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 including an acid-labile group; a second polymer including a structural unit represented by formula (1); and a radiation-sensitive acid generator. In the formula (1), A represents an oxygen atom or a sulfur atom; a sum of m and n is 2 or 3, wherein m is 1 or 2, and n is 1 or 2; X represents a single bond or a divalent organic group having 1 to 20 carbon atoms; and R 1 represents a monovalent organic group including a fluorine atom.
1 . A radiation-sensitive resin composition comprising:
a first polymer comprising a structural unit comprising an acid-labile group;
a second polymer comprising a structural unit represented by formula (1); and
a radiation-sensitive acid generator,
wherein, in the formula (1), A represents an oxygen atom or a sulfur atom; a sum of m and n is 2 or 3, wherein m is 1 or 2, and n is 1 or 2; X represents a single bond or a divalent organic group having 1 to 20 carbon atoms; and R 1 represents a monovalent organic group comprising a fluorine atom.
2 . The radiation-sensitive resin composition according to claim 1 , wherein R 1 in the formula (1) represents a group defined as (1-1) or (1-2):
(1-1): a group represented by *—COO—R 1a , wherein R 1a represents a substituted or unsubstituted monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms, or a monovalent organic group comprising —O—, —CO—, or —COO— between two carbon atoms in a C—C bond constituting a substituted or unsubstituted monovalent fluorinated hydrocarbon group having 2 to 20 carbon atoms; and * denotes a site of bonding to X in the formula (1); and
(1-2): a substituted or unsubstituted monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms, or a group comprising —O—, —CO—, or —COO— between two carbon atoms in a C—C bond constituting a substituted or unsubstituted monovalent fluorinated hydrocarbon group having 2 to 20 carbon atoms, wherein the group defined as (1-2) does not fall under the group defined as (1-1).
3 . The radiation-sensitive resin composition according to claim 2 , wherein R 1a in the group defined as (1-1) represents a substituted or unsubstituted monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms, —R 1b —COO—R 1c , or —R 1d —O—R 1e ,
wherein
R 1b represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted divalent fluorinated hydrocarbon group having 1 to 20 carbon atoms, or a divalent organic group comprising a lactone structure and having 4 to 20 carbon atoms,
R 1c represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms or a substituted or unsubstituted monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms,
wherein at least one of R 1b and R 1c comprises a fluorine atom,
R 1d represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted divalent fluorinated hydrocarbon group having 1 to 20 carbon atoms, or a divalent organic group comprising a lactone structure and having 4 to 20 carbon atoms, and
R 1e represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms, or —R 1f —O—R 1g ,
wherein
R 1f represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms or a substituted or unsubstituted divalent fluorinated hydrocarbon group having 1 to 20 carbon atoms, and
R 1g represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms or a substituted or unsubstituted monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms,
wherein at least one of R 1d and R 1e comprises a fluorine atom.
4 . The radiation-sensitive resin composition according to claim 2 , wherein the group defined as (1-2) represents a substituted or unsubstituted monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms,*—CO—R 2a , *—R 2b —COO—R 2c , or *—R 2d —O—R 2e ,
wherein
R 2a represents a substituted or unsubstituted monovalent fluorinated hydrocarbon group having 10 to 20 carbon atoms,
R 2b represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted divalent fluorinated hydrocarbon group having 1 to 20 carbon atoms, or a divalent organic group comprising a lactone structure and having 4 to 20 carbon atoms,
R 2c represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms or a substituted or unsubstituted monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms,
wherein at least one of R 2b and R 2c comprises a fluorine atom,
R 2d represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted divalent fluorinated hydrocarbon group having 1 to 20 carbon atoms, or a divalent organic group comprising a lactone structure and having 4 to 20 carbon atoms, and
R 2e represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms, or —R 2f —O—R 2g ,
wherein
R 2f represents a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms or a substituted or unsubstituted divalent fluorinated hydrocarbon group having 1 to 20 carbon atoms, and
R 2g represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms or a substituted or unsubstituted monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms,
wherein at least one of R 2d and R 2e comprises a fluorine atom.
5 . The radiation-sensitive resin composition according to claim 1 , wherein X in the formula (1) represents a single bond, a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent organic group comprising a lactone structure and having 4 to 20 carbon atoms, —X 1 —O—, or —X 2 —NH—,
wherein X 1 and X 2 each independently represent a divalent hydrocarbon group having 1 to 20 carbon atoms.
6 . The radiation-sensitive resin composition according to claim 5 , wherein each divalent hydrocarbon group having 1 to 20 carbon atoms which may be represented by each of X in the formula (1), X 1 , and X 2 independently represents a divalent chain hydrocarbon group having 1 to 4 carbon atoms, a divalent alicyclic hydrocarbon group having 6 to 10 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms.
7 . A method of forming a resist pattern, the method comprising:
applying the radiation-sensitive resin composition according to claim 1 directly or indirectly on a substrate to form a resist film;
exposing the resist film; and
developing the resist film exposed.
8 . The method according to claim 7 , wherein R 1 in the formula (1) is a group defined as (1-1) or (1-2):
(1-1): a group represented by *—COO—R 1a , wherein R 1a represents a substituted or unsubstituted monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms, or a monovalent organic group comprising —O—, —CO—, or —COO— between two carbon atoms in a C—C bond constituting a substituted or unsubstituted monovalent fluorinated hydrocarbon group having 2 to 20 carbon atoms; and * denotes a site of bonding to X in the formula (1); and
(1-2): a substituted or unsubstituted monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms, or a group comprising —O—, —CO—, or —COO— between two carbon atoms in a C—C bond constituting a substituted or unsubstituted monovalent fluorinated hydrocarbon group having 2 to 20 carbon atoms, wherein the group defined as (1-2) does not fall under the group defined as (1-1).
9 . The method according to claim 7 , wherein X in the formula (1) represents a single bond, a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent organic group comprising a lactone structure and having 4 to 20 carbon atoms, —X 1 —O—, or —X 2 —NH—,
wherein X 1 and X 2 each independently represent a divalent hydrocarbon group having 1 to 20 carbon atoms.
10 . The method according to claim 9 , wherein each divalent hydrocarbon group having 1 to 20 carbon atoms which may be represented by each of X in the formula (1), X 1 , and X 2 independently represents a divalent chain hydrocarbon group having 1 to 4 carbon atoms, a divalent alicyclic hydrocarbon group having 6 to 10 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms.
11 . A polymer comprising a structural unit represented by formula (1):
wherein, in the formula (1), A represents an oxygen atom or a sulfur atom; a sum of m and n is 2 or 3, wherein m is 1 or 2, and n is 1 or 2; X represents a single bond or a divalent organic group having 1 to 20 carbon atoms; and R 1 represents a monovalent organic group comprising a fluorine atom.
12 . The polymer according to claim 11 , wherein R 1 in the formula (1) is a group defined as (1-1) or (1-2):
(1-1): a group represented by *—COO—R 1a , wherein R 1a represents a substituted or unsubstituted monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms, or a monovalent organic group comprising —O—, —CO—, or —COO— between two carbon atoms in a C—C bond constituting a substituted or unsubstituted monovalent fluorinated hydrocarbon group having 2 to 20 carbon atoms; and * denotes a site of bonding to X in the formula (1); and
(1-2): a substituted or unsubstituted monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms, or a group comprising —O—, —CO—, or —COO— between two carbon atoms in a C—C bond constituting a substituted or unsubstituted monovalent fluorinated hydrocarbon group having 2 to 20 carbon atoms, wherein the group defined as (1-2) does not fall under the group defined as (1-1).
13 . The polymer according to claim 11 , wherein X in the formula (1) represents a single bond, a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent organic group comprising a lactone structure and having 4 to 20 carbon atoms, —X 1 —O—, or —X 2 —NH—,
wherein X 1 and X 2 each independently represent a divalent hydrocarbon group having 1 to 20 carbon atoms.
14 . The polymer according to claim 13 , wherein each divalent hydrocarbon group having 1 to 20 carbon atoms which may be represented by each of X in the formula (1), X 1 , and X 2 independently represents a divalent chain hydrocarbon group having 1 to 4 carbon atoms, a divalent alicyclic hydrocarbon group having 6 to 10 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms.
15 . A compound represented by formula (i):
wherein, in the formula (i), A represents an oxygen atom or a sulfur atom; a sum of m and n is 2 or 3, wherein m is 1 or 2, and n is 1 or 2; X represents a single bond or a divalent organic group having 1 to 20 carbon atoms; and R 1 represents a monovalent organic group comprising a fluorine atom.
16 . The compound according to claim 15 , wherein R 1 in the formula (i) is a group defined as (1-1) or (1-2):
(1-1): a group represented by *—COO—R 1a , wherein R 1a represents a substituted or unsubstituted monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms, or a monovalent organic group comprising —O—, —CO—, or —COO— between two carbon atoms in a C—C bond constituting a substituted or unsubstituted monovalent fluorinated hydrocarbon group having 2 to 20 carbon atoms; and * denotes a site of bonding to X in the formula (i); and
(1-2): a substituted or unsubstituted monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms, or a group comprising —O—, —CO—, or —COO— between two carbon atoms in a C—C bond constituting a substituted or unsubstituted monovalent fluorinated hydrocarbon group having 2 to 20 carbon atoms, wherein the group defined as (1-2) does not fall under the group defined as (1-1).
17 . The compound according to claim 15 , wherein X in the formula (i) represents a single bond, a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent organic group comprising a lactone structure and having 4 to 20 carbon atoms, —X 1 —O—, or —X 2 —NH—,
wherein X 1 and X 2 each independently represent a divalent hydrocarbon group having 1 to 20 carbon atoms.
18 . The compound according to claim 17 , wherein each divalent hydrocarbon group having 1 to 20 carbon atoms which may be represented by each of X in the formula (i), X 1 , and X 2 independently represents a divalent chain hydrocarbon group having 1 to 4 carbon atoms, a divalent alicyclic hydrocarbon group having 6 to 10 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms.