Resist polymer and resist composition
View Patent ↗The resist polymer of the present invention comprises a specific constitutional unit having a cyano group, a constitutional unit having an acid-dissociable group, and a specific constitutional unit having a lactone skeleton. When the above polymer is used as a resist resin in DUV excimer laser lithography or electron beam lithography, it exhibits high sensitivity and high resolution, and provides a good resist pattern shape, having a small degree of occurrence of line edge roughness or generation of microgels.
1. A resist polymer, consisting essentially of constitutional units derived from (meth)acrylate monomers, wherein the constitutional units comprise:
a constitutional unit of formula (1);
a constitutional unit having an acid-dissociable group; and
a constitutional unit having a lactone skeleton of at least one selected from the group consisting of formulas (4-1), (4-2), (4-3), (4-5), and (4-6):
wherein,
R 01 represents a hydrogen atom or a methyl group; R 02 represents a hydrogen atom; Z represents an atomic group that constitutes a bridged cyclic hydrocarbon group together with carbon atoms constituting an ester bond and a carbon atom to which cyano group binds; and p is 1,
wherein, in formula (4-1),
R 41 represents a hydrogen atom or a methyl group; i is 0; X 5 represents a linear or branched alkyl group having 1 to 6 carbon atoms that may have, as a substituent, at least one selected from the group consisting of a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, and an amino group, a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, or an amino group; and n5 represents an integer between 0 and 4, and m represents 1 or 2, provided that when n5 is 2 or greater, X 5 may be a plurality of different groups,
wherein, in formula (4-2),
R 42 represents a hydrogen atom or a methyl group; each of R 201 and R 202 independently represents a hydrogen atom; each of A 1 and A 2 independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, or a carboxy group esterified with alcohol having 1 to 6 carbon atoms, or A 1 and A 2 together represent —O—, —S—, —NH—, or a methylene chain having 1 to 6 carbon atoms {—(CH 2 ) k — (wherein k represents an integer between 1 and 6)}; X 6 represents a linear or branched alkyl group having 1 to 6 carbon atoms that may have, as a substituent, at least one selected from the group consisting of a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, and an amino group, a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, or an amino group; and n6 represents an integer between 0 and 4, provided that when n6 is 2 or greater, X 6 may be a plurality of different groups,
wherein,
in formula (4-3), R 43 represents a hydrogen atom or a methyl group; each of R 203 and R 204 independently represents a hydrogen atom; each of A 3 and A 4 independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, or a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, or A 3 and A 4 together represent —O—, —S—, —NH—, or a methylene chain having 1 to 6 carbon atoms {—(CH 2 ) 1 — (wherein 1 represents an integer between 1 and 6)} ; X 7 represents a linear or branched alkyl group having 1 to 6 carbon atoms that may have, as a substituent, at least one selected from the group consisting of a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, and an amino group, a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, or an amino group; and n7 represents an integer between 0 and 4, provided that when n7 is 2 or greater, X 7 may be a plurality of different groups,
wherein,
in formula (4-5), R 45 represents a hydrogen atom or a methyl group; each of R 8 and R 9 independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms; each of R 52 , R 62 , and R 72 independently represents a hydrogen atom or a methyl group; each of Y 12 Y 22 and Y 32 independently represents —CH 2 —or —CO—O—, and at least one of them represents —CO—O—; X 9 represents a linear or branched alkyl group having 1 to 6 carbon atoms that may have, as a substituent, at least one selected from the group consisting of a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, and an amino group, a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, or an amino group; and n9 represents an integer between 0 and 4, provided that when n9 is 2 or greater, X 9 may be a plurality of different groups,
wherein,
in formula (4-6), R 46 represents a hydrogen atom or a methyl group; R 10 represents a hydrogen atom or a linear or branched alkyl group having 1 to 8 carbon atoms; each of R 53 , R 63 , and R 73 independently represents a hydrogen atom or a methyl group; each of Y 13 , Y 23 , and Y 33 independently represents —CH 2 —or —CO—O—, and at least one of them represents —CO—O—; X 10 represents a linear or branched alkyl group having 1 to 6 carbon atoms that may have, as a substituent, at least one selected from the group consisting of a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, and an amino group, a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, or an amino group; and n10 represents an integer between 0 and 4, provided that when n10 is 2 or greater, X 10 may be a plurality of different groups.
2. The resist polymer according to claim 1 , wherein said bridged cyclic hydrocarbon group has a skeleton selected from the group consisting of a cyclic terpene hydrocarbon, an adamantane ring, a tetracyclododecane ring, a dicylclopentane ring, and a tricyclodecane ring.
3. The resist polymer according to claim 1 , wherein the constitutional unit of formula (1) is a constitutional unit of formula (2):
wherein, in formula (2), R 01 represents a hydrogen atom or a methyl group.
4. The resist polymer according to claim 1 , wherein, in said formula (1),
a cyano group is bonded to a carbon atom that is adjacent to the ester carbon atom.
5. The resist polymer according to claim 1 , wherein said constitutional unit having a lactone skeleton is at least one selected from the group consisting of formulas (4-1), (4-2),and (4-3).
6. The resist polymer according to claim 1 , wherein a total ratio of the constitutional unit represented by said formula (1) is between 5% and 30% by mole,
a total ratio of the constitutional unit having an acid-dissociable group is between 30% and 60% by mole, and
a total ratio of the constitutional unit having a lactone skeleton is between 30% and 60% by mole.
7. The resist polymer according to claim 1 , wherein said constitutional unit having an acid-dissociable group has an alicyclic skeleton.
8. The resist polymer according to claim 7 , wherein said constitutional unit having an acid-dissociable group is at least one selected from the group consisting of formulas (3-1-1), (3-2-1), and (3-3-1):
wherein, in formula (3-1-1),
R 31 represents a hydrogen atom or a methyl group; R 1 represents an alkyl group having 1 to 3 carbon atoms; X 1 represents a linear or branched alkyl group having 1 to 6 carbon atoms that may have, as a substituent, at least one selected from the group consisting of a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, and an amino group, a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, or an amino group; and n1 represents an integer between 0 and 4, and when n1 is 2 or greater, X 1 may be a plurality of different groups,
wherein, in formula (3-2-1),
R 32 represents a hydrogen atom or a methyl group; each of R 2 and R 3 independently represents an alkyl group having 1 to 3 carbon atoms; X 2 represents a linear or branched alkyl group having 1 to 6 carbon atoms that may have, as a substituent, at least one selected from the group consisting of a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, and an amino group, a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, or an amino group; and n2 represents an integer between 0 and 4, and when n2 is 2 or greater, X 2 may be a plurality of different groups, and
wherein, in formula (3-3-1),
R 33 represents a hydrogen atom or a methyl group; R 4 represents an alkyl group having 1 to 3 carbon atoms; X 3 represents a linear or branched alkyl group having 1 to 6 carbon atoms that may have, as a substituent, at least one selected from the group consisting of a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, and an amino group, a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, or an amino group; and n3 represents an integer between 0 and 4, and q represents 0 or 1, provided that when n3 is 2 or greater, X 3 may be a plurality of different groups.
9. The resist polymer according to claim 1 , wherein said constitutional unit having an acid-dissociable group is a constitutional unit of formula (3-5):
wherein, in formula (3-5), R 35 represents a hydrogen atom or a methyl group.
10. The resist polymer according to claim 1 , wherein the constitutional units comprise:
at least one constitutional unit of formula (1);
at least one constitutional unit selected from the group consisting of formulas (3-1-1), (3-2-1), (3-3-1), and (3-5); and
at least one constitutional unit selected from the group consisting of formulas (4-1), (4-2), (4-3), (4-5), and (4-6):
wherein, in formula (3-1-1),
R 31 represents a hydrogen atom or a methyl group; R 1 represents an alkyl group having 1 to 3 carbon atoms; X 1 represents a linear or branched alkyl group having 1 to 6 carbon atoms that may have, as a substituent, at least one selected from the group consisting of a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, and an amino group, a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, or an amino group; and n1 represents an integer between 0 and 4, and when n1 is 2 or greater, X 1 may be a plurality of different groups,
wherein, in formula (3-2-1),
R 32 represents a hydrogen atom or a methyl group; each of R 2 and R 3 independently represents an alkyl group having 1 to 3 carbon atoms; X 2 represents a linear or branched alkyl group having 1 to 6 carbon atoms that may have, as a substituent, at least one selected from the group consisting of a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, and an amino group, a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, or an amino group; and n2 represents an integer between 0 and 4, and when n2 is 2 or greater, X 2 may be a plurality of different groups, and
wherein, in formula (3-3-1),
R 33 represents a hydrogen atom or a methyl group; R 4 represents an alkyl group having 1 to 3 carbon atoms; X 3 represents a linear or branched alkyl group having 1 to 6 carbon atoms that may have, as a substituent, at least one selected from the group consisting of a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, and an amino group, a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, or an amino group; and n3 represents an integer between 0 and 4, and q represents 0 or 1, provided that when n3 is 2 or greater, X 3 may be a plurality of different groups, and
wherein, in formula (3-5),
R 35 represents a hydrogen atom or a methyl group.
11. The resist polymer according to claim 10 , wherein the constitutional units comprise:
at least one constitutional unit of formula (1);
at least one constitutional unit selected from the group consisting of formulas (3-1-1), (3-2-1), (3-3-1), and (3-5); and
at least one constitutional unit selected from the group consisting of formulas (4-1), (4-2), and (4-3).
12. The resist polymer according to claim 1 , wherein the constitutional units comprise:
at least one constitutional unit of formula (2);
at least one constitutional unit selected from the group consisting of formulas (3-1-1), (3-3-1), and (3-5); and
at least one constitutional unit of formula (4-7):
wherein in formula (2), R 01 represents a hydrogen atom or a methyl group;
wherein, in formula (3-1-1),
R 31 represents a hydrogen atom or a methyl group; R 1 represents an alkyl group having 1 to 3 carbon atoms; X 1 represents a linear or branched alkyl group having 1 to 6 carbon atoms that may have, as a substituent, at least one selected from the group consisting of a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, and an amino group, a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, or an amino group; and n1 represents an integer between 0 and 4, and when n1 is 2 or greater, X 1 may be a plurality of different groups,
wherein, in formula (3-3-1),
R 33 represents a hydrogen atom or a methyl group; R 4 represents an alkyl group having 1 to 3 carbon atoms; X 3 represents a linear or branched alkyl group having 1 to 6 carbon atoms that may have, as a substituent, at least one selected from the group consisting of a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, and an amino group, a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, or an amino group; and n3 represents an integer between 0 and 4, and q represents 0 or 1, provided that when n3 is 2 or greater, X 3 may be a plurality of different groups,
wherein in formula (3-5),
R 35 represents a hydrogen atom or a methyl group, and
wherein, in formula (4-7), R 47 represents a hydrogen atom or a methyl group.
13. The resist polymer according to claim 12 , wherein a total ratio of the at least one constitutional unit of formula (2) is between 5% and 30% by mole,
a total ratio of the at least one constitutional unit selected from the group consisting of formulas (3-1-1), (3-3-1), and (3-5) is between 30% and 60% by mole, and
a total ratio of the constitutional unit of formula (4-7) is between 30% and 60% by mole.
14. The resist polymer according to claim 1 , wherein the constitutional units comprise:
at least one constitutional unit of formula (2);
at least one constitutional unit selected from the group consisting of formulas (3-1-1), (3-3-1), and (3-5), and
at least one constitutional unit of formula (4-8):
wherein in formula (2), R 01 represents a hydrogen atom or a methyl group;
wherein, in formula (3-1-1),
R 31 represents a hydrogen atom or a methyl group; R 1 represents an alkyl group having 1 to 3 carbon atoms; X 1 represents a linear or branched alkyl group having 1 to 6 carbon atoms that may have, as a substituent, at least one selected from the group consisting of a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, and an amino group, a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, or an amino group; and n1 represents an integer between 0 and 4, and when n1 is 2 or greater, X 1 may be a plurality of different groups,
wherein, in formula (3-3-1),
R 33 represents a hydrogen atom or a methyl group; R 4 represents an alkyl group having 1 to 3 carbon atoms; X 3 represents a linear or branched alkyl group having 1 to 6 carbon atoms that may have, as a substituent, at least one selected from the group consisting of a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, and an amino group, a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, or an amino group; and n3 represents an integer between 0 and 4, and q represents 0 or 1, provided that when n3 is 2 or greater, X 3 may be a plurality of different groups,
wherein in formula (3-5),
R 35 represents a hydrogen atom or a methyl group, and
wherein, in formula (4-8), R 48 represents a hydrogen atom or a methyl group.
15. The resist polymer according to claim 14 , wherein a total ratio of the at least one constitutional unit of formula (2) is between 5% and 30% by mole,
a total ratio of at least one constitutional unit selected from the group consisting of formulas (3-1-1), (3-3-1), and (3-5) is between 30% and 60% by mole, and
a total ratio of the constitutional unit of formula (4-8) is between 30% and 60% by mole.
16. The resist polymer according to claim 14 , wherein the constitutional units comprise:
at least one constitutional unit of formula (2);
at least one constitutional unit of formula (3-1-1); and
at least one constitutional unit of formula (4-8).
17. The resist polymer according to claim 16 , wherein
a total ratio of the constitutional unit of formula (2) is between 5% and 30% by mole,
a total ratio of the constitutional unit of formula (3-1-1) is between 30% and 60% by mole, and
a total ratio of the constitutional unit of formula (4-8) is between 30% and 60% by mole.
18. The resist polymer according to claim 1 , wherein the constitutional units comprise:
at least one constitutional unit of formula (2);
at least one constitutional unit selected from the group consisting of formulas (3-1-1), (3-3-1), and (3-5); and
at least one constitutional unit represented by formula (4-9):
wherein in formula (2), R 01 represents a hydrogen atom or a methyl group;
wherein, in formula (3-1-1),
R 31 represents a hydrogen atom or a methyl group; R 1 represents an alkyl group having 1 to 3 carbon atoms; X 1 represents a linear or branched alkyl group having 1 to 6 carbon atoms that may have, as a substituent, at least one selected from the group consisting of a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, and an amino group, a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, or an amino group; and n1 represents an integer between 0 and 4, and when n1 is 2 or greater, X 1 may be a plurality of different groups,
wherein, in formula (3-3-1),
R 33 represents a hydrogen atom or a methyl group; R 4 represents an alkyl group having 1 to 3 carbon atoms; X 3 represents a linear or branched alkyl group having 1 to 6 carbon atoms that may have, as a substituent, at least one selected from the group consisting of a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, and an amino group, a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, or an amino group; and n3 represents an integer between 0 and 4, and q represents 0 or 1, provided that when n3 is 2 or greater, X 3 may be a plurality of different groups,
wherein in formula (3-5),
R 35 represents a hydrogen atom or a methyl group, and
wherein, in formula (4-9), R 49 represents a hydrogen atom or a methyl group.
19. The resist polymer according to claim 18 , wherein
a total ratio of the at least one constitutional unit of formula (2) is between 5% and 30% by mole,
a total ratio of the at least one constitutional unit selected from the group consisting of formulas (3-1-1), (3-3-1), and (3-5) is between 30% and 60% by mole, and
a total ratio of the constitutional unit of formula (4-9) is between 30% and 60% by mole.
20. The resist polymer according to claim 1 , wherein the constitutional units comprise:
at least one constitutional unit selected from the group consisting of formulas (2) and (1-1);
at least one constitutional unit selected from the group consisting of formulas (3-1-1), (3-3-1), and (3-5); and
at least one constitutional unit selected from the group consisting of formulas (4-2) and (4-3):
wherein in formula (2), R 01 represents a hydrogen atom or a methyl group;
wherein, in formula (3-1-1),
R 31 represents a hydrogen atom or a methyl group; R 1 represents an alkyl group having 1 to 3 carbon atoms; X 1 represents a linear or branched alkyl group having 1 to 6 carbon atoms that may have, as a substituent, at least one selected from the group consisting of a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, and an amino group, a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, or an amino group; and n1 represents an integer between 0 and 4, and when n1 is 2 or greater, X 1 may be a plurality of different groups,
wherein, in formula (3-3-1),
R 33 represents a hydrogen atom or a methyl group; R 4 represents an alkyl group having 1 to 3 carbon atoms; X 3 represents a linear or branched alkyl group having 1 to 6 carbon atoms that may have, as a substituent, at least one selected from the group consisting of a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, and an amino group, a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, or an amino group; and n3 represents an integer between 0 and 4, and q represents 0 or 1, provided that when n3 is 2 or greater, X 3 may be a plurality of different groups,
wherein in formula (3-5),
R 35 represents a hydrogen atom or a methyl group.
21. The resist polymer according to claim 20 , wherein
a total ratio of the at least one constitutional unit of formula (2) is between 5% and 30% by mole,
a total ratio of the at least one constitutional unit selected from the group consisting of formulas (3-1-1), (3-3-1), and (3-5) is between 30% and 60% by mole, and
a total ratio of the at least one constitutional unit selected from the group consisting of formulas (4-2) and (4-3) is between 30% and 60% by mole.
22. The resist polymer according to claim 1 , wherein the constitutional units comprise:
at least one constitutional unit of formula (1);
at least one constitutional unit selected from the group consisting of formulas (3-1-1), (3-2-1), and (3-3-1); and
at least one constitutional unit selected from the group consisting of formulas (4-7) and (4-8)
wherein, in formula (3-1-1),
R 31 represents a hydrogen atom or a methyl group; R 1 represents an alkyl group having 1 to 3 carbon atoms; X 1 represents a linear or branched alkyl group having 1 to 6 carbon atoms that may have, as a substituent, at least one selected from the group consisting of a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, and an amino group, a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, or an amino group; and n1 represents an integer between 0 and 4, and when n1 is 2 or greater, X 1 may be a plurality of different groups,
wherein, in formula (3-2-1),
R 32 represents a hydrogen atom or a methyl group; each of R 2 and R 3 independently represents an alkyl group having 1 to 3 carbon atoms; X 2 represents a linear or branched alkyl group having 1 to 6 carbon atoms that may have, as a substituent, at least one selected from the group consisting of a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, and an amino group, a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, or an amino group; and n2 represents an integer between 0 and 4, and when n2 is 2 or greater, X 2 may be a plurality of different groups,
wherein, in formula (3-3-1),
R 33 represents a hydrogen atom or a methyl group; R 4 represents an alkyl group having 1 to 3 carbon atoms; X 3 represents a linear or branched alkyl group having 1 to 6 carbon atoms that may have, as a substituent, at least one selected from the group consisting of a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, and an amino group, a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, or an amino group; and n3 represents an integer between 0 and 4, and q represents 0 or 1, provided that when n3 is 2 or greater, X 3 may be a plurality of different groups, and
wherein, in formula (4-7), R 47 represents a hydrogen atom or a methyl group, and
wherein, in formula (4-8), R 48 represents a hydrogen atom or a methyl group.
23. The resist polymer according to claim 22 , wherein
a total ratio of the constitutional unit of formula (1) is between 5% and 30% by mole,
a total ratio of the at least one constitutional unit selected from the group consisting of formulas (3-1-1), (3-2-1), and (3-3-1) is between 30% and 60% by mole, and
a total ratio of the at least one constitutional unit selected from the group consisting of formulas (4-7) and (4-8) is between 30% and 60% by mole.
24. The resist polymer according to claim 1 , wherein the constitutional units further comprise at least one constitutional unit selected from the group consisting of formulas (3-1-2) and (3-4):
wherein, in formula (3-1-2),
R 31 represents a hydrogen atom or a methyl group; R 11 represents a hydrogen atom; X 1 represents a linear or branched alkyl group having 1 to 6 carbon atoms that may have, as a substituent, at least one selected from the group consisting of a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, a cyano group, and an amino group, a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, or an amino group; and n1 represents an integer between 0 and 4, and when n1 is 2 or greater, X 1 may be a plurality of different groups, and
wherein, in formula (3-4),
R 34 represents a hydrogen atom or a methyl group; X 4 represents a linear or branched alkyl group having 1 to 6 carbon atoms that may have, as a substituent, at least one selected from the group consisting of a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, and an amino group, a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, or an amino group; and n4 represents an integer between 0 and 4, and when n4 is 2 or greater, X 4 may be a plurality of different groups.
25. The resist polymer according to claim 1 , which has a mass average molecular weight between 1,000 and 100,000.
26. The resist polymer according to claim 1 , which is produced by carrying out polymerization, while adding dropwise to a polymerization reactor a solution containing monomers that become constitutional units of a polymer of interest as a result of the polymerization.
27. A resist composition, which comprises the resist polymer according to claim 1 .
28. A method of producing a pattern, which comprises:
applying the resist composition according to claim 27 onto a substrate to be processed;
exposing the substrate to a light with a wavelength of 250 nm or shorter; and
developing the exposed resist composition with a developing solution.
29. The method of producing a pattern according to claim 28 , wherein the light used for exposure is an ArF excimer laser.
30. A method of producing a pattern, which comprises:
applying the resist composition according to claim 27 onto a substrate to be processed,
exposing the substrate to an electron beam, and
developing the exposed resist composition with a developing solution.
31. A chemically amplified resist composition, which comprises the resist polymer according to claim 1 and a photoacid generator.
32. The chemically amplified resist composition according to claim 31 , which further comprises a nitrogen-containing compound.
33. The resist polymer according to claim 1 , which has a mass average molecular weight between 5,000 and 8,000.
34. A resist composition, which comprises the resist polymer according to claim 33 .
35. A method of producing a pattern, which comprises:
applying the resist composition according to claim 34 onto a substrate to be processed;
exposing the substrate to a light with a wavelength of 250 nm or shorter; and
developing the exposed resist composition with a developing solution.
36. The method of producing a pattern according to claim 35 , wherein the light used for exposure is an ArF excimer laser.
37. A method of producing a pattern, which comprises:
applying the resist composition according to claim 34 onto a substrate to be processed;
exposing the substrate to an electron beam; and
developing the exposed resist composition with a developing solution.
38. A chemically amplified resist composition, which comprises the resist polymer according to claim 33 and a photoacid generator.
39. The chemically amplified resist composition according to claim 38 , which further comprises a nitrogen-containing compound.
40. A resist polymer consisting essentially of constitutional units derived from (meth)acrylate monomers, wherein the constitutional units comprise:
at least one constitutional unit of formula (2);
at least one constitutional unit selected from the group consisting of formulas (3-1-1), (3-3-1), and (3-5) ; and
at least one constitutional unit of formula (4- 11):
wherein in formula (2), R 01 represents a hydrogen atom or a methyl group;
wherein, in formula (3-1-1),
R 31 represents a hydrogen atom or a methyl group; R 1 represents an alkyl group having 1 to 3 carbon atoms; X 1 represents a linear or branched alkyl group having 1 to 6 carbon atoms that may have, as a substituent, at least one selected from the group consisting of a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, and an amino group, a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, or an amino group; and n1 represents an integer between 0 and 4, and when n1 is 2 or greater, X 1 may be a plurality of different groups,
wherein, in formula (3-3-1),
R 33 represents a hydrogen atom or a methyl group; R 4 represents an alkyl group having 1 to 3 carbon atoms; X 3 represents a linear or branched alkyl group having 1 to 6 carbon atoms that may have, as a substituent, at least one selected from the group consisting of a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, and an amino group, a hydroxy group, a carboxy group, an acyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a carboxy group that is esterified with alcohol having 1 to 6 carbon atoms, or an amino group; and n3 represents an integer between 0 and 4, and q represents 0 or 1, provided that when n3 is 2 or greater, X 3 may be a plurality of different groups,
wherein in formula (3-5),
R 35 represents a hydrogen atom or a methyl group, and
wherein, in formula (4-11), R 411 represents a hydrogen atom or a methyl group.
41. The resist polymer according to claim 40 , wherein
a total ratio of the at least one constitutional unit of formula (2) is between 5% and 30% by mole,
a total ratio of the at least one constitutional unit selected from the group consisting of formulas (3-1-1), (3-3-1), and (3-5) is between 30% and 60% by mole, and
a total ratio of the constitutional unit of formula (4-11) is between 30% and 60% by mole.
42. A resist composition, which comprises the resist polymer according to claim 40 .
43. A chemically amplified resist composition, which comprises the resist polymer according to claim 40 and a photoacid generator.
44. The chemically amplified resist composition according to claim 43 , which further comprises a nitrogen-containing compound.
45. A method of producing a pattern, which comprises:
applying the chemically amplified resist composition according to claim 43 onto a substrate to be processed;
exposing the substrate to a light with a wavelength of 250 nm or shorter; and
developing it with a developing solution.
46. The method of producing a pattern according to claim 45 , wherein the light used for exposure is an ArF excimer laser.
47. A method of producing a pattern, which comprises:
applying the chemically amplified resist composition according to claim 43 onto a substrate to be processed;
exposing the substrate to an electron beam; and
developing it with a developing solution.