# US 2018/0024435 A1 · Resist composition and patterning process using the same

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- Number: US 2018/0024435 A1
- Document ID: US20180024435A1
- Status: Published application
- Kind: A1
- Application number: 15/634,469
- Filed: 2017-06-27
- Published: 2018-01-25
- Earliest claimed: 2016-07-22
- Assignees: Shin-Etsu Chemical Co., Ltd.
- Applicants: Shin-Etsu Chemical Co., Ltd.
- Inventors: Jun HATAKEYAMA; Koji HASEGAWA; Masayoshi SAGEHASHI
- Web page: https://patentgrep.com/patent/US20180024435A1

## CPC

- C08F 220/22: Esters containing halogen
- C08F 28/02: by a bond to sulfur
- C08F 220/24: containing perhaloalkyl radicals
- C08F 220/283: {and containing one or more carboxylic moiety in the chain, e.g. acetoacetoxyethyl(meth)acrylate}
- C08F 220/56: Acrylamide; Methacrylamide
- C08F 224/00: Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a heterocyclic ring containing oxygen (cyclic esters of polyfunctional acids C08F218/00; cyclic anhydrides of unsaturated acids C08F220/00, C08F222/00)
- 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 7/0048: {characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents}
- 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 7/162: {Coating on a rotating support, e.g. using a whirler or a spinner}
- G03F 7/168: {Finishing the coated layer, e.g. drying, baking, soaking}
- G03F 7/2004: {characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light}
- G03F 7/2006: {using coherent light; using polarised light}
- G03F 7/2037: {Exposure with X-ray radiation or corpuscular radiation, through a mask with a pattern opaque to that radiation}
- G03F 7/2039: {X-ray radiation}
- G03F 7/30: Imagewise removal using liquid means
- G03F 7/322: {Aqueous alkaline compositions}
- G03F 7/38: Treatment before imagewise removal, e.g. prebaking {(G03F7/265 takes precedence)}
- C08F 212/20: {Fluorine}
- C08F 212/22: {Oxygen}
- C08F 212/32: containing two or more rings
- C08F 220/1807: {C7-(meth)acrylate, e.g. heptyl (meth)acrylate or benzyl (meth)acrylate}
- C08F 220/1809: {C9-(meth)acrylate}
- C08F 220/282: {and containing two or more oxygen atoms}
- C08F 220/301: {and one oxygen in the alcohol moiety}
- C08F 220/302: {and two or more oxygen atoms in the alcohol moiety}
- C08F 220/303: {and one or more carboxylic moieties in the chain}
- C08F 220/382: {and containing oxygen, e.g. 2-sulfoethyl (meth)acrylate}
- 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 resist composition containing a base resin composed of a polymer compound that contains a repeating unit “a” shown by formula (1) and a repeating unit “b” having either or both of a carboxyl group in which a hydrogen atom is substituted with an acid-labile group and a phenolic hydroxyl group in which a hydrogen atom is substituted with an acid-labile group, with a weight average molecular weight of 1,000 to 500,000. There can be provided a resist composition that has high sensitivity and high resolution, and can give a pattern with low dimensional variation and good pattern profile after exposure. wherein R1 represents a hydrogen atom or a methyl group; Z represents a hydroxybenzoquinone group, or a hydroxynaphthoquinone group optionally containing a substituent; and a fraction “a” of the repeating unit “a” satisfies 0<a<1.0, and a fraction “b” of the repeating unit “b” satisfies 0<b<1.0.

## Claims

### Claim 1

A resist composition comprising a polymer compound as a base resin,
the polymer compound comprising a repeating unit “a” shown by the following general formula (1) and a repeating unit “b” having either or both of a carboxyl group in which a hydrogen atom is substituted with an acid-labile group and a phenolic hydroxyl group in which a hydrogen atom is substituted with an acid-labile group, the polymer compound having a weight average molecular weight of 1,000 to 500,000,
wherein R1 represents a hydrogen atom or a methyl group; Z represents a hydroxybenzoquinone group, or a hydroxynaphthoquinone group optionally containing a substituent; and a fraction “a” of the repeating unit “a” satisfies 0<a<1.0, and a fraction “b” of the repeating unit “b” satisfies 0<b<1.0.

### Claim 2 (depends on 1)

The resist composition according to claim 1, wherein the repeating unit “a” comprises a repeating unit a1 shown by the following general formula (1-1) having a hydroxybenzoquinone group,
wherein R1 is as defined above; and a1 represents a number satisfying 0<a1<1.0.

### Claim 3 (depends on 1)

The resist composition according to claim 1, wherein the repeating unit “a” comprises a repeating unit a2 shown by the following general formula (1-2) having a hydroxynaphthoquinone group,
wherein R1 is as defined above; R2 represents a hydrogen atom, a halogen atom, or a linear or branched alkyl group having 1 to 4 carbon atoms; “m” represents 1 or 2; and a2 represents a number satisfying 0<a2<1.0.

### Claim 4 (depends on 1)

The resist composition according to claim 1, wherein the repeating unit “b” comprises one or more repeating units selected from a repeating unit b1 shown by the following general formula (2-1) and a repeating unit b2 shown by the following general formula (2-2),
wherein R3 and R5 represent a hydrogen atom or a methyl group; R4 and R5 represent an acid-labile group; R6 represents a single bond or a linear or branched alkylene group having 1 to 6 carbon atoms and optionally containing an ether group or an ester group; R7 represents a hydrogen atom, a fluorine atom, a trifluoromethyl group, a cyano group, or a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms; “p” represents 1 or 2; “q” represents an integer of 0 to 4; p+q≦5; Y1 represents a linking group having 1 to 12 carbon atoms and containing an ester group, an ether group, or a lactone ring, or represents a single bond, a phenylene group, or a naphthylene group; Y2 represents a single bond, an ester bond, or —C(═O)—NH—; b1 and b2 represent a number satisfying 0≦b1<1.0, 0≦b2<1.0, 0<b1+b2<1.0, and 0.1≦a+b1+b2≦1.0.

### Claim 5 (depends on 2)

The resist composition according to claim 2, wherein the repeating unit “b” comprises one or more repeating units selected from a repeating unit b1 shown by the following general formula (2-1) and a repeating unit b2 shown by the following general formula (2-2),
wherein R3 and R5 represent a hydrogen atom or a methyl group; R4 and R8 represent an acid-labile group; R6 represents a single bond or a linear or branched alkylene group having 1 to 6 carbon atoms and optionally containing an ether group or an ester group; R7 represents a hydrogen atom, a fluorine atom, a trifluoromethyl group, a cyano group, or a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms; “p” represents 1 or 2; “q” represents an integer of 0 to 4; p+q 5; Y1 represents a linking group having 1 to 12 carbon atoms and containing an ester group, an ether group, or a lactone ring, or represents a single bond, a phenylene group, or a naphthylene group; Y2 represents a single bond, an ester bond, or —C(═O)—NH—; b1 and b2 represent a number satisfying 0≦b1<1.0, 0≦b2<1.0, 0<b1+b2<1.0, and 0.1≦a+b1+b2≦1.0.

### Claim 6 (depends on 3)

The resist composition according to claim 3, wherein the repeating unit “b” comprises one or more repeating units selected from a repeating unit b1 shown by the following general formula (2-1) and a repeating unit b2 shown by the following general formula (2-2),
wherein R3 and R5 represent a hydrogen atom or a methyl group; R4 and R8 represent an acid-labile group; R6 represents a single bond or a linear or branched alkylene group having 1 to 6 carbon atoms and optionally containing an ether group or an ester group; R7 represents a hydrogen atom, a fluorine atom, a trifluoromethyl group, a cyano group, or a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms; “p” represents 1 or 2; “q” represents an integer of 0 to 4; p+q≦5; Y1 represents a linking group having 1 to 12 carbon atoms and containing an ester group, an ether group, or a lactone ring, or represents a single bond, a phenylene group, or a naphthylene group; Y2 represents a single bond, an ester bond, or —C(═O)—NH—; b1 and b2 represent a number satisfying 0≦b1<1.0, 0≦b2<1.0, 0<b1+b2<1.0, and 0.1≦a+b1+b2≦1.0.

### Claim 7 (depends on 1)

The resist composition according to claim 1, wherein the polymer compound further comprises a repeating unit “c” having an adhesion group selected from a hydroxyl group, a carboxyl group, a lactone ring, a carbonate group, a thiocarbonate group, a carbonyl group, a cyclic acetal group, an ether group, an ester group, a sulfonate ester group, a cyano group, an amide group, and —O—C(═O)-G-, where G represents a sulfur atom or —NH—, and a intramolecular fraction c1 of the repeating unit “c” satisfies 0<c1≦0.9.

### Claim 8 (depends on 2)

The resist composition according to claim 2, wherein the polymer compound further comprises a repeating unit “c” having an adhesion group selected from a hydroxyl group, a carboxyl group, a lactone ring, a carbonate group, a thiocarbonate group, a carbonyl group, a cyclic acetal group, an ether group, an ester group, a sulfonate ester group, a cyano group, an amide group, and —O—C(═O)-G-, where G represents a sulfur atom or —NH—, and a intramolecular fraction c1 of the repeating unit “c” satisfies 0<c1≦0.9.

### Claim 9 (depends on 3)

The resist composition according to claim 3, wherein the polymer compound further comprises a repeating unit “c” having an adhesion group selected from a hydroxyl group, a carboxyl group, a lactone ring, a carbonate group, a thiocarbonate group, a carbonyl group, a cyclic acetal group, an ether group, an ester group, a sulfonate ester group, a cyano group, an amide group, and —O—C(═O)-G-, where G represents a sulfur atom or —NH—, and a intramolecular fraction c1 of the repeating unit “c” satisfies 0<c1≦0.9.

### Claim 10 (depends on 4)

The resist composition according to claim 4, wherein the polymer compound further comprises a repeating unit “c” having an adhesion group selected from a hydroxyl group, a carboxyl group, a lactone ring, a carbonate group, a thiocarbonate group, a carbonyl group, a cyclic acetal group, an ether group, an ester group, a sulfonate ester group, a cyano group, an amide group, and —O—C(═O)-G-, where G represents a sulfur atom or —NH—, and a intramolecular fraction c1 of the repeating unit “c” satisfies 0<c1≦0.9.

### Claim 11 (depends on 1)

The resist composition according to claim 1, wherein the polymer compound further comprises one or more repeating units “d” selected from repeating units d1 to d3 shown by the following general formulae (3-1) to (3-3) having a sulfonium salt,
wherein R20, R24, and R28 represent a hydrogen atom or a methyl group; R21 represents a single bond, a phenylene group, —O—R—, or —C(═O)—V—R—, where V represents an oxygen atom or —NH—, and R represents a phenylene group or a linear, branched, or cyclic alkylene group or alkenylene group having 1 to 6 carbon atoms and optionally containing a carbonyl group, an ester group, an ether group, or a hydroxyl group; Rf1 to Rf4 represent a fluorine atom, a hydrogen atom, or a trifluoromethyl group, provided that one or more of Rf1 to Rf4 are a fluorine atom or a trifluoromethyl group; R22, R23, R25, R26, R27, R29, R30, and R31 are the same or different and represent a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a thiophenyl group optionally containing a carbonyl group, an ester group, or an ether group, in which two or more of R25, R26, and R27 may be bonded to each other to form a ring together with the sulfur atom in the formula, and when the ring is formed, an oxygen atom may be contained therein; Y3 represents a single bond or a linking group having 1 to 12 carbon atoms and optionally containing an ester group, an ether group, or a lactone ring; Y4 represents a single bond, a methylene group, an ethylene group, a phenylene group, a fluorinated phenylene group, —O—R32—, or —C(═O)—W—R32—, where W represents an oxygen atom or —NH—, and R32 represents a phenylene group or a linear, branched, or cyclic alkylene group or alkenylene group having 1 to 6 carbon atoms and optionally containing a carbonyl group, an ester group, an ether group, or a hydroxyl group; M− represents a non-nucleophilic counter ion; and d1, d2, and d3 represent a number satisfying 0≦d1≦0.5, 0≦d2≦0.5, 0≦d3≦0.5, and 0<d1+d2+d3≦0.5.

### Claim 12 (depends on 2)

The resist composition according to claim 2, wherein the polymer compound further comprises one or more repeating units “d” selected from repeating units d1 to d3 shown by the following general formulae (3-1) to (3-3) having a sulfonium salt,
wherein R20, R24, and R28 represent a hydrogen atom or a methyl group; R21 represents a single bond, a phenylene group, —O—R—, or —C(═O)—V—R—, where V represents an oxygen atom or —NH—, and R represents a phenylene group or a linear, branched, or cyclic alkylene group or alkenylene group having 1 to 6 carbon atoms and optionally containing a carbonyl group, an ester group, an ether group, or a hydroxyl group; Rf1 to Rf4 represent a fluorine atom, a hydrogen atom, or a trifluoromethyl group, provided that one or more of Rf1 to Rf4 are a fluorine atom or a trifluoromethyl group; R22, R23, R25, R26, R27, R29, R30, and R31 are the same or different and represent a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a thiophenyl group optionally containing a carbonyl group, an ester group, or an ether group, in which two or more of R25, R26, and R27 may be bonded to each other to form a ring together with the sulfur atom in the formula, and when the ring is formed, an oxygen atom may be contained therein; Y3 represents a single bond or a linking group having 1 to 12 carbon atoms and optionally containing an ester group, an ether group, or a lactone ring; Y4 represents a single bond, a methylene group, an ethylene group, a phenylene group, a fluorinated phenylene group, —O—R32—, or —C(═O)—W—R32—, where W represents an oxygen atom or —NH—, and R32 represents a phenylene group or a linear, branched, or cyclic alkylene group or alkenylene group having 1 to 6 carbon atoms and optionally containing a carbonyl group, an ester group, an ether group, or a hydroxyl group; M− represents a non-nucleophilic counter ion; and d1, d2, and d3 represent a number satisfying 0≦d1≦0.5, 0≦d2≦0.5, 0≦d3≦0.5, and 0<d1+d2+d3≦0.5.

### Claim 13 (depends on 3)

The resist composition according to claim 3, wherein the polymer compound further comprises one or more repeating units “d” selected from repeating units d1 to d3 shown by the following general formulae (3-1) to (3-3) having a sulfonium salt,
wherein R20, R24, and R25 represent a hydrogen atom or a methyl group; R21 represents a single bond, a phenylene group, —O—R—, or —C(═O)—V—R—, where V represents an oxygen atom or —NH—, and R represents a phenylene group or a linear, branched, or cyclic alkylene group or alkenylene group having 1 to 6 carbon atoms and optionally containing a carbonyl group, an ester group, an ether group, or a hydroxyl group; Rf1 to Rf4 represent a fluorine atom, a hydrogen atom, or a trifluoromethyl group, provided that one or more of Rf1 to Rf4 are a fluorine atom or a trifluoromethyl group; R22, R23, R25, R26, R27, R29, R30, and R31 are the same or different and represent a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a thiophenyl group optionally containing a carbonyl group, an ester group, or an ether group, in which two or more of R25, R26, and R27 may be bonded to each other to form a ring together with the sulfur atom in the formula, and when the ring is formed, an oxygen atom may be contained therein; Y3 represents a single bond or a linking group having 1 to 12 carbon atoms and optionally containing an ester group, an ether group, or a lactone ring; Y4 represents a single bond, a methylene group, an ethylene group, a phenylene group, a fluorinated phenylene group, —O—R32—, or —C(═O)—W—R32—, where W represents an oxygen atom or —NH—, and R32 represents a phenylene group or a linear, branched, or cyclic alkylene group or alkenylene group having 1 to 6 carbon atoms and optionally containing a carbonyl group, an ester group, an ether group, or a hydroxyl group; M− represents a non-nucleophilic counter ion; and d1, d2, and d3 represent a number satisfying 0≦d1≦0.5, 0≦d2≦0.5, 0≦d3≦0.5, and 0<d1+d2+d3≦0.5.

### Claim 14 (depends on 4)

The resist composition according to claim 4, wherein the polymer compound further comprises one or more repeating units “d” selected from repeating units d1 to d3 shown by the following general formulae (3-1) to (3-3) having a sulfonium salt,
wherein R20, R24, and R28 represent a hydrogen atom or a methyl group; R21 represents a single bond, a phenylene group, —O—R—, or —C(═O)—V—R—, where V represents an oxygen atom or —NH—, and R represents a phenylene group or a linear, branched, or cyclic alkylene group or alkenylene group having 1 to 6 carbon atoms and optionally containing a carbonyl group, an ester group, an ether group, or a hydroxyl group; Rf1 to Rf4 represent a fluorine atom, a hydrogen atom, or a trifluoromethyl group, provided that one or more of Rf1 to Rf4 are a fluorine atom or a trifluoromethyl group; R22, R23, R25, R26, R27, R29, R30, and R31 are the same or different and represent a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a thiophenyl group optionally containing a carbonyl group, an ester group, or an ether group, in which two or more of R25, R26, and R27 may be bonded to each other to form a ring together with the sulfur atom in the formula, and when the ring is formed, an oxygen atom may be contained therein; Y3 represents a single bond or a linking group having 1 to 12 carbon atoms and optionally containing an ester group, an ether group, or a lactone ring; Y4 represents a single bond, a methylene group, an ethylene group, a phenylene group, a fluorinated phenylene group, —O—R32—, or —C(═O)—W—R32—, where W represents an oxygen atom or —NH—, and R32 represents a phenylene group or a linear, branched, or cyclic alkylene group or alkenylene group having 1 to 6 carbon atoms and optionally containing a carbonyl group, an ester group, an ether group, or a hydroxyl group; M− represents a non-nucleophilic counter ion; and d1, d2, and d3 represent a number satisfying 0≦d1≦0.5, 0≦d2≦0.5, 0≦d3≦0.5, and 0<d1+d2+d3≦0.5.

### Claim 15 (depends on 7)

The resist composition according to claim 7, wherein the polymer compound further comprises one or more repeating units “d” selected from repeating units d1 to d3 shown by the following general formulae (3-1) to (3-3) having a sulfonium salt,
wherein R20, R24, and R28 represent a hydrogen atom or a methyl group; R21 represents a single bond, a phenylene group, —O—R—, or —C(═O)—V—R—, where V represents an oxygen atom or —NH—, and R represents a phenylene group or a linear, branched, or cyclic alkylene group or alkenylene group having 1 to 6 carbon atoms and optionally containing a carbonyl group, an ester group, an ether group, or a hydroxyl group; Rf1 to Rf4 represent a fluorine atom, a hydrogen atom, or a trifluoromethyl group, provided that one or more of Rf1 to Rf4 are a fluorine atom or a trifluoromethyl group; R22, R23, R25, R26, R27, R29, R30, and R31 are the same or different and represent a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a thiophenyl group optionally containing a carbonyl group, an ester group, or an ether group, in which two or more of R25, R26, and R27 may be bonded to each other to form a ring together with the sulfur atom in the formula, and when the ring is formed, an oxygen atom may be contained therein; Y3 represents a single bond or a linking group having 1 to 12 carbon atoms and optionally containing an ester group, an ether group, or a lactone ring; Y4 represents a single bond, a methylene group, an ethylene group, a phenylene group, a fluorinated phenylene group, —O—R32—, or —C(═O)—W—R32—, where W represents an oxygen atom or —NH—, and R32 represents a phenylene group or a linear, branched, or cyclic alkylene group or alkenylene group having 1 to 6 carbon atoms and optionally containing a carbonyl group, an ester group, an ether group, or a hydroxyl group; M− represents a non-nucleophilic counter ion; and d1, d2, and d3 represent a number satisfying 0≦d1≦0.5, 0≦d2≦0.5, 0≦d3≦0.5, and 0<d1+d2+d3≦0.5.

### Claim 16 (depends on 1)

The resist composition according to claim 1, wherein the resist composition is a chemically amplified resist composition further containing one or more materials selected from an organic solvent, an acid generator, a basic compound, and a surfactant.

### Claim 17 (depends on 2)

The resist composition according to claim 2, wherein the resist composition is a chemically amplified resist composition further containing one or more materials selected from an organic solvent, an acid generator, a basic compound, and a surfactant.

### Claim 18 (depends on 3)

The resist composition according to claim 3, wherein the resist composition is a chemically amplified resist composition further containing one or more materials selected from an organic solvent, an acid generator, a basic compound, and a surfactant.

### Claim 19 (depends on 1)

A patterning process comprising:
applying the resist composition according to claim 1 on a substrate; performing exposure with a high energy beam after a heat treatment; and performing development with a developer.

### Claim 20 (depends on 19)

The patterning process according to claim 19, wherein the high energy beam is an i-line beam, a KrF excimer laser beam, an ArF excimer laser beam, an electron beam, or a soft X-ray having a wavelength of 3 to 15 nm.