Carboxylate, carboxylic acid generator, resin, resist composition and method for producing resist pattern
A carboxylate represented by formula (I), a resin comprising a structural unit derived from the carboxylate represented by formula (I), a resit composition comprising the carboxylate represented by formula (I) or a resin comprising a structural unit derived from the carboxylate represented by formula (I).
1 . A carboxylate represented by formula (I):
wherein, in formula (I),
R 4 ,
R 5 and R 6 each independently represent a fluorine atom, an iodine atom or a perfluoroalkyl group having 1 to 4 carbon atoms,
R 7 , R 8 and R 9 each independently represent a halogen atom, a haloalkyl group having 1 to 12 carbon atoms or a hydrocarbon group having 1 to 18 carbon atoms, wherein each of the hydrocarbon group may have a substituent, and a —CH 2 — included in each of the haloalkyl group and the hydrocarbon group may be replaced by —O—, —CO—, —S— or —SO 2 —,
A 1 , A 2 and A 3 each independently represent a hydrocarbon group having 1 to 20 carbon atoms, wherein each of the hydrocarbon group may have a substituent, and a —CH 2 — included in each of the hydrocarbon group may be replaced by —O—, —CO—, —S— or —SO 2 —,
m1 represents an integer of 1 to 5, and when m1 is 2 or more, a plurality of groups in parentheses may be the same or different from each other,
m2 represents an integer of 0 to 5, and when m2 is 2 or more, a plurality of groups in parentheses may be the same or different from each other,
m3 represents an integer of 0 to 5, and when m3 is 2 or more, a plurality of groups in parentheses may be the same or different from each other,
m4 represents an integer of 0 to 5, and when m4 is 2 or more, a plurality of R 4 may be the same or different from each other,
m5 represents an integer of 0 to 5, and when m5 is 2 or more, a plurality of R 5 may be the same or different from each other,
m6 represents an integer of 0 to 5, and when m6 is 2 or more, a plurality of R 6 may be the same or different from each other,
m7 represents an integer of 0 to 4, and when m7 is 2 or more, a plurality of R 7 may be the same or different from each other,
m8 represents an integer of 0 to 5, and when m8 is 2 or more, a plurality of R 8 may be the same or different from each other,
m9 represents an integer of 0 to 5, and when m9 is 2 or more, a plurality of R 9 may be the same or different from each other,
in which 1≤m1+m7≤5, 0≤m2+m8≤5, 0≤m3+m9≤5, and m4, m5 and m6 are not 0,
X 0 represents a single bond or a hydrocarbon group having 1 to 72 carbon atoms which may have a substituent, and a —CH 2 — included in the hydrocarbon group may be replaced by —O—, —S—, —CO— or —SO 2 —,
X 10 represents a single bond, *—C—OO—, *—O—CO—, or *-Ax-Ph-Ay-,
Ph represents a phenylene group which may have a substituent,
Ax represents a single bond, an ether bond, an ester bond or a carbonic acid ester bond,
Ay represents a single bond, an ether bond, an ester bond or a carbonic acid ester bond,
* represents a bonding site to carbon atoms to which —R bb1 is bonded,
** represents a bonding site to L 10 ,
L 10 represents a single bond or a hydrocarbon group having 1 to 36 carbon atoms which may have a substituent, and a —CH 2 — included in the hydrocarbon group may be replaced by —O—, —S—, —SO 2 — or —CO—, and
R bb1 is a hydrogen atom, a halogen atom, or an alkyl having 1 to 6 carbon atoms which may have a halogen atom.
2 . The carboxylate according to claim 1 , wherein A 1 is ***—X 01 -L 01 - or ***-L 01 -X 01 —,
A 2 is ***—X 02 -L 02 - or ***-L 02 -X 02 —,
A 3 is ***—X 03 -L 03 - or ***-L 03 -X 03 —,
X 01 , X 02 and X 03 each independently represent —O—, —CO—, —S— or —SO 2 —,
L 01 , L 02 and L 03 each independently represent a single bond or a hydrocarbon group having 1 to 18 carbon atoms, and
each *** represents a bonding site to the benzene ring to which S* is bonded.
3 . The carboxylate according to claim 2 , wherein X 01 , X 02 and X 03 are oxygen atoms.
4 . The carboxylate according to claim 2 , wherein L 01 , L 02 and L 03 are each independently a single bond or an alkanediyl group having 1 to 6 carbon atoms.
5 . The carboxylate according to claim 1 , wherein X 0 is an aliphatic hydrocarbon group having 1 to 72 carbon atoms which may have a substituent, and a —CH 2 — included in the aliphatic hydrocarbon group may be replaced by —O—, —S—, —CO— or —SO 2 — or
an aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a substituent.
6 . The carboxylate according to claim 5 , wherein X 0 includes
an alicyclic hydrocarbon group having 3 to 36 carbon atoms which may have a fluorine atom, a perfluoroalkyl group having 1 to 4 carbon atoms or a hydroxy group and a —CH 2 — included in the alicyclic hydrocarbon group may be replaced by —O—, —S—, —CO— or —SO 2 —,
a group obtained by combining an alicyclic hydrocarbon group having 3 to 36 carbon atoms with a chain hydrocarbon group having 1 to 18 carbon atoms, a —CH 2 — included in the alicyclic hydrocarbon group may be replaced by —O—, —S—, —CO— or —SO 2 —, a —CH 2 — included in the chain hydrocarbon group may be replaced by —O— or —CO—, and the alicyclic hydrocarbon group and the chain hydrocarbon group may have a fluorine atom, a perfluoroalkyl group having 1 to 4 carbon atoms or a hydroxy group, or
an aromatic hydrocarbon group having 6 to 36 carbon atoms which may have a fluorine atom, a perfluoroalkyl group having 1 to 4 carbon atoms or a hydroxy group.
7 . The carboxylate according to claim 5 , wherein X 0 includes the alicyclic hydrocarbon group, and
the alicyclic hydrocarbon group is a cycloalkanediyl group having 5 or 6 carbon atoms,
an adamandiyl group,
a norbornanediyl group, or
a polycyclic alicyclic hydrocarbon group in which a cycloalkanediyl group having 5 or 6 carbon atoms and an adamantanediyl group are spiro-bonded,
a —CH 2 — included in the adamantanediyl group, the norbornanediyl group and the cycloalkanediyl group may be replaced by —O— or —CO—,
a —CH 2 —CH 2 — included in the adamantanediyl group and the norbornanediyl group may be replaced by —O—CO—, and
the cycloalkanediyl group may be an acetal ring.
8 . The carboxylate according to claim 6 , wherein X 0 is a phenylene group which may have a substituent, and
L 10 is a single bond, and X 10 is a single bond or a *—CO—O—**, and
* and ** are bonding sites, and ** represents a bonding site to L 10 .
9 . The carboxylate according to claim 1 , wherein X 10 is a single bond or a group represented by any one of formula (X 1 -1), formula (X 1 -2′) to formula (X 1 -7′) and formula (X 1 -8):
wherein, in formula (X 1 -1), formula (X 1 -2′) to formula (X 1 -7′) and formula (X 1 -8),
* and ** are bonding sites, and ** represents a bonding site to L 10 ,
Rx represents a halogen atom, a hydroxy group, an alkyl fluoride group having 1 to 6 carbon atoms, an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and
mx represents an integer of 0 to 4.
10 . The carboxylate according to claim 1 , wherein L 10 is a single bond or an alkanediyl group having 1 to 4 carbon atoms, a —CH 2 — included in the alkanediyl group may be replaced by —O— or —CO—.
11 . A resist composition comprising
the carboxylate according to claim 1 or a resin including a structural unit derived from the carboxylate according to claim 1 .
12 . The resist composition according to claim 11 , further comprising;
a resin including a structural unit having an acid labile group,
wherein the acid-labile group includes at least one selected from the group consisting of a structural unit represented by formula (a1-0), a structural unit represented by formula (a1-1) and a structural unit represented by formula (a1-2):
wherein, in formula (a1-0), formula (a1-1) and formula (a1-2),
L a01 , L a1 and L a2 each independently represent —O— or *—O—(CH 2 ) k1 —CO—O—, k1 represents an integer of 1 to 7, and * represents a bonding site to —CO—,
R a01 , R a4 and R a5 each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom,
R a02 , R a03 and R a04 each independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group obtained by combining these groups,
R a6 and R a7 each independently represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms, or a group formed by combining these groups,
m1 represents an integer of 0 to 14,
n1 represents an integer of 0 to 10, and
n1′ represents an integer of 0 to 3.
13 . The resist composition according to claim 11 , further comprising:
a resin including a structural unit represented by formula (a2-A):
wherein, in formula (a2-A),
R a50 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom,
R a51 represents a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an alkoxyalkoxy group having 2 to 12 carbon atoms, an alkylcarbonyl group having 2 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, an acryloyloxy group or a methacryloyloxy group,
A a50 represents a single bond or * —X a51 -(A a52 -X a52 ) nb —, and * represents a bond to carbon atoms to which —R a50 is bonded,
A a52 represents an alkanediyl group having 1 to 6 carbon atoms,
X a51 and X a52 each independently represent —O—, —CO—O— or —O—CO—,
nb represents 0 or 1, and
mb represents an integer of 0 to 4, and when mb is an integer of 2 or more, a plurality of R a51 may be the same or different from each other.
14 . The resist composition according to claim 11 , further comprising:
an acid generator including a salt represented by formula (B1):
wherein, in formula (B1),
Q b1 and Q b2 each independently represent a hydrogen atom, a fluorine atom, a perfluoroalkyl group having 1 to 6 carbon atoms or an alkyl group having 1 to 6 carbon atoms,
L b1 represents a divalent saturated hydrocarbon group having 1 to 24 carbon atoms, a —CH 2 — included in the divalent saturated hydrocarbon group may be replaced by —O— or —CO—, and a hydrogen atom included in the divalent saturated hydrocarbon group may be substituted with a fluorine atom or a hydroxy group,
Y represents a methyl group which may have a substituent or an alicyclic hydrocarbon group having 3 to 24 carbon atoms which may have a substituent, and a —CH 2 — included in the alicyclic hydrocarbon group may be replaced by —O—, —S—, —SO 2 — or —CO—, and
Z + represents an organic cation.
15 . A method for producing a resist pattern, which comprises:
(1) a step of applying the resist composition according to claim 11 on a substrate,
(2) a step of drying the applied composition to form a composition layer,
(3) a step of exposing the composition layer,
(4) a step of heating the exposed composition layer, and
(5) a step of developing the heated composition layer.
16 . A resist composition comprising
the carboxylate according to claim 1 and
a resin including a structural unit having an acid labile group.
17 . A resist composition comprising
a resin including a structural unit derived from the carboxylate according to claim 1 and a structural unit having an acid labile group.
18 . A resin comprising a structural unit derived from a carboxylate represented by formula (IP):
wherein, in formula (IP),
R 4 , R 5 , R 6 , R 7 , R 8 and R 9 each independently represent a halogen atom, a haloalkyl group having 1 to 12 carbon atoms or a hydrocarbon group having 1 to 18 carbon atoms, wherein each of the hydrocarbon group may have a substituent, and a —CH 2 — included in each of the haloalkyl group and the hydrocarbon group may be replaced by —O—, —CO—, —S— or —SO 2 —,
A 1 , A 2 and A 3 each independently represent a hydrocarbon group having 1 to 20 carbon atoms, wherein each of the hydrocarbon group may have a substituent, and a —CH 2 — included in each of the hydrocarbon group may be replaced by —O—, —CO—, —S— or —SO 2 —,
m1 represents an integer of 1 to 5, and when m1 is 2 or more, a plurality of groups in parentheses may be the same or different from each other,
m2 represents an integer of 0 to 5, and when m2 is 2 or more, a plurality of groups in parentheses may be the same or different from each other,
m3 represents an integer of 0 to 5, and when m3 is 2 or more, a plurality of groups in parentheses may be the same or different from each other,
m4 represents an integer of 0 to 5, and when m4 is 2 or more, a plurality of R 4 may be the same or different from each other,
m5 represents an integer of 0 to 5, and when m5 is 2 or more, a plurality of R 5 may be the same or different from each other,
m6 represents an integer of 0 to 5, and when m6 is 2 or more, a plurality of R 6 may be the same or different from each other,
m7 represents an integer of 0 to 4, and when m7 is 2 or more, a plurality of R 7 may be the same or different from each other,
m8 represents an integer of 0 to 5, and when m8 is 2 or more, a plurality of R 8 may be the same or different from each other,
m9 represents an integer of 0 to 5, and when m9 is 2 or more, a plurality of R 9 may be the same or different from each other,
in which 1≤m1+m7≤5, 0≤m2+m8≤5, 0≤m3+m9≤5,
X 0 represents a single bond or a hydrocarbon group having 1 to 72 carbon atoms which may have a substituent, and a —CH 2 — included in the hydrocarbon group may be replaced by —O—, —S—, —CO— or —SO 2 —,
X 10 represents a single bond, *—C—OO—, *—O—CO—, or *-Ax-Ph-Ay-,
Ph represents a phenylene group which may have a substituent,
Ax represents a single bond, an ether bond, an ester bond or a carbonic acid ester bond,
Ay represents a single bond, an ether bond, an ester bond or a carbonic acid ester bond,
* represents a bonding site to carbon atoms to which —R bb1 is bonded,
** represents a bonding site to L 10 ,
L 10 represents a single bond or a hydrocarbon group having 1 to 36 carbon atoms which may have a substituent, and a —CH 2 — included in the hydrocarbon group may be replaced by —O—, —S—, —SO 2 — or —CO—, and
R bb1 is a hydrogen atom, a halogen atom, or an alkyl having 1 to 6 carbon atoms which may have a halogen atom, and
a structural unit represented by formula (a3-4):
wherein, in formula (a3-4),
L a7 represents —O—, *—O-L a8 -O—, *—O-L a8 -CO—O—, *—O-L a8 -CO—O-L a9 -CO—O— or *—O-L a8 -O—CO-L a9 -O—,
L as and L as each independently represent an alkanediyl group having 1 to 6 carbon atoms,
* represents a bonding site to a carbonyl group,
R a24 represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom,
X a3 represents —CH 2 — or an oxygen atom,
R a25 represents a carboxy group, a cyano group or an aliphatic hydrocarbon group having 1 to 4 carbon atoms,
w1 represents an integer of 0 to 8, and
when w1 is 2 or more, a plurality of R a25 may be the same or different from each other.
19 . A resist composition comprising
a carboxylate represented by formula (I) and
a resin including a structural unit derived from the carboxylate represented by formula (I):
wherein, in formula (I),
R 4 , R 5 , R 6 , R 7 , R 8 and R 9 each independently represent a halogen atom, a haloalkyl group having 1 to 12 carbon atoms or a hydrocarbon group having 1 to 18 carbon atoms, wherein each of the hydrocarbon group may have a substituent, and a —CH 2 — included in each of the haloalkyl group and the hydrocarbon group may be replaced by —O—, —CO—, —S— or —SO 2 —,
A 1 , A 2 and A 3 each independently represent a hydrocarbon group having 1 to 20 carbon atoms, wherein each of the hydrocarbon group may have a substituent, and a —CH 2 — included in each of the hydrocarbon group may be replaced by —O—, —CO—, —S— or —SO 2 —,
m1 represents an integer of 1 to 5, and when m1 is 2 or more, a plurality of groups in parentheses may be the same or different from each other,
m2 represents an integer of 0 to 5, and when m2 is 2 or more, a plurality of groups in parentheses may be the same or different from each other,
m3 represents an integer of 0 to 5, and when m3 is 2 or more, a plurality of groups in parentheses may be the same or different from each other,
m4 represents an integer of 0 to 5, and when m4 is 2 or more, a plurality of R 4 may be the same or different from each other,
m5 represents an integer of 0 to 5, and when m5 is 2 or more, a plurality of R 5 may be the same or different from each other,
m6 represents an integer of 0 to 5, and when m6 is 2 or more, a plurality of R 6 may be the same or different from each other,
m7 represents an integer of 0 to 4, and when m7 is 2 or more, a plurality of R 7 may be the same or different from each other,
m8 represents an integer of 0 to 5, and when m8 is 2 or more, a plurality of R 8 may be the same or different from each other,
m9 represents an integer of 0 to 5, and when m9 is 2 or more, a plurality of R 9 may be the same or different from each other,
in which 1≤m1+m7≤5, 0≤m2+m8≤5, 0≤m3+m9≤5,
X 0 represents a single bond or a hydrocarbon group having 1 to 72 carbon atoms which may have a substituent, and a —CH 2 — included in the hydrocarbon group may be replaced by —O—, —S—, —CO— or —SO 2 —,
X 10 represents a single bond, *—C—OO—, *—O—CO—, or *-Ax-Ph-Ay-,
Ph represents a phenylene group which may have a substituent,
Ax represents a single bond, an ether bond, an ester bond or a carbonic acid ester bond,
Ay represents a single bond, an ether bond, an ester bond or a carbonic acid ester bond,
* represents a bonding site to carbon atoms to which —R bb1 is bonded,
** represents a bonding site to L 10 ,
L 10 represents a single bond or a hydrocarbon group having 1 to 36 carbon atoms which may have a substituent, and a —CH 2 — included in the hydrocarbon group may be replaced by —O—, —S—, —SO 2 — or —CO—, and
R bb1 is a hydrogen atom, a halogen atom, or an alkyl having 1 to 6 carbon atoms which may have a halogen atom.