# US 2020/0401045 A1 · Active-ray-sensitive or radiation-sensitive resin composition, resist film, pattern formation method, and method for manufacturing electronic device

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- Number: US 2020/0401045 A1
- Document ID: US20200401045A1
- Status: Published application
- Kind: A1
- Application number: 17/001,805
- Filed: 2020-08-25
- Published: 2020-12-24
- Earliest claimed: 2018-02-28
- Assignees: FUJIFILM Corporation
- Applicants: FUJIFILM Corporation
- Inventors: Daisuke ASAKAWA; Hironori OKA; Kyohei SAKITA; Michihiro SHIRAKAWA; Akiyoshi GOTO
- Web page: https://patentgrep.com/patent/US20200401045A1

## CPC

- G03F 7/0045: {with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors}
- C08F 220/1804: {C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate}
- C08F 220/1808: {C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate}
- C08F 220/283: {and containing one or more carboxylic moiety in the chain, e.g. acetoacetoxyethyl(meth)acrylate}
- C09D 133/14: of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
- G03F 7/0046: {with perfluoro compounds, e.g. for dry lithography (G03F7/0048 takes precedence)}
- G03F 7/038: Macromolecular compounds which are rendered insoluble or differentially wettable (G03F7/075 takes precedence; macromolecular azides G03F7/012; macromolecular diazonium compounds G03F7/021)
- G03F 7/039: Macromolecular compounds which are photodegradable, e.g. positive electron resists (G03F7/075 takes precedence; macromolecular quinonediazides G03F7/023)
- G03F 7/0397: {the macromolecular compound having an alicyclic moiety in a side chain}
- G03F 7/11: having cover layers or intermediate layers, e.g. subbing layers {(G03F7/091 - G03F7/093, B41N3/03 take precedence)}
- G03F 7/322: {Aqueous alkaline compositions}
- G03F 7/325: {Non-aqueous compositions}
- C08F 220/24: containing perhaloalkyl radicals
- C08F 220/346: {and further oxygen}
- C08F 220/382: {and containing oxygen, e.g. 2-sulfoethyl (meth)acrylate}
- 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)
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)

## Abstract

An object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition which is capable of forming a pattern having an excellent pattern line width roughness (LWR). In addition, another object of the present invention is to provide: a resist film, a pattern forming method, and a method for manufacturing an electronic device, each of which uses the actinic ray-sensitive or radiation-sensitive resin composition. The actinic ray-sensitive or radiation-sensitive resin composition of the present invention includes a resin including a repeating unit derived from a monomer having a salt structure and a repeating unit having a group whose polarity increases through decomposition by the action of an acid, the salt structure consists of an anionic structure moiety and an actinic ray-sensitive decomposable or radiation-sensitive decomposable cationic structure moiety, and a pKa of a monomer obtained by substituting the cationic structure moiety in the salt structure with a hydrogen atom is −0.80 or more.

## Claims

### Claim 1

An actinic my-sensitive or radiation-sensitive resin composition comprising a resin including a repeating unit derived from a monomer having a salt structure and a repeating unit having a group whose polarity increases through decomposition by the action of an acid,
wherein the salt structure consists of an anionic structure moiety and an actinic my-sensitive decomposable or radiation-sensitive decomposable cationic structure moiety, and
a pKa of a monomer obtained by substituting the cationic structure moiety in the salt structure with a hydrogen atom is −0.80 or more.

### Claim 2 (depends on 1)

The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1,
wherein the monomer having the salt structure is a monomer represented by General Formula (X1),
in the formula, P11 represents a polymerizable group,
Y11− represents a group selected from the group consisting of anionic functional groups represented by General Formulae (Y1) to (Y8),
Z11+ represents an actinic ray-sensitive decomposable or radiation-sensitive decomposable cation,
m represents an integer of 1 or more,
L11 represents a single bond or an m+1-valent linking group,
provided that in a case where Y11− is the anionic functional group represented by General Formula (Y1), L11 represents *1—CO—O-LS1-*2,
LS1 represents a divalent linking group not including —O—CO—,
*1 represents a bonding position to P11 and *2 represents a bonding position to Y11−, and
in a case where Y11− is an anionic functional group represented by General Formula (Y2), L11 includes neither a phenylene group nor a lactone structure,
in General Formula (Y1), * represents a bonding position to L11 in General Formula (X1),
in General Formula (Y2), R11 and R12 each independently represent a hydrogen atom or a monovalent organic group,
provided that in a case where one of R11 and R12 represents a fluorine atom or a fluoroalkyl group, the other of R11 and R12 represents a hydrogen atom or a monovalent organic group different from the fluorine atom and the fluoroalkyl group,
R11 and R12 may be bonded to each other to form a ring,
R11 and R12 may be each independently bonded to L11 in General Formula (X1) to form a ring,
provided that the ring formed by the bonding of R11 and L11 in General Formula (X1) and the ring formed by the bonding of R12 and L11 in General Formula (X) include no benzene ring, and
* represents a bonding position to L11,
in General Formula (Y3), R13 represents a monovalent organic group,
provided that in a case where a group adjacent to a sulfur atom in R13 is a carbon atom, the carbon atom has no fluorine atom as a substituent,
R13 may be bonded to L11 in General Formula (X1) to form a ring, and
* represents a bonding position to L11,
in General Formula (Y4), L12 represents a single bond or a divalent linking group,
R14, R15, and R16 each independently represent a hydrogen atom or a monovalent organic group,
provided that in a case where two of R14, R15, and R16 represent a fluorine atom or a fluoroalkyl group, one of R14, R15, and R16 represents a hydrogen atom or a monovalent organic group different from the fluorine atom and the fluoroalkyl group,
in a case where two of R14, R15, and R16 each represent a fluorine atom or a fluoroalkyl group, and a group adjacent to an amido group in L12 is a carbon atom, the carbon atom does not have two or more fluorine atoms and fluoroalkyl groups as a substituent,
R14, R15, and R16 may be bonded to each other to form a ring,
R14, R15, and R16 may be each independently bonded to L12 to form a ring,
R14, R15, and R16 may be each independently bond to L11 in General Formula (X1) to form a ring, and
* represents a bonding position to L11,
in General Formula (Y5), L13 represents a single bond or a divalent linking group,
R17, R18, and R19 each independently represent a hydrogen atom or a monovalent organic group,
provided that in a case where two or more of R17, R18, or R19 each represent a fluorine atom or a fluoroalkyl group, and a group adjacent to a sulfonamido group in L13 is a carbon atom, the carbon atom does not have two or more fluorine atoms and fluoroalkyl groups as a substituent,
R17, R18, and R19 may be bonded to each other to form a ring,
R17, R18, and R19 may be each independently bonded to L13 to form a ring,
R17, R18, and R19 may be each independently bonded to L11 in General Formula (X1) to form a ring, and
* represents a bonding position to L11,
in General Formula (Y6), R20 represents a monovalent organic group,
R20 may be bonded to L11 in General Formula (X1) to form a ring, and
* represents a bonding position to L11,
in General Formula (Y7), * represents a bonding position to L11, and
provided that the atom bonded to * in L11 is a carbon atom which is not a carbonyl group,
in General Formula (Y8), L14 represents a single bond or a divalent linking group,
R21, R22, R23, R24, and R25 each independently represent a hydrogen atom or a monovalent organic group,
R23, R24, and R25 may be bonded to each other to form a ring,
R23, R24, and R25 may be each independently bonded to L14, R21, and R22 to form a ring,
R21, R22, and L14 may be bonded to each other to form a ring, and
R23, R24, and R25 may be each independently bonded to L11 in General Formula (X1) to form a ring.

### Claim 3 (depends on 1)

The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, further comprising a photoacid generator that generates an acid upon irradiation with actinic rays or radiation.

### Claim 4 (depends on 3)

The actinic ray-sensitive or radiation-sensitive resin composition according to claim 3,
wherein a pKa of an acid generated from the photoacid generator is smaller than a pKa of a monomer obtained by substituting the cationic structure moiety in the salt structure with a hydrogen atom.

### Claim 5 (depends on 1)

A resist film formed using the actinic my-sensitive or radiation-sensitive resin composition according to claim 1.

### Claim 6 (depends on 1)

A pattern forming method comprising:
a resist film forming step of forming a resist film using the actinic ray-sensitive or radiation-sensitive resin composition according to claim 1;
an exposing step of exposing the resist film; and
a developing step of developing the exposed resist film using a developer.

### Claim 7 (depends on 6)

A method for manufacturing an electronic device, comprising the pattern forming method according to claim 6.

### Claim 8 (depends on 2)

The actinic my-sensitive or radiation-sensitive resin composition according to claim 2, further comprising a photoacid generator that generates an acid upon irradiation with actinic rays or radiation.

### Claim 9 (depends on 8)

The actinic ray-sensitive or radiation-sensitive resin composition according to claim 8,
wherein a pKa of an acid generated from the photoacid generator is smaller than a pKa of a monomer obtained by substituting the cationic structure moiety in the salt structure with a hydrogen atom.

### Claim 10 (depends on 2)

A resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to claim 2.

### Claim 11 (depends on 2)

A pattern forming method comprising:
a resist film forming step of forming a resist film using the actinic ray-sensitive or radiation-sensitive resin composition according to claim 2;
an exposing step of exposing the resist film; and
a developing step of developing the exposed resist film using a developer.

### Claim 12 (depends on 11)

A method for manufacturing an electronic device, comprising the pattern forming method according to claim 11.

### Claim 13 (depends on 3)

A resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to claim 3.

### Claim 14 (depends on 3)

A pattern forming method comprising:
a resist film forming step of forming a resist film using the actinic ray-sensitive or radiation-sensitive resin composition according to claim 3;
an exposing step of exposing the resist film; and
a developing step of developing the exposed resist film using a developer.

### Claim 15 (depends on 14)

A method for manufacturing an electronic device, comprising the pattern forming method according to claim 14.

### Claim 16 (depends on 4)

A resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to claim 4.

### Claim 17 (depends on 4)

A pattern forming method comprising:
a resist film forming step of forming a resist film using the actinic ray-sensitive or radiation-sensitive resin composition according to claim 4;
an exposing step of exposing the resist film; and
a developing step of developing the exposed resist film using a developer.

### Claim 18 (depends on 17)

A method for manufacturing an electronic device, comprising the pattern forming method according to claim 17.