Radiation-sensitive resin composition, monomer, polymer, and production method of radiation-sensitive resin composition
A radiation-sensitive resin composition includes a solvent and a polymer. The polymer includes a repeating unit represented by a formula (I), a repeating unit represented by a formula (II), or a both thereof. Each of R 1 to R 3 independently represents a hydroxyl group, or the like. At least one of R 1 represents a group having two or more heteroatoms. l is an integer from 1 to 5. Each of m and n is independently an integer from 0 to 5. Each of R 7 and R 11 independently represents a hydrogen atom, or the like. Each of R 8 to R 10 independently represents a hydrogen atom, or the like. A represents —O—, or the like. D represents a substituted or unsubstituted methylene group, or the like.
1. A radiation-sensitive resin composition comprising:
a polymer; and
a solvent,
said polymer including a following repeating unit represented by a general formula (I), a following repeating unit represented by a general formula (II), or both thereof,
wherein
each of R 1 to R 3 independently represents a hydroxyl group, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, —S—R 6 , or a group having two or more heteroatoms,
wherein
R 6 represents a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group,
at least one R 1 represents the group having two or more heteroatoms,
the group having two or more heteroatoms represented by the at least one R 1 includes a heteroatomic group represented by —OSO 2 —, —SO 2 —, —CONH—, or —SO 2 N(Ry)-, wherein Ry represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted aryl group, and
the heteroatomic group is directly bonded to the benzene ring bonded to S + ,
l is an integer from 1 to 5,
each of m and n is independently an integer from 0 to 5,
each of R 7 and R 11 independently represents a hydrogen atom, a halogen atom, a cyano group, or a substituted or unsubstituted alkyl group,
each of R 8 to R 10 independently represents a hydrogen atom, a hydroxyl group, a halogen atom, a nitro group, a carboxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted alkoxy group,
A represents —O— or —NR 12 —, wherein R 12 represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and
D represents a substituted or unsubstituted methylene group, a substituted or unsubstituted alkylene group, or a substituted or unsubstituted arylene group.
2. The radiation-sensitive resin composition according to claim 1 , wherein said group having two or more heteroatoms is —OSO 2 -Rx, —SO 2 -Rx, or both thereof, wherein each of Rx independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted aryl group.
3. The radiation-sensitive resin composition according to claim 1 , wherein said polymer further includes a structural unit containing an acid-labile group.
4. The radiation-sensitive resin composition according to claim 3 , wherein said acid-labile group-containing structural unit comprises a structural unit represented by a following general formula (c-1),
wherein
R 12 represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group, and
each of R 13 independently represents a linear or branched alkyl group having 1 to 4 carbon atoms, a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a group derived therefrom, or a substituted or unsubstituted aryl group having 6 to 22 carbon atoms, or
two of R 13 bond to each other to form a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a group derived therefrom, together with a carbon atom that is bonded to the two of R 13 , and one of R 13 other than the two of R 13 represents a linear or branched alkyl group having 1 to 4 carbon atoms, a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a group derived therefrom, or a substituted or unsubstituted aryl group having 6 to 22 carbon atoms.
5. The radiation-sensitive resin composition according to claim 1 , further comprising a compound represented by a following general formula (B1),
wherein
each of R 13 independently represents a monovalent organic group,
Z − represents R 15 O − or R 15 COO − , wherein R 15 represents a monovalent organic group, and each of q is independently an integer from 0 to 5.
6. A radiation-sensitive resin composition comprising:
a polymer;
a cation; and
a solvent,
wherein said polymer includes a following repeating unit represented by a general formula (I-a), a following repeating unit represented by a general formula (II-a), or both thereof, and said cation is represented by a general formula (III),
wherein
each of R 7 and R 11 independently represents a hydrogen atom, a halogen atom, a cyano group, or a substituted or unsubstituted alkyl group,
each of R 8 to R 10 independently represents a hydrogen atom, a hydroxyl group, a halogen atom, a nitro group, a carboxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted alkoxy group,
A represents —O— or —NR 12 —, wherein R 12 represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and
D represents a substituted or unsubstituted methylene group, a substituted or unsubstituted alkylene group, or a substituted or unsubstituted arylene group,
wherein
each of R 1 to R 3 independently represents a hydroxyl group, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, —S—R 6 , or a group having two or more heteroatoms,
wherein
R 6 represents a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group,
at least one R 1 represents the group having two or more heteroatoms,
the group having two or more heteroatoms represented by the at least one R 1 includes a heteroatomic group represented by —OSO 2 —, —SO 2 —, —CONH—, or —SO 2 N(Ry)-, wherein Ry represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted aryl group, and
the heteroatomic group is directly bonded to the benzene ring bonded to S + ,
l is an integer from 1 to 5, and
each of m and n is independently an integer from 0 to 5.
7. The radiation-sensitive resin composition according to claim 6 , wherein said group having two or more heteroatoms is —OSO 2 -Rx, —SO 2 -Rx, or both thereof, wherein each of Rx independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted aryl group.
8. The radiation-sensitive resin composition according to claim 6 , wherein said polymer further includes a structural unit containing an acid-labile group.
9. The radiation-sensitive resin composition according to claim 8 , wherein said acid-labile group-containing structural unit comprises a structural unit represented by a following general formula (c-1),
wherein
R 12 represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group, and
each of R 13 independently represents a linear or branched alkyl group having 1 to 4 carbon atoms, a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a group derived therefrom, or a substituted or unsubstituted aryl group having 6 to 22 carbon atoms, or
two of R 13 bond to each other to form a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a group derived therefrom, together with a carbon atom that is bonded to the two of R 13 , and one of R 13 other than the two of R 13 represents a linear or branched alkyl group having 1 to 4 carbon atoms, a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a group derived therefrom, or a substituted or unsubstituted aryl group having 6 to 22 carbon atoms.
10. The radiation-sensitive resin composition according to claim 6 , further comprising a compound represented by a following general formula (B1),
wherein
each of R 13 independently represents a monovalent organic group,
Z − represents R 15 O − or R 15 COO − , wherein R 15 represents a monovalent organic group, and
each of q is independently an integer from 0 to 5.
11. A monomer represented by a following general formula (I-m) or a following general formula (II-m),
wherein
each of R 1 to R 3 independently represents a hydroxyl group, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, —S—R 6 , or a group having two or more heteroatoms,
wherein
R 6 represents a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group,
at least one R 1 represents the group having two or more heteroatoms,
the group having two or more heteroatoms represented by the at least one R 1 includes a heteroatomic group represented by —OSO 2 —, —SO 2 —, —CONH—, or —SO 2 N(Ry)-, wherein Ry represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted aryl group, and
the heteroatomic group is directly bonded to the benzene ring bonded to S + ,
l is an integer from 1 to 5,
each of m and n is independently an integer from 0 to 5,
each of R 7 and R 11 independently represents a hydrogen atom, a halogen atom, a cyano group, or a substituted or unsubstituted alkyl group,
each of R 8 to R 10 independently represents a hydrogen atom, a hydroxyl group, a halogen atom, a nitro group, a carboxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted alkoxy group,
A represents —O— or —NR 12 —, wherein R 12 represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and
D represents a substituted or unsubstituted methylene group, a substituted or unsubstituted alkylene group, or a substituted or unsubstituted arylene group.
12. A polymer comprising:
a following repeating unit represented by a general formula (I), a following repeating unit represented by a general formula (II) or both thereof,
wherein
each of R 1 to R 3 independently represents a hydroxyl group, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, —S—R 6 , or a group having two or more heteroatoms,
wherein
R 6 represents a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group,
at least one R 1 represents the group having two or more heteroatoms,
the group having two or more heteroatoms represented by the at least one R 1 includes a heteroatomic group represented by —OSO 2 —, —SO 2 —, —CONH—, or —SO 2 N(Ry)-, wherein Ry represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted aryl group, and
the heteroatomic group is directly bonded to the benzene ring bonded to S + ,
l is an integer from 1 to 5,
each of m and n is independently an integer from 0 to 5,
each of R 7 and R 11 independently represents a hydrogen atom, a halogen atom, a cyano group, or a substituted or unsubstituted alkyl group,
each of R 8 to R 10 independently represents a hydrogen atom, a hydroxyl group, a halogen atom, a nitro group, a carboxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted alkoxy group,
A represents —O— or —NR 12 —, wherein R 12 represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and
D represents a substituted or unsubstituted methylene group, a substituted or unsubstituted alkylene group, or a substituted or unsubstituted arylene group.
13. A production method of a radiation-sensitive resin composition, comprising:
mixing a polymer and a solvent, the polymer comprising a following repeating unit represented by a general formula (I), a following repeating unit represented by a general formula (II), or both thereof,
wherein
each of R 1 to R 3 independently represents a hydroxyl group, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, —S—R 6 , or a group having two or more heteroatoms,
wherein
R 6 represents a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group,
at least one R 1 represents the group having two or more heteroatoms,
the group having two or more heteroatoms represented by the at least one R 1 includes a heteroatomic group represented by —OSO 2 —, —SO 2 —, —CONH—, or —SO 2 N(Ry)-, wherein Ry represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted aryl group, and
the heteroatomic group is directly bonded to the benzene ring bonded to S + ,
l is an integer from 1 to 5,
each of m and n is independently an integer from 0 to 5,
each of R 7 and R 11 independently represents a hydrogen atom, a halogen atom, a cyano group, or a substituted or unsubstituted alkyl group,
each of R 8 to R 10 independently represents a hydrogen atom, a hydroxyl group, a halogen atom, a nitro group, a carboxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted alkoxy group,
A represents —O— or —NR 12 —, wherein R 12 represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and
D represents a substituted or unsubstituted methylene group, a substituted or unsubstituted alkylene group, or a substituted or unsubstituted arylene group.