# US 12,222,648 B2 · Salt, acid generator, resist composition and method for producing resist pattern

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- Number: US 12,222,648 B2
- Document ID: US12222648B2
- Status: Granted
- Kind: B2
- Application number: 17/521,141
- Filed: 2021-11-08
- Published: 2022-05-12
- Granted: 2025-02-11
- Earliest claimed: 2020-11-12
- Assignees: Sumitomo Chemical Company, Limited
- Applicants: Sumitomo Chemical Company, Limited
- Inventors: Masahiko Shimada; Koji Ichikawa
- Web page: https://patentgrep.com/patent/US12222648B2

## CPC

- G03F 7/0397: {the macromolecular compound having an alicyclic moiety in a side chain}
- C07C 25/18: Polycyclic aromatic halogenated hydrocarbons
- C07C 309/12: containing esterified hydroxy groups bound to the carbon skeleton
- C07C 309/17: containing carboxyl groups bound to the carbon skeleton
- C07C 381/12: Sulfonium compounds
- C07D 307/00: Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D 307/93: condensed with a ring other than six-membered
- C07D 327/08: [b,e]-condensed with two six-membered carbocyclic rings
- C07D 333/76: Dibenzothiophenes
- C07D 493/04: Ortho-condensed systems
- G03F 7/0045: {with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors}
- G03F 7/0046: {with perfluoro compounds, e.g. for dry lithography (G03F7/0048 takes precedence)}
- G03F 7/0392: {the macromolecular compound being present in a chemically amplified positive photoresist composition}
- C07C 2603/74: Adamantanes
- G03F: PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR; (phototypographic composing devices B41B; photosensitive materials or processes for photographic purposes G03C; electrophotography, sensitive layers or processes therefor G03G)
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)

## Abstract

Disclosed are a salt represented by formula (I), an acid generator and a resist composition: wherein Q1 and Q2 each represent a fluorine atom or a perfluoroalkyl group; R11 and R12 each represent a hydrogen atom, a fluorine atom or a perfluoroalkyl group; z represents an integer of 0 to 6; X1 and X2 each represent *—CO—O—, *—O—CO—, etc.; L1 represents a single bond or a hydrocarbon group which may have a substituent; A1 represents a group having a lactone structure which may have a substituent; L2 and L3 each represent a single bond or an alkanediyl group; R1 represents an iodine atom or a haloalkyl group; R2 represents a halogen atom, a hydroxy group, a haloalkyl group or an alkyl group; m2 represents an integer of 0 to 4; and Z+ represents an organic cation.

## Claims

### Claim 1

A salt represented by formula (I):
wherein, in formula (I),
Q1 and Q2 each independently represent a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms,
R11 and R12 each independently represent a hydrogen atom, a fluorine atom or a perfluoroalkyl group having 1 to 6 carbon atoms,
z represents 0,
X1 and X2 each independently represent *—CO—O—, *—O—CO—, *—O—CO—O— or *—O—, and represents a bonding site to C(R11)(R12) or C(Q1)(Q2) or A1 or L2,
L1 represents a single bond or a hydrocarbon group having 1 to 28 carbon atoms which may have a substituent, and —CH2— included in the hydrocarbon group may be replaced by —O—, —S—, —SO2— or —CO—,
A1 represents a group having a lactone structure which may have a substituent,
L2 and L3 each independently represent a single bond or an alkanediyl group having 1 to 6 carbon atoms,
R1 represents an iodine atom or a haloalkyl group having 1 to 12 carbon atoms,
one of R2 represents a halogen atom, and the other of R2 represents a hydroxy group,
m2 is 2, and
Z+ represents an organic cation.

### Claim 2 (depends on 1)

The salt according to claim 1, wherein L1 represents a single bond or *-L4-CO—O—, wherein L4 represents a cyclic hydrocarbon group having 3 to 18 carbon atoms or a group obtained by combining a cyclic hydrocarbon group having 3 to 18 carbon atoms with an alkanediyl group having 1 to 4 carbon atoms, the cyclic hydrocarbon group may have a substituent, —CH2— included in the cyclic hydrocarbon group may be replaced by —O—, —S—, —CO— or —SO2—, —CH2— included in the alkanediyl group may be replaced by —O— or —CO—, and * represents a bonding site to X1.

### Claim 3 (depends on 1)

The salt according to claim 1, wherein A1 is a group represented by formula (R10-1), formula (R10-2), formula (R10-3) or formula (R10-4):
wherein, in formula (R10-1) to formula (R10-4),
* represents a bonding site,
Z12 represents an oxygen atom, a sulfur atom or a methylene group,
R11, R12, R13 and R14 each independently represent a hydroxy group, a carboxy group, a halogen atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyl group having 2 to 13 carbon atoms, an alkylcarbonyloxy group having 2 to 13 carbon atoms, or a group obtained by combining these groups,
m11 represents an integer of 0 to 5, and when m11 is 2 or more, a plurality of R11 may be the same or different from each other,
m12 represents an integer of 0 to 5, and when m12 is 2 or more, a plurality of R12 may be the same or different from each other,
m13 represents an integer of 0 to 5, and when m13 is 2 or more, a plurality of R13 may be the same or different from each other,
m14 represents an integer of 0 to 5, and when m14 is 2 or more, a plurality of R14 may be the same or different from each other, and
n10 represents an integer of 1 to 3.

### Claim 4 (depends on 1)

The salt according to claim 1, wherein A1 is a group represented by the following formula (L4-1), formula (L4-2) or formula (L4-3) (the group may have a substituent, and * represents a bonding site).

### Claim 5 (depends on 1)

The salt according to claim 1, wherein L2 and L3 each independently represent a single bond or an alkanediyl group having 1 to 3 carbon atoms.

### Claim 6 (depends on 1)

The salt according to claim 1, wherein R1 is an iodine atom or a perfluoroalkyl group having 1 to 3 carbon atoms.

### Claim 7 (depends on 1)

The salt according to claim 1, wherein one of R2 is an iodine atom or a fluorine atom, and the other of R2 is a hydroxy group.

### Claim 8 (depends on 1)

An acid generator comprising the salt according to claim 1.

### Claim 9 (depends on 8)

A resist composition comprising the acid generator according to claim 8 and a resin having an acid-labile group.

### Claim 10 (depends on 9)

The resist composition according to claim 9, wherein the resin having an 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),
La01, La1 and La2 each independently represent —O— or *—O—(CH2)k1—CO—O—, k1 represents an integer of 1 to 7, and * represents a bonding site to —CO—,
Ra01, Ra4 and Ra5 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,
Ra02, Ra03 and Ra04 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,
Ra6 and Ra7 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.

### Claim 11 (depends on 9)

The resist composition according to claim 9, wherein the resin having an acid-labile group includes a structural unit represented by formula (a2-A):
wherein, in formula (a2-A),
Ra50 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms which may have a halogen atom,
Ra51 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,
Aa50 represents a single bond or *—Xa51-(Aa52-Xa52)nb—, and * represents a bonding site to carbon atoms to which —Ra50 is bonded,
Aa52 represents an alkanediyl group having 1 to 6 carbon atoms,
Xa51 and Xa52 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 Ra51 may be the same or different from each other.

### Claim 12 (depends on 9)

The resist composition according to claim 9, further comprising a salt generating an acid having an acidity lower than that of an acid generated from the acid generator.

### Claim 13 (depends on 9)

A method for producing a resist pattern, which comprises:
(1) a step of applying the resist composition according to claim 9 on a substrate,
(2) a step of drying the applied resist 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.