Composition for forming antireflection film, layered product, and method of forming resist pattern
An antireflection film-forming composition which has excellent applicability, is significantly inhibited from generating ultrafine microbubbles, gives an antireflection film capable of sufficiently reducing the standing-wave effect, and has excellent solubility in water and an alkaline developing solution. The antireflection film-forming composition contains: (A) a copolymer (salt) of a sulfonic acid group-containing acrylamide derivative represented by, e.g., 2-(meth)acrylamido-2-methylpropanesulfonic acid and a fluoroalkyl group-containing acrylic acid ester derivative represented by, e.g., 2,2,3,3,3-pentafluoropropyl (meth)acrylate; and (B) a surfactant whose 0.1 wt. % aqueous solution has a surface tension as measured at 25° C. of 45 mN/m or lower.
1. An antireflection film-forming composition comprising:
(A) a copolymer having at least one repeating unit represented by the following formula (1) and at least one repeating unit represented by the following formula (2) and/or a salt of the copolymer; and
(B) a fluorine-containing anionic surfactant, fluorine-containing cationic surfactant or fluorine-containing amphoteric surfactant, the surface tension of an aqueous solution of the surfactant at 25° C. and at a concentration of 0.1% b by weight being 45 mN/m or less:
wherein in formula (1) R 1 represents a hydrogen atom or a monovalent organic group and R 2 represents a divalent organic group; and
wherein in formula (2) R 3 represents a hydrogen atom or a monovalent organic group, Rf represents a fluoroalkyl group, and X represents a direct bond, an alkylene group or a fluoroalkylene group.
2. The antireflection film composition according to claim 1 , further comprising a solvent comprising water and/or a monovalent alcohol.
3. The antireflection film-forming composition according to claim 1 , wherein the content of the component (B) is 0.001 to 50% by weight in relation to the component (A).
4. The antireflection film composition according to claim 3 , further comprising a solvent comprising water and/or a monovalent alcohol.
5. An antireflection film-forming composition comprising:
(A) a copolymer having at least one repeating unit represented by the following formula (1) and at least one repeating unit represented by the following formula (2) and/or a salt of the copolymer;
(B) a fluorine-containing anionic surfactant, fluorine-containing cationic surfactant or fluorine-containing amphoteric surfactant, the surface tension of an aqueous solution of the surfactant at 25° C. and at a concentration of 0.1% by weight being 45 mN/m or less; and
(C) a fluoroalkylsulfonic acid having 4 to 12 carbon atoms or a salt thereof and/or a fluoroalkylcarboxylic acid having 4 to 12 carbon atoms or a salt thereof:
wherein in formula (1) R 1 represents a hydrogen atom or a monovalent organic group and R 2 represents a divalent organic group; and
wherein in formula (2) R 3 represents a hydrogen atom or a monovalent organic group, Rf represents a fluoroalkyl group, and X represents a direct bond, an alkylene group or a fluoroalkylene group.
6. The antireflection film composition according to claim 5 , further comprising a solvent comprising water and/or a monovalent alcohol.
7. The antireflection film-forming composition according to claim 5 , wherein the content of the component (B) is 0.001 to 50% by weight in relation to the component (A) and the content of the component (C) is 0.001 to 50% by weight in relation to the component (B).
8. The antireflection film composition according to claim 7 , further comprising a solvent comprising water and/or a monovalent alcohol.
9. A layered product fabricated by forming on a resist coating film an antireflection film formed of an antireflection film-forming composition, wherein the antireflection film-forming composition comprises:
(A) a copolymer having at least one repeating unit represented by the following formula (1) and at least one repeating unit represented by the following formula (2) and/or a salt of the copolymer; and
(B) a fluorine-containing anionic surfactant, fluorine-containing cationic surfactant or fluorine-containing amphoteric surfactant, the surface tension of an aqueous solution of the surfactant at 25° C. and at a concentration of 0.1% b by weight being 45 mN/m or less:
wherein in formula (1) R 1 represents a hydrogen atom or a monovalent organic group and R 2 represents a divalent organic group; and
wherein in formula (2) R 3 represents a hydrogen atom or a monovalent organic group, Rf represents a fluoroalkyl group, and X represents a direct bond, an alkylene group or a fluoroalkylene group.
10. A method of forming a resist pattern on a substrate, the method comprising:
forming a resist coating film formed on a substrate;
forming, on said resist coating film, an antireflection film from an antireflection film-forming composition and thereafter irradiating said resist coating film with radiation in a predetermined pattern and then conducting development to remove said antireflection film, wherein the antireflection film-forming composition comprises:
(A) a copolymer having at least one repeating unit represented by the following formula (1) and at least one repeating unit represented by the following formula (2) and/or a salt of the copolymer, and
(B) a fluorine-containing anionic surfactant, fluorine-containing cationic surfactant or fluorine-containing amphoteric surfactant, the surface tension of an aqueous solution of the surfactant at 25° C. and at a concentration of 0.1%b by weight being 45 mN/m or less:
wherein in formula (1) R 1 represents a hydrogen atom or a monovalent organic group and R 2 represents a divalent organic group; and
wherein in formula (2) R 3 represents a hydrogen atom or a monovalent organic group, Rf represents a fluoroalkyl group, and X represents a direct bond, an alkylene group or a fluoroalkylene group.
11. The method of forming a resist pattern according to claim 10 , wherein the antireflection film and the resist coating film are simultaneously removed at the time of the development by conducting the development with an alkaline developer.
12. A layered product fabricated by forming on a resist coating film an antireflection film formed of an antireflection film-forming composition, wherein the antireflection film-forming composition comprises:
(A) a copolymer having at least one repeating unit represented by the following formula (1) and at least one repeating unit represented by the following formula (2) and/or a salt of the copolymer;
(B) a fluorine-containing anionic surfactant, fluorine-containing cationic surfactant or fluorine-containing amphoteric surfactant, the surface tension of an aqueous solution of the surfactant at 25° C. and at a concentration of 0.1% by weight being 45 mN/m or less; and
(C) a fluoroalkylsulfonic acid having 4 to 12 carbon atoms or a salt thereof and/or a fluoroalkylcarboxylic acid having 4 to 12 carbon atoms or a salt thereof:
wherein in formula (1) R 1 a hydrogen atom or a monovalent organic group and R 2 represents a divalent organic group; and
wherein in formula (2) R 3 represents a hydrogen atom or a monovalent organic group, Rf represents a fluoroalkyl group, and X represents a direct bond, an alkylene group or a fluoroalkylene group.
13. A method of forming a resist pattern on a substrate, the method comprising:
forming a resist coating film on a substrate;
forming, on said resist coating film, an antireflection film from an antireflection film-forming composition, and thereafter irradiating said resist coating film with radiation in a predetermined pattern and then conducting development to remove said antireflection film, wherein the antireflection film-forming composition comprises:
(A) a copolymer having at least one repeating unit represented by the following formula (1) and at least one repeating unit represented by the following formula (2) and/or a salt of the copolymer;
(B) a fluorine-containing anionic surfactant, fluorine-containing cationic surfactant or fluorine-containing amphoteric surfactant, the surface tension of an aqueous solution of the surfactant at 25° C. and at a concentration of 0.1% by weight being 45 mN/m or less; and
(C) a fluoroalkylsulfonic acid having 4 to 12 carbon atoms or a salt thereof and/or a fluoroalkylcarboxylic acid having 4 to 12 carbon atoms or a salt thereof:
wherein in formula (1) R 1 a hydrogen atom or a monovalent organic group and R 2 represents a divalent organic group; and
wherein in formula (2) R 3 represents a hydrogen atom or a monovalent organic group, Rf represents a fluoroalkyl group, and X represents a direct bond, an alkylene group or a fluoroalkylene group.
14. The method of forming a resist pattern according to claim 13 , wherein that the antireflection film and the resist coating film are simultaneously removed at the time of the development by conducting the development with an alkaline developer.