# US 9,040,222 B2 · Polymerizable tertiary ester compound, polymer, resist composition, and patterning process

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- Number: US 9,040,222 B2
- Document ID: US9040222B2
- Status: Granted
- Kind: B2
- Application number: 13/743,019
- Filed: 2013-01-16
- Published: 2013-07-25
- Granted: 2015-05-26
- Earliest claimed: 2012-01-24
- Assignees: Shin-Etsu Chemical Co., Ltd.
- Applicants: Shin-Etsu Chemical Co., Ltd.
- Inventors: Yuki Suka; Jun Hatakeyama; Koji Hasegawa
- Web page: https://patentgrep.com/patent/US9040222B2

## CPC

- C07C 69/653: Acrylic acid esters; Methacrylic acid esters; Haloacrylic acid esters; Halomethacrylic acid esters
- C08F 220/26: Esters containing oxygen in addition to the carboxy oxygen
- G03F 7/0046: {with perfluoro compounds, e.g. for dry lithography (G03F7/0048 takes precedence)}
- G03F 7/039: Macromolecular compounds which are photodegradable, e.g. positive electron resists (G03F7/075 takes precedence; macromolecular quinonediazides G03F7/023)
- G03F 7/0392: {the macromolecular compound being present in a chemically amplified positive photoresist composition}
- 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 7/2041: {in the presence of a fluid, e.g. immersion; using fluid cooling means}
- G03F 7/30: Imagewise removal using liquid means
- G03F 7/325: {Non-aqueous compositions}
- C07C 2601/02: with a three-membered ring
- C07C 2601/04: with a four-membered ring
- C07C 2601/08: the ring being saturated
- C07C 2601/14: The ring being saturated
- C07C 2602/42: the bicyclo ring system containing seven carbon atoms
- C08F 220/24: containing perhaloalkyl radicals
- C08F 220/283: {and containing one or more carboxylic moiety in the chain, e.g. acetoacetoxyethyl(meth)acrylate}
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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 polymerizable tertiary ester compound represented by the following general formula (1a) or (1b). There is provided a polymerizable ester compound useful as a monomer for a base resin of a resist composition having a high resolution and a reduced pattern edge roughness in photolithography using a high-energy beam such as an ArF excimer laser light as a light source, especially in immersion lithography, a polymer containing a polymer of the ester compound, a resist composition containing the polymer as a base resin, and a patterning process using the resist composition.

## Claims

### Claim 1

A polymerizable tertiary ester compound represented by the following general formula (1a) or (1b),
wherein R1a represents a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group; R1b represents a methyl group; each of R2 and R3 independently represents a linear, a branched, or a cyclic monovalent hydrocarbon group having 1 to 15 carbon atoms, or R2 and R3 may combine with each other to form a non-aromatic ring having 3 to 8 carbon atoms together with the carbon atoms to which they are bonded; Z represents a divalent group forming a substituted or an unsubstituted cyclopropane, cyclobutane, cyclopentane, cyclohexane, or norbornane ring together with the carbon atom to which it is bonded; Aa represents a linear, a branched, or a cyclic divalent hydrocarbon group having 1 to 10 carbon atoms; Ab represents a linear, a branched, or a cyclic divalent hydrocarbon group having 1 to 6 carbon atoms; Ac represents a single bond or a linear, a branched, or a cyclic divalent hydrocarbon group having 1 to 10 carbon atoms; R4 represents a hydrogen atom, or a linear, a branched, or a cyclic monovalent hydrocarbon group having 1 to 15 carbon atoms, and when R4 is a monovalent hydrocarbon group, —CH2— may be substituted with —O— or —C(═O)—.

### Claim 2 (depends on 1)

The polymerizable tertiary ester compound according to claim 1, wherein in the general formula (1a), any one or more of R2, R3, and Aa has a cyclic structure.

### Claim 3

A polymer comprising any one or more kinds of repeating units represented by the following general formulae (2a) and (2b),
wherein R1a represents a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group; R1b represents a methyl group; each of R2 and R3 independently represents a linear, a branched, or a cyclic monovalent hydrocarbon group having 1 to 15 carbon atoms, or R2 and R3 may combine with each other to form a non-aromatic ring having 3 to 8 carbon atoms together with the carbon atoms to which they are bonded; Z represents a divalent group forming a substituted or an unsubstituted cyclopropane, cyclobutane, cyclopentane, cyclohexane, or norbornane ring together with the carbon atom to which it is bonded; Aa represents a linear, a branched, or a cyclic divalent hydrocarbon group having 1 to 10 carbon atoms; Ab represents a linear, a branched, or a cyclic divalent hydrocarbon group having 1 to 6 carbon atoms; Ac represents a single bond or a linear, a branched, or a cyclic divalent hydrocarbon group having 1 to 10 carbon atoms; R4 represents a hydrogen atom, or a linear, a branched, or a cyclic monovalent hydrocarbon group having 1 to 15 carbon atoms, and when R4 is a monovalent hydrocarbon group, —CH2— may be substituted with —O— or —C(═O)—.

### Claim 4 (depends on 3)

The polymer according to claim 3, wherein in the general formula (2a), any one or more of R2, R3, and Aa has a cyclic structure.

### Claim 5 (depends on 4)

The polymer according to claim 4, further comprising any one or more kinds of repeating units of represented by the following general formulae (3a) to (3d),
wherein R1 is as defined above; XA represents an acid labile group; each of XB and XC independently represents a single bond, or a linear or a branched divalent hydrocarbon group having 1 to 4 carbon atoms; YA represents a substituent having a lactone, sultone, hydroxy, carboxyl, ester, ether, carbonyl, amido, or cyano structure; ZA represents a hydrogen atom, or a fluoroalkyl group having 1 to 15 carbon atoms, or a fluoroalcohol-containing substituent having 1 to 15 carbon atoms; and k1A represents an integer of 1 to 3.

### Claim 6 (depends on 5)

The polymer according to claim 5, further comprising any one or more kinds of repeating units of represented by the following general formulae (d1) to (d3),
wherein each of R20, R24, and R28 independently represents a hydrogen atom or a methyl group; R21 represents a single bond, a phenylene group, —O—R33—, or —C(═O)—Y—R33—; Y represents an oxygen atom or NH; R33 represents a linear, a branched, or a cyclic alkylene group having 1 to 6 carbon atoms, an alkenylene group, or a phenylene group, optionally containing a carbonyl group (—CO—), an ester group (—COO—), an ether group (—O—), or a hydroxy group; R22, R23, R25, R26, R27, R29, R30, and R31 represent the same or different linear, branched, or cyclic alkyl groups having 1 to 12 carbon atoms, optionally containing a carbonyl group, an ester group, or an ether group, or represent an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a thiophenyl group; Z0 represents a single bond, a methylene group, an ethylene group, a phenylene group, a fluorinated phenylene group, —O—R32—, or —C(═O)—Z1—R32—; Z1 represents an oxygen atom or NH; R32 represents a linear, a branched, or a cyclic alkylene group having 1 to 6 carbon atoms, an alkenylene group, or a phenylene group, optionally containing a carbonyl group, an ester group, an ether group, or a hydroxy group; and M− represents a non-nucleophilic counter ion.

### Claim 7 (depends on 4)

The polymer according to claim 4, further comprising any one or more kinds of repeating units of represented by the following general formulae (d1) to (d3),
wherein each of R20, R24, and R28 independently represents a hydrogen atom or a methyl group; R21 represents a single bond, a phenylene group, —O—R33—, or —C(═O)—Y—R33—; Y represents an oxygen atom or NH; R33 represents a linear, a branched, or a cyclic alkylene group having 1 to 6 carbon atoms, an alkenylene group, or a phenylene group, optionally containing a carbonyl group (—CO—), an ester group (—COO—), an ether group (—O—), or a hydroxy group; R22, R23, R25, R26, R27, R29, R30, and R31 represent the same or different linear, branched, or cyclic alkyl groups having 1 to 12 carbon atoms, optionally containing a carbonyl group, an ester group, or an ether group, or represent an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a thiophenyl group; Z0 represents a single bond, a methylene group, an ethylene group, a phenylene group, a fluorinated phenylene group, —O—R32—, or —C(═O)—Z1—R32—; Z1 represents an oxygen atom or NH; R32 represents a linear, a branched, or a cyclic alkylene group having 1 to 6 carbon atoms, an alkenylene group, or a phenylene group, optionally containing a carbonyl group, an ester group, an ether group, or a hydroxy group; and M− represents a non-nucleophilic counter ion.

### Claim 8 (depends on 3)

The polymer according to claim 3, further comprising any one or more kinds of repeating units of represented by the following general formulae (3a) to (3d),
wherein R1 is as defined above; XA represents an acid labile group; each of XB and XC independently represents a single bond, or a linear or a branched divalent hydrocarbon group having 1 to 4 carbon atoms; YA represents a substituent having a lactone, sultone, hydroxy, carboxyl, ester, ether, carbonyl, amido, or cyano structure; ZA represents a hydrogen atom, or a fluoroalkyl group having 1 to 15 carbon atoms, or a fluoroalcohol-containing substituent having 1 to 15 carbon atoms; and k1A represents an integer of 1 to 3.

### Claim 9 (depends on 7)

The polymer according to claim 7, further comprising any one or more kinds of repeating units of represented by the following general formulae (d1) to (d3),
wherein each of R20, R24, and R28 independently represents a hydrogen atom or a methyl group; R21 represents a single bond, a phenylene group, —O—R33—, or —C(═O)—Y—R33—; Y represents an oxygen atom or NH; R33 represents a linear, a branched, or a cyclic alkylene group having 1 to 6 carbon atoms, an alkenylene group, or a phenylene group, optionally containing a carbonyl group (—CO—), an ester group (—COO—), an ether group (—O—), or a hydroxy group; R22, R23, R25, R26, R27, R29, R30, and R31 represent the same or different linear, branched, or cyclic alkyl groups having 1 to 12 carbon atoms, optionally containing a carbonyl group, an ester group, or an ether group, or represent an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a thiophenyl group; Z0 represents a single bond, a methylene group, an ethylene group, a phenylene group, a fluorinated phenylene group, —O—R32—, or —C(═O)—Z1—R32—; Z1 represents an oxygen atom or NH; R32 represents a linear, a branched, or a cyclic alkylene group having 1 to 6 carbon atoms, an alkenylene group, or a phenylene group, optionally containing a carbonyl group, an ester group, an ether group, or a hydroxy group; and M− represents a non-nucleophilic counter ion.

### Claim 10 (depends on 3)

The polymer according to claim 3, further comprising any one or more kinds of repeating units of represented by the following general formulae (d1) to (d3),
wherein each of R20, R24, and R28 independently represents a hydrogen atom or a methyl group; R21 represents a single bond, a phenylene group, —O—R33—, or —C(═O)—Y—R33—; Y represents an oxygen atom or NH; R33 represents a linear, a branched, or a cyclic alkylene group having 1 to 6 carbon atoms, an alkenylene group, or a phenylene group, optionally containing a carbonyl group (—CO—), an ester group (—COO—), an ether group (—O—), or a hydroxy group; R22, R23, R25, R26, R27, R29, R30, and R31 represent the same or different linear, branched, or cyclic alkyl groups having 1 to 12 carbon atoms, optionally containing a carbonyl group, an ester group, or an ether group, or represent an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a thiophenyl group; Z0 represents a single bond, a methylene group, an ethylene group, a phenylene group, a fluorinated phenylene group, —O—R32—, or —C(═O)—Z1—R32—; Z1 represents an oxygen atom or NH; R32 represents a linear, a branched, or acyclic alkylene group having 1 to 6 carbon atoms, an alkenylene group, or a phenylene group, optionally containing a carbonyl group, an ester group, an ether group, or a hydroxy group; and M− represents a non-nucleophilic counter ion.

### Claim 11 (depends on 3)

A resist composition comprising the polymer of claim 3 as a base resin.

### Claim 12 (depends on 11)

The resist composition according to claim 11, comprising any one or more of an organic solvent and an acid generator.

### Claim 13 (depends on 11)

A patterning process comprising the steps of applying the resist composition of claim 11 to a substrate; performing exposure to a high-energy beam or an electron beam through a photomask after heat treatment; and performing development with a developer.

### Claim 14 (depends on 13)

The patterning process according to claim 13, wherein in the development step, a non-exposed area of the resist film is dissolved in a developer containing an organic solvent to form a negative pattern.

### Claim 15 (depends on 13)

The patterning process according to claim 13 wherein in the exposure step, a liquid having a high index of refraction of 1.0 or more is placed between the resist film and a projection lens to perform immersion lithography.

### Claim 16 (depends on 15)

The patterning process according to claim 15, wherein in the immersion lithography, a top coat is applied to the resist film, and a liquid having a high index of refraction of 1.0 or more is placed between the top coat and the projection lens to perform immersion lithography.