Radiation-sensitive resin composition, method of forming resist pattern, polymer, and compound
A radiation-sensitive resin composition includes: a first polymer including a structural unit which includes an acid-labile group; a second polymer including a structural unit represented by formula (1); and a radiation-sensitive acid generator. R 1 represents a monovalent organic group having 1 to 20 carbon atoms; R 2 represents a monovalent organic group having 1 to 20 carbon atoms; X represents a divalent organic group having 1 to 20 carbon atoms; and Y represents a divalent hydrocarbon group having 1 to 20 carbon atoms. The divalent organic group represented by X, the monovalent organic group represented by R 2 , or both has a fluorine atom.
1. A radiation-sensitive resin composition comprising:
a first polymer comprising a structural unit which comprises an acid-labile group;
a second polymer comprising:
a structural unit represented by formula (1); and
a structural unit which comprises an acid-labile group and which is represented by at least one formula selected from the group consisting of formula (2-1A), formula (2-1B), formula (2-2A), and formula (2-2B); and
a radiation-sensitive acid generator,
wherein, in the formula (1), one of R 1 and R 2 represents a substituted or unsubstituted hydrocarbon group which is a substituted or unsubstituted monovalent chain hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or combinations thereof; the other one of R 1 and R 2 represents a substituted or unsubstituted hydrocarbon group which is a substituted or unsubstituted monovalent chain hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or combinations thereof; provided that in a case where R 1 or R 2 comprises a methylene group, the methylene group is optionally replaced with an ester group, an ether group, or both; X represents a divalent organic group having 1 to 20 carbon atoms; and Y represents a divalent hydrocarbon group having 1 to 20 carbon atoms, wherein the divalent organic group represented by X, the monovalent organic group represented by R 2 , or both has a fluorine atom,
wherein R T represents a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group; R X represents a monovalent hydrocarbon group having 1 to 20 carbon atoms; R Y and R Z each independently represent a monovalent hydrocarbon group having 1 to 20 carbon atoms, or R Y and R Z taken together represent an alicyclic structure having 3 to 20 ring atoms, together with the carbon atom to which R Y and R Z bond; R U represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms; and R Y and R W each independently represent a monovalent hydrocarbon group having 1 to 20 carbon atoms, or R Y and R W taken together represent an aliphatic heterocyclic structure having 4 to 20 ring atoms, together with the carbon atom to which R″ bonds and the oxygen atom adjacent to the carbon atom.
2. The radiation-sensitive resin composition according to claim 1 , wherein
X represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms, —X 1 —O—, or —X 2 —NH—, wherein
X 1 and X 2 each independently represent a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms.
3. The radiation-sensitive resin composition according to claim 2 , wherein the divalent hydrocarbon group having 1 to 20 carbon atoms represented by X 1 and the divalent hydrocarbon group having 1 to 20 atoms represented by X 2 are each independently a divalent aliphatic hydrocarbon group having 1 to 4 carbon atoms.
4. The radiation-sensitive resin composition according to claim 1 , wherein in the formula (1), condition (a), condition (b), or both is satisfied:
(a) X represents —X 1 —O—, or —X 2 —NH—, wherein X 1 and X 2 each independently represent a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms;
(b) R 1 , R 2 , or both represents a group in which at least one methylene group in a substituted or unsubstituted hydrocarbon group having at least 2 carbon atoms is replaced with an ester group, an ether group, or both.
5. The radiation-sensitive resin composition according to claim 1 , wherein in the formula (1), X represents —X 1 —O— or —X 2 —NH—, wherein X 1 and X 2 each independently represent a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms.
6. The radiation-sensitive resin composition according to claim 1 , wherein in the formula (1), R 1 represents a group in which at least one methylene group in a substituted or unsubstituted hydrocarbon group having at least 2 carbon atoms is replaced with an ester group, an ether group, or both.
7. The radiation-sensitive resin composition according to claim 1 , wherein in the formula (1), R 2 represents a group in which at least one methylene group in a substituted or unsubstituted hydrocarbon group having at least 2 carbon atoms is replaced with an ester group.
8. A method of forming a resist pattern, the method comprising:
forming a resist film directly or indirectly on a substrate by applying the radiation-sensitive resin composition according to claim 1 ;
exposing the resist film; and
developing the resist film exposed.
9. A polymer comprising:
a structural unit represented by formula (1); and
a structural unit which comprises an acid-labile group and which is represented by at least one formula selected from the group consisting of formula (2-1A), formula (2-1B), formula (2-2A), and formula (2-2B):
wherein, in the formula (1), one of R 1 and R 2 represents a substituted or unsubstituted hydrocarbon group which is a substituted or unsubstituted monovalent chain hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or combinations thereof; the other one of R 1 and R 2 represents a substituted or unsubstituted hydrocarbon group which is a substituted or unsubstituted monovalent chain hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or combinations thereof; provided that in a case where R 1 or R 2 comprises a methylene group, the methylene group optionally replaced with an ester group, an ether group, or both; X represents a divalent organic group having 1 to 20 carbon atoms; and Y represents a divalent hydrocarbon group having 1 to 20 carbon atoms, wherein the divalent organic group represented by X, the monovalent organic group represented by R 2 , or both has a fluorine atom,
wherein R T represents a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group; R X represents a monovalent hydrocarbon group having 1 to 20 carbon atoms; R Y and R Z each independently represent a monovalent hydrocarbon group having 1 to 20 carbon atoms, or R Y and R 2 taken together represent an alicyclic structure having 3 to 20 ring atoms, together with the carbon atom to which R Y and R Z bond; R U represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms; and R Y and R W each independently represent a monovalent hydrocarbon group having 1 to 20 carbon atoms, or R Y and R W taken together represent an aliphatic heterocyclic structure having 4 to 20 ring atoms, together with the carbon atom to which R″ bonds and the oxygen atom adjacent to the carbon atom.
10. The radiation-sensitive resin composition according to claim 1 , wherein the second polymer further comprises a structural unit which comprises a group represented by formula (m-12) and/or a group represented by formula (m-14):
11. The polymer according to claim 9 , further comprising a structural unit which comprises a group represented by formula (m-12) and/or a group represented by formula (m-14):
12. The radiation-sensitive resin composition according to claim 1 , wherein an amount of the structural unit which comprises an acid-labile group in the second polymer is 10 to 50 mol % relative to total structural units in the second polymer.
13. The polymer according to claim 9 , wherein an amount of the structural unit which comprises an acid-labile group in the polymer is 10 to 50 mol % relative to total structural units in the polymer.
14. The polymer according to claim 9 , wherein in the formula (1), R 1 represents a group in which at least one methylene group in a substituted or unsubstituted hydrocarbon group having at least 2 carbon atoms is replaced with an ester group, an ether group, or both.
15. The polymer according to claim 9 , wherein in the formula (1), R 2 represents a group in which at least one methylene group in a substituted or unsubstituted hydrocarbon group having at least 2 carbon atoms is replaced with an ester group.
16. The radiation-sensitive resin composition according to claim 1 , wherein the monovalent organic group having 1 to 20 carbon atoms represented by R 2 is —(CH 2 ) 3 CF 2 (CF 3 ).
17. The polymer according to claim 9 , wherein the monovalent organic group having 1 to 20 carbon atoms represented by R 2 is (CH 2 ) 3 CF 2 (CF 3 ).
18. The radiation-sensitive resin composition according to claim 1 , wherein R 1 represents a group in which at least one methylene group in a substituted or unsubstituted hydrocarbon group having at least 2 carbon atoms is replaced with an ester group.
19. The polymer according to claim 9 , wherein R 1 represents a group in which at least one methylene group in a substituted or unsubstituted hydrocarbon group having at least 2 carbon atoms is replaced with an ester group.
20. The radiation-sensitive resin composition according to claim 1 , wherein R 2 represents an unsubstituted hydrocarbon group which is an unsubstituted monovalent chain hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, an unsubstituted monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or combinations thereof.