# US 9,436,083 B2 · Chemically-amplified negative resist composition and resist patterning process using the same

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- Number: US 9,436,083 B2
- Document ID: US9436083B2
- Status: Granted
- Kind: B2
- Application number: 14/637,013
- Filed: 2015-03-03
- Published: 2015-09-24
- Granted: 2016-09-06
- Earliest claimed: 2014-03-24
- Assignees: Shin-Etsu Chemical Co., Ltd.
- Applicants: Shin-Etsu Chemical Co., Ltd.
- Inventors: Daisuke Domon; Keiichi Masunaga; Satoshi Watanabe
- Web page: https://patentgrep.com/patent/US9436083B2

## CPC

- G03F 7/0382: {the macromolecular compound being present in a chemically amplified negative photoresist composition}
- 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 7/30: Imagewise removal using liquid means
- 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)

## Abstract

The present invention provides a chemically-amplified negative resist composition including a sulfonium salt capable of providing a pattern having an extremely high resolution with reduced line edge roughness, and also provides a resist patterning process using the same. The present invention was accomplished by a chemically-amplified negative resist composition including (A) a salt represented by the following general formula (1) and (B) a resin containing one or more kinds of repeating unit represented by the following general formulae (UN-1) and (UN-2) and a resist patterning process using the same.

## Claims

### Claim 1

A chemically-amplified negative resist composition for high energy beam exposure comprising: (A) a salt represented by the following general formula (1); and (B) a resin containing one or more kinds of repeating units represented by the following general formulae (UN-1) and (UN-2),
wherein R0 represents a hydrogen atom, or a linear monovalent hydrocarbon group having 1 to 20 carbon atoms or a branched or a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms with which a hetero atom may be substituted or in which a hetero atom may be included; each R01 and R02 independently represents a hydrogen atom, or a linear monovalent hydrocarbon group having 1 to 20 carbon atoms or a branched or a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms, and R01 and R02 may mutually be bonded to form a cyclic structure together with a carbon atom bonded by the same and a carbon atom between the same, and at least one of R0, R01 and R02 has a cyclic structure; each R101, R102 and R103 independently represents a linear monovalent hydrocarbon group having 1 to 20 carbon atoms or a branched or a cyclic monovalent hydrocarbon group having 3 to 20 carbon atoms with which a hetero atom may be substituted or in which a hetero atom may be included, and two or more of R101, R102 and R103 may mutually be bonded to form a cyclic structure together with a sulfur atom in the formula; and L represents a single bond or any of an ester bond, a sulfonic acid ester bond, a carbonate bond and a carbamate bond each of which is formed together with an adjacent oxygen atom,
wherein each A and B represents a single bond or an alkylene group having 1 to 10 carbon atoms that may contain an ether bond in a chain of the alkylene group; each R1 independently represents a hydrogen atom or a methyl group; RX represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; X represents a hydrogen atom, a linear, a branched or a cyclic alkyl group, substituted or unsubstituted, having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, an alkylthioalkyl group having 2 to 20 carbon atoms, a halogen atom, a nitro group, a cyano group, a sulfinyl group, or a sulfonyl group; Y represents an alkyl group having 1 to 20 carbon atoms or an acyl group having 1 to 20 carbon atoms; “a” and “c” represent an integer of 0 to 4; “b” represents an integer of 1 to 5; “d” represents an integer of 0 to 5; P and Q represent 0 or 1; and “s” and “t” represent an integer of 0 to 2.

### Claim 2 (depends on 1)

The resist composition according to claim 1, wherein the resin further contains one or more kinds of repeating unit represented by the following general formulae (UN-3) and (UN-4),
wherein “f” represents an integer of 0 to 6; R3 represents any of a hydrogen atom, an alkyl group or a primary or a secondary alkoxy group having 1 to 6 carbon atoms that may be halogen-substituted, and an alkylcarbonyloxy group having 1 to 7 carbon atoms that may be halogen-substituted; “g” represents an integer of 0 to 4; and R4 represents any of a hydrogen atom, an alkyl group or a primary or a secondary alkoxy group having 1 to 6 carbon atoms that may be halogen-substituted, and an alkylcarbonyloxy group having 1 to 7 carbon atoms that may be halogen-substituted.

### Claim 3 (depends on 2)

The resist composition according to claim 2, wherein the resist composition further contains an acid generator that generates sulfonic acid by the high energy beam exposure.

### Claim 4 (depends on 3)

The resist composition according to claim 3, wherein the resist composition further contains a crosslinking agent.

### Claim 5 (depends on 4)

The resist composition according to claim 4, wherein as a basic component, one or more compound represented by the following general formulae (7) to (9) are further contained,
wherein each R12 and R13 represents a linear, a branched or a cyclic alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a hydroxyalkyl group having 2 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, an acyloxyalkyl group having 2 to 20 carbon atoms, or an alkylthioalkyl group having 2 to 20 carbon atoms, and R12 and R13 may be bonded to form a cyclic structure together with a nitrogen atom bonded by the same; R14 represents a hydrogen atom, a linear, a branched or a cyclic alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a hydroxyalkyl group having 2 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, an acyloxyalkyl group having 2 to 20 carbon atoms, an alkylthioalkyl group having 2 to 20 carbon atoms, or a halogen atom; R15 represents a single bond, a linear, a branched or a cyclic alkylene group having 1 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms,
wherein R12, R13, R14 and R15 are the same as before; R16 represents a linear or a branched alkylene group having 2 to 20 carbon atoms that can be substituted, and one or more of a carbonyl group, an ether group, an ester group, and sulfide may be contained between carbons of the alkylene group; R17 represents a linear, a branched or a cyclic alkylene group having 1 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms.

### Claim 6 (depends on 3)

The resist composition according to claim 3, wherein as a basic component, one or more compound represented by the following general formulae (7) to (9) are further contained,
wherein each R12 and R13 represents a linear, a branched or a cyclic alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a hydroxyalkyl group having 2 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, an acyloxyalkyl group having 2 to 20 carbon atoms, or an alkylthioalkyl group having 2 to 20 carbon atoms, and R12 and R13 may be bonded to form a cyclic structure together with a nitrogen atom bonded by the same; R14 represents a hydrogen atom, a linear, a branched or a cyclic alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a hydroxyalkyl group having 2 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, an acyloxyalkyl group having 2 to 20 carbon atoms, an alkylthioalkyl group having 2 to 20 carbon atoms, or a halogen atom; R15 represents a single bond, a linear, a branched or a cyclic alkylene group having 1 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms,
wherein R12, R13, R14 and R15 are the same as before; R16 represents a linear or a branched alkylene group having 2 to 20 carbon atoms that can be substituted, and one or more of a carbonyl group, an ether group, an ester group, and sulfide may be contained between carbons of the alkylene group; R17 represents a linear, a branched or a cyclic alkylene group having 1 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms.

### Claim 7 (depends on 2)

The resist composition according to claim 2, wherein the resist composition further contains a crosslinking agent.

### Claim 8 (depends on 7)

The resist composition according to claim 7, wherein as a basic component, one or more compound represented by the following general formulae (7) to (9) are further contained,
wherein each R12 and R13 represents a linear, a branched or a cyclic alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a hydroxyalkyl group having 2 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, an acyloxyalkyl group having 2 to 20 carbon atoms, or an alkylthioalkyl group having 2 to 20 carbon atoms, and R12 and R13 may be bonded to form a cyclic structure together with a nitrogen atom bonded by the same; R14 represents a hydrogen atom, a linear, a branched or a cyclic alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a hydroxyalkyl group having 2 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, an acyloxyalkyl group having 2 to 20 carbon atoms, an alkylthioalkyl group having 2 to 20 carbon atoms, or a halogen atom; R15 represents a single bond, a linear, a branched or a cyclic alkylene group having 1 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms,
wherein R12, R13, R14 and R15 are the same as before; R16 represents a linear or a branched alkylene group having 2 to 20 carbon atoms that can be substituted, and one or more of a carbonyl group, an ether group, an ester group, and sulfide may be contained between carbons of the alkylene group; R17 represents a linear, a branched or a cyclic alkylene group having 1 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms.

### Claim 9 (depends on 2)

The resist composition according to claim 2, wherein as a basic component, one or more compound represented by the following general formulae (7) to (9) are further contained,
wherein each R12 and R13 represents a linear, a branched or a cyclic alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a hydroxyalkyl group having 2 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, an acyloxyalkyl group having 2 to 20 carbon atoms, or an alkylthioalkyl group having 2 to 20 carbon atoms, and R12 and R13 may be bonded to form a cyclic structure together with a nitrogen atom bonded by the same; R14 represents a hydrogen atom, a linear, a branched or a cyclic alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a hydroxyalkyl group having 2 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, an acyloxyalkyl group having 2 to 20 carbon atoms, an alkylthioalkyl group having 2 to 20 carbon atoms, or a halogen atom; R15 represents a single bond, a linear, a branched or a cyclic alkylene group having 1 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms,
wherein R12, R13, R14 and R15 are the same as before; R16 represents a linear or a branched alkylene group having 2 to 20 carbon atoms that can be substituted, and one or more of a carbonyl group, an ether group, an ester group, and sulfide may be contained between carbons of the alkylene group; R17 represents a linear, a branched or a cyclic alkylene group having 1 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms.

### Claim 10 (depends on 1)

The resist composition according to claim 1, wherein the resist composition further contains an acid generator that generates sulfonic acid by the high energy beam exposure.

### Claim 11 (depends on 10)

The resist composition according to claim 10, wherein the resist composition further contains a crosslinking agent.

### Claim 12 (depends on 11)

The resist composition according to claim 11, wherein as a basic component, one or more compound represented by the following general formulae (7) to (9) are further contained,
wherein each R12 and R13 represents a linear, a branched or a cyclic alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a hydroxyalkyl group having 2 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, an acyloxyalkyl group having 2 to 20 carbon atoms, or an alkylthioalkyl group having 2 to 20 carbon atoms, and R12 and R13 may be bonded to form a cyclic structure together with a nitrogen atom bonded by the same; R14 represents a hydrogen atom, a linear, a branched or a cyclic alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a hydroxyalkyl group having 2 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, an acyloxyalkyl group having 2 to 20 carbon atoms, an alkylthioalkyl group having 2 to 20 carbon atoms, or a halogen atom; R15 represents a single bond, a linear, a branched or a cyclic alkylene group having 1 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms,
wherein R12, R13, R14 and R15 are the same as before; R16 represents a linear or a branched alkylene group having 2 to 20 carbon atoms that can be substituted, and one or more of a carbonyl group, an ether group, an ester group, and sulfide may be contained between carbons of the alkylene group; R17 represents a linear, a branched or a cyclic alkylene group having 1 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms.

### Claim 13 (depends on 10)

The resist composition according to claim 10, wherein as a basic component, one or more compound represented by the following general formulae (7) to (9) are further contained,
wherein each R12 and R13 represents a linear, a branched or a cyclic alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a hydroxyalkyl group having 2 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, an acyloxyalkyl group having 2 to 20 carbon atoms, or an alkylthioalkyl group having 2 to 20 carbon atoms, and R12 and R13 may be bonded to form a cyclic structure together with a nitrogen atom bonded by the same; R14 represents a hydrogen atom, a linear, a branched or a cyclic alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a hydroxyalkyl group having 2 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, an acyloxyalkyl group having 2 to 20 carbon atoms, an alkylthioalkyl group having 2 to 20 carbon atoms, or a halogen atom; R15 represents a single bond, a linear, a branched or a cyclic alkylene group having 1 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms,
wherein R12, R13, R14 and R15 are the same as before; R16 represents a linear or a branched alkylene group having 2 to 20 carbon atoms that can be substituted, and one or more of a carbonyl group, an ether group, an ester group, and sulfide may be contained between carbons of the alkylene group; R17 represents a linear, a branched or a cyclic alkylene group having 1 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms.

### Claim 14 (depends on 1)

The resist composition according to claim 1, wherein the resist composition further contains a crosslinking agent.

### Claim 15 (depends on 14)

The resist composition according to claim 14, wherein as a basic component, one or more compound represented by the following general formulae (7) to (9) are further contained,
wherein each R12 and R13 represents a linear, a branched or a cyclic alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a hydroxyalkyl group having 2 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, an acyloxyalkyl group having 2 to 20 carbon atoms, or an alkylthioalkyl group having 2 to 20 carbon atoms, and R12 and R13 may be bonded to form a cyclic structure together with a nitrogen atom bonded by the same; R14 represents a hydrogen atom, a linear, a branched or a cyclic alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a hydroxyalkyl group having 2 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, an acyloxyalkyl group having 2 to 20 carbon atoms, an alkylthioalkyl group having 2 to 20 carbon atoms, or a halogen atom; R15 represents a single bond, a linear, a branched or a cyclic alkylene group having 1 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms,
wherein R12, R13, R14 and R15 are the same as before; R16 represents a linear or a branched alkylene group having 2 to 20 carbon atoms that can be substituted, and one or more of a carbonyl group, an ether group, an ester group, and sulfide may be contained between carbons of the alkylene group; R17 represents a linear, a branched or a cyclic alkylene group having 1 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms.

### Claim 16 (depends on 1)

The resist composition according to claim 1, wherein as a basic component, one or more compound represented by the following general formulae (7) to (9) are further contained,
wherein each R12 and R13 represents a linear, a branched or a cyclic alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a hydroxyalkyl group having 2 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, an acyloxyalkyl group having 2 to 20 carbon atoms, or an alkylthioalkyl group having 2 to 20 carbon atoms, and R12 and R13 may be bonded to form a cyclic structure together with a nitrogen atom bonded by the same; R14 represents a hydrogen atom, a linear, a branched or a cyclic alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a hydroxyalkyl group having 2 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, an acyloxyalkyl group having 2 to 20 carbon atoms, an alkylthioalkyl group having 2 to 20 carbon atoms, or a halogen atom; R15 represents a single bond, a linear, a branched or a cyclic alkylene group having 1 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms,
wherein R12, R13, R14 and R15 are the same as before; R16 represents a linear or a branched alkylene group having 2 to 20 carbon atoms that can be substituted, and one or more of a carbonyl group, an ether group, an ester group, and sulfide may be contained between carbons of the alkylene group; R17 represents a linear, a branched or a cyclic alkylene group having 1 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms.

### Claim 17 (depends on 1)

A resist patterning process comprising steps of: applying the resist composition according to claim 1 on a substrate to be processed to obtain a resist film; pattern-exposing by a high energy beam; and developing by using an alkaline developer to obtain a resist pattern.

### Claim 18 (depends on 17)

The resist patterning process according to claim 17, wherein an EUV or an electron beam is used as the high energy beam.

### Claim 19 (depends on 17)

The resist patterning process according to claim 17, wherein a top surface of the substrate to be processed is composed of a material containing chrome.

### Claim 20 (depends on 17)

The resist patterning process according to claim 17, wherein a photo mask blank is used as the substrate to be processed.