Radiation-sensitive resin composition, resist pattern-forming method and acid diffusion control agent
A radiation-sensitive resin composition includes: a first polymer having a first structural unit that includes an acid-labile group; a radiation-sensitive acid generator; and a first compound capable of forming a salt through a structural change in a molecule thereof upon irradiation with a radioactive ray. Basicity of the first compound preferably changes upon irradiation with a radioactive ray. The first compound preferably generates an acid upon irradiation with a radioactive ray. The first compound is preferably represented by formula (1). In formula (1), Ar 1 represents a substituted or unsubstituted heteroarenediyl group having 4 to 30 ring atoms and having at least one nitrogen atom as a ring-constituting atom.
1. A radiation-sensitive resin composition comprising:
a first polymer comprising a first structural unit that comprises an acid-labile group;
a radiation-sensitive acid generator; and
a first compound capable of forming a salt through a structural change in a molecule thereof upon irradiation with a radioactive ray, wherein the first compound is not a salt and represented by formula (1):
wherein, in the formula (1),
Ar 1 represents a substituted or unsubstituted heteroarenediyl group having 4 to 30 ring atoms and having at least one nitrogen atom as a ring-constituting atom;
Ar 2 represents a substituted or unsubstituted aryl group having 6 to 30 ring atoms, at least one ring atom of the aryl group being a carbon atom having a hydrogen atom bound thereto, or a substituted or unsubstituted heteroaryl group having 4 to 30 ring atoms, at least one ring atom of the heteroaryl group being a carbon atom having a hydrogen atombound thereto;
Ar 3 represents an aryl group having 6 to 30 ring atoms, the aryl group being unsubstituted except that one of the ring atoms of the aryl group is a carbon atom having a single leaving group bound thereto, wherein the leaving group leaves upon irradiation with a radioactive ray to generate an acid, or a heteroaryl group having 4 to 30 ring atoms, the heteroaryl group being unsubstituted except that one of the ring atoms of the heteroaryl group is a carbon atom having a single leaving group bound thereto, wherein the leaving group leaves upon irradiation with a radioactive ray to generate an acid,
wherein number of covalent bonds constituting a shortest bond path between the carbon atom to which the hydrogen atom bonds in Ar 2 the carbon atom to which the leaving group bonds in Ar 3 is no less than 4 and no greater than 7.
2. The radiation-sensitive resin composition according to claim 1 , wherein basicity of the first compound changes upon irradiation with a radioactive ray.
3. A radiation-sensitive resin composition comprising:
a first polymer comprising a first structural unit that comprises an acid-labile group;
a radiation-sensitive acid generator; and
a first compound capable of forming a salt through a structural change in a molecule thereof upon irradiation with a radioactive ray, wherein the first compound is not a salt and is represented by formula (1-1):
wherein, in the formula (1-1),
R 1 and R 2 each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, or R 1 and R 2 taken together represent a ring structure having 4 to 20 ring atoms together with the carbon atom to which R 1 and R 2 bond;
R 3 represents a monovalent organic group having 1 to 20 carbon atoms; n is an integer of 0 to 4, wherein in a case in which n is no less than 2, a plurality of R 3 s are identical or different, and the plurality of R 3 s optionally taken together represent a ring structure having 4 to 20 ring atoms together with the carbon chain to the which the plurality of R 3 s bond;
R 4 represents a monovalent organic group having 1 to 20 carbon atoms other than a leaving group, the leaving group leaving upon irradiation with a radioactive ray to generate an acid, m is an integer of 0 to 4, wherein in a case in which m is no less than 2, a plurality of R 4 s are identical or different, and the plurality of R 4 s optionally taken together represent a ring structure having 4 to 20 ring atoms together with the carbon chain to which the plurality of R 4 s bond; and X represents a monovalent leaving group, the monovalent leaving group leaving upon irradiation with a radioactive ray to generate an acid.
4. The radiation-sensitive resin composition according to claim 1 , wherein the first structural unit is a structural unit represented by formula (2), a structural unit that comprises an acetal structure or a combination thereof,
wherein, in the formula (2), R 5 represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group; R 6 represents a monovalent hydrocarbon group having 1 to 20 carbon atoms; and R 7 and R 8 each independently represent a monovalent hydrocarbon group having 1 to 20 carbon atoms, or R 7 and R 8 taken together represent an alicyclic structure having 3 to 20 ring atoms together with the carbon atom to which R 7 and R 8 bond.
5. A resist pattern-forming method comprising:
applying the radiation-sensitive resin composition according to claim 1 on one face side of a substrate;
exposing the resist film obtained after the applying; and
developing the resist film exposed.
6. The radiation-sensitive resin composition according to claim 5 , wherein the monovalent leaving group is a group obtained by removing an acidic hydrogen atom from a hydrohalogenic acid or from a sulfonic acid.
7. The resist pattern-forming method according to claim 5 , wherein basicity of the first compound changes upon irradiation with a radioactive ray.
8. The resist pattern-forming method according to claim 5 , wherein the first structural unit is a structural unit represented by formula (2), a structural unit that comprises an acetal structure or a combination thereof,
wherein, in the formula (2), R 5 represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group; R 6 represents a monovalent hydrocarbon group having 1 to 20 carbon atoms; and R 7 and R 8 each independently represent a monovalent hydrocarbon group having 1 to 20 carbon atoms, or R 7 and R 8 taken together represent an alicyclic structure having 3 to 20 ring atoms together with the carbon atom to which R 7 and R 8 bond.
9. The radiation-sensitive resin composition according to claim 1 , wherein the leaving group is a group obtained by removing an acidic hydrogen atom from a hydrohalogenic acid or from a sulfonic acid.
10. The radiation-sensitive resin composition according to claim 1 , wherein the leaving group is a group obtained by removing an acidic hydrogen atom from a hydrohalogenic acid or from trifluoromethanesulfonic acid.
11. The radiation-sensitive resin composition according to claim 1 , wherein in the formula (1), in the definition of Ar', the heteroarenediyl group is unsubstituted or substituted with a methyl group, tert-butyl group, a fluorine atom, or a cyano group; and in the definition of Ar 2 , the aryl group and the heteroaryl group are each independently unsubstituted or substituted with a hydrogen atom, a halogen atom, a hydroxy group, a nitro group, an amino group, a fluorinated alkyl group, or an alkyl group.
12. The radiation-sensitive resin composition according to claim 5 , wherein basicity of the first compound changes upon irradiation with a radioactive ray.
13. The radiation-sensitive resin composition according to claim 5 , wherein the first structural unit is a structural unit represented by formula (2), a structural unit that comprises an acetal structure or a combination thereof,
wherein, in the formula (2), R 5 represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group; R 6 represents a monovalent hydrocarbon group having 1 to 20 carbon atoms; and R 7 and R 8 each independently represent a monovalent hydrocarbon group having 1 to 20 carbon atoms, or R 7 and R 8 taken together represent an alicyclic structure having 3 to 20 ring atoms together with the carbon atom to which R 7 and R 8 bond.
14. The resist pattern-forming method according to claim 7 , wherein the leaving group is a group obtained by removing an acidic hydrogen atom from a hydrohalogenic acid or from a sulfonic acid.
15. The resist pattern-forming method according to claim 7 , wherein the leaving group is a group obtained by removing an acidic hydrogen atom from a hydrohalogenic acid or from trifluoromethanesulfonic acid.
16. The resist pattern-forming method according to claim 5 , wherein in the formula (1), in the definition of AO, the heteroarenediyl group is unsubstituted or substituted with a methyl group, tert-butyl group, a fluorine atom, or a cyano group; and in the definition of Ar 2 , the aryl group and the heteroaryl group are each independently unsubstituted or substituted with a hydrogen atom, a halogen atom, a hydroxy group, a nitro group, an amino group, a fluorinated alkyl group, or an alkyl group.
17. A resist pattern-forming method comprising:
applying the radiation-sensitive resin composition according to claim 5 on one face side of a substrate;
exposing the resist film obtained after the applying; and
developing the resist film exposed.
18. The resist pattern-forming method according to claim 17 , wherein basicity of the first compound changes upon irradiation with a radioactive ray.
19. The resist pattern-forming method according to claim 17 , wherein the first structural unit is a structural unit represented by formula (2), a structural unit that comprises an acetal structure or a combination thereof,
wherein, in the formula (2), R 5 represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group; R 6 represents a monovalent hydrocarbon group having 1 to 20 carbon atoms; and R 7 and R 8 each independently represent a monovalent hydrocarbon group having 1 to 20 carbon atoms, or R 7 and R 8 taken together represent an alicyclic structure having 3 to 20 ring atoms together with the carbon atom to which R 7 and R 8 bond.
20. The resist pattern-forming method according to claim 17 , wherein the monovalent leaving group is a group obtained by removing an acidic hydrogen atom from a hydrohalogenic acid or from a sulfonic acid.