonium or 1,1-di(perfluoromethyl)-2-perfluoroethylethenylpolyoxyethylene ether.
14. The pattern formation method of claim 12 ,
wherein said fluorine-based surface active agent having said 1,1-di(perfluoroisopropyl)-2-perfluoromethylethenyl group is 1,1-di(perfluoroisopropyl)-2-perfluoromethylethenyloxybenzyltrimethylammonium or 1,1-di(perfluoroisopropyl)-2-perfluoromethylethenylpolyoxyethylene ether.
15. The pattern formation method of claim 1 ,
wherein said liquid is water or perfluoropolyether.
16. The pattern formation method of claim 1 ,
wherein said liquid is an acidic solution.
17. The pattern formation method of claim 16 ,
wherein said acidic solution is a phosphoric acid aqueous solution or a cesium sulfate aqueous solution.
18. The pattern formation method of claim 1 ,
wherein said exposing light is KrF excimer laser, ArF excimer laser, F 2 laser, ArKr laser or Ar 2 laser.
19. The pattern formation method of claim 1 ,
wherein the thickness of the barrier film is between 0.01 μm and 0.15 μm.
20. The pattern formation method of claim 2 ,
wherein the annealing temperature of the barrier film is in the range of 100° C. to 150° C.
21. The pattern formation method of claim 1 ,
wherein the liquid is provided on the barrier film by a puddle method.
22. A pattern formation method comprising the steps of:
forming a resist film made of a chemically amplified resist on a substrate;
forming a barrier film on said resist film;
performing pattern exposure by selectively irradiating said resist film with exposing light with a liquid provided on said barrier film; and
removing said barrier film and forming a resist pattern made of said resist film by developing said resist film after the pattern exposure,
wherein said barrier film includes an alkali-soluble polymer and a fluorine-based surface active agent, and
said barrier film prevents a component of said resist film from eluting into said liquid or prevents said liquid from permeating into said resist film.
23. The pattern formation method of claim 22 , further comprising, before the step of performing pattern exposure, a step of annealing said barrier film.
24. The pattern formation method of claim 22 ,
wherein said barrier film has solubility different depending upon a value of hydrogen ion exponent (pH).
25. The pattern formation method of claim 24 ,
wherein said barrier film is soluble in a solution with a value of hydrogen ion exponent (pH) larger than 7.
26. The pattern formation method of claim 24 ,
wherein said barrier film includes a polymer having a sulfonamide structure.
27. The pattern formation method of claim 26 ,
wherein said polymer is polyvinyl sulfonamide or a polyvinyl sulfonamide derivative.
28. The pattern formation method of claim 27 ,
wherein said polyvinyl sulfonamide derivative is polyvinylsulfone alkylamide, polyvinylsulfone alkylamide fluoride or polyvinylsulfone substituted alkylamide.
29. The pattern formation method of claim 28 ,
wherein a substituent group of said polyvinylsulfone substituted alkylamide is a hydroxyl group, an alkoxy group, an oxo group, an amino group or an alkylamino group.
30. The pattern formation method of claim 22 ,
wherein said alkali-soluble polymer is at least one of polyvinyl hexafluoroisopropyl alcohol, polyvinyl alcohol, polyacrylic acid, polystyrenesulfonic acid, hydroxyethyl cellulose, polyisoprenesulfonic acid, polyvinyl pyrrolidone and pullulan.
31. The pattern formation method of claim 22 ,
wherein said fluorine-based surface active agent has a group with a double bond.
32. The pattern formation method of claim 31 ,
wherein said group with a double bond is a perfluoroalkenyl group.
33. The pattern formation method of claim 32 ,
wherein said perfluoroalkenyl group is a 1,1-di(perfluoromethyl)-2-perfluoroethylethenyl group or a 1,1-di(perfluoroisopropyl)-2-perfluoromethylethenyl group.
34. The pattern formation method of claim 33 ,
wherein said fluorine-based surface active agent having said 1,1-di(perfluoromethyl)-2-perfluoroethylethenyl group is 1,1-di(perfluoromethyl)-2-perfluoroethylethenyloxybenzyltrimethylammonium or 1,1-di(perfluoromethyl)-2-perfluoroethylethenylpolyoxyethylene ether.
35. The pattern formation method of claim 33 ,
wherein said fluorine-based surface active agent having said 1,1-di(perfluoroisopropyl)-2-perfluoromethylethenyl group is 1,1-di(perfluoroisopropyl)-2-perfluoromethylethenyloxybenzyltrimethylammonium or 1,1-di(perfluoroisopropyl)-2-perfluoromethylethenylpolyoxyethylene ether.
36. The pattern formation method of claim 22 ,
wherein said liquid is water or perfluoropolyether.
37. The pattern formation method of claim 22 ,
wherein said liquid is an acidic solution.
38. The pattern formation method of claim 37 ,
wherein said acidic solution is a phosphoric acid aqueous solution or a cesium sulfate aqueous solution.
39. The pattern formation method of claim 22 ,
wherein said exposing light is KrF excimer laser, ArF excimer laser, F 2 laser, ArKr laser or Ar 2 laser.
40. The pattern formation method of claim 1 ,
wherein the step of forming a barrier film is performed by spin-coating a barrier film material.
41. The pattern formation method of claim 22 ,
wherein the step of forming a barrier film is performed by spin-coating a barrier film material.
42. The pattern formation method of claim 22 ,
wherein the thickness of the barrier film is between 0.01 μm and 0.15 μm.
43. The pattern formation method of claim 23 ,
wherein the annealing temperature of the barrier film is in the range of 100° C. to 150° C.
44. The pattern formation method of claim 22 , wherein the liquid is provided on the barrier film by a puddle method.