# US 2021/0341839 A1 · Fluorocarboxylic acid-containing monomer, fluorocarboxylic acid-containing polymer, resist composition and patterning process

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- Number: US 2021/0341839 A1
- Document ID: US20210341839A1
- Status: Published application
- Kind: A1
- Application number: 17/223,256
- Filed: 2021-04-06
- Published: 2021-11-04
- Earliest claimed: 2020-04-28
- Assignees: Shin-Etsu Chemical Co., Ltd.
- Applicants: Shin-Etsu Chemical Co., Ltd.
- Inventors: Jun Hatakeyama; Masahiro Fukushima
- Web page: https://patentgrep.com/patent/US20210341839A1

## CPC

- G03F 7/0392: {the macromolecular compound being present in a chemically amplified positive photoresist composition}
- C07C 69/653: Acrylic acid esters; Methacrylic acid esters; Haloacrylic acid esters; Halomethacrylic acid esters
- C08F 212/20: {Fluorine}
- C08F 212/24: {Phenols or alcohols}
- C08F 220/22: Esters containing halogen
- C08F 220/24: containing perhaloalkyl radicals
- C08F 220/281: {and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate}
- C08F 220/282: {and containing two or more oxygen atoms}
- C08F 220/283: {and containing one or more carboxylic moiety in the chain, e.g. acetoacetoxyethyl(meth)acrylate}
- C08F 220/301: {and one oxygen in the alcohol moiety}
- C08F 220/303: {and one or more carboxylic moieties in the chain}
- C09D 125/18: Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
- 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 7/0382: {the macromolecular compound being present in a chemically amplified negative 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)}
- C07C 2601/08: the ring being saturated
- 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
- 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

A fluorocarboxylic acid-containing polymer comprising recurring units having formula (A1), but not acid labile group-containing recurring units is provided. A resist composition comprising the same offers a high sensitivity and is unsusceptible to nano-bridging or pattern collapse independent of whether it is of positive or negative tone.

## Claims

### Claim 1

A fluorocarboxylic acid-containing monomer having the formula (A):
wherein RA is hydrogen or methyl,
R1 and R2 are each independently hydrogen, or a C1-C10 saturated hydrocarbyl group, C2-C8 unsaturated aliphatic hydrocarbyl group, optionally substituted C6-C10 aryl group, or C4-C10 monovalent group obtained by combining the foregoing, with the proviso that R2 is other than hydrogen when R1 is a C1-C4 alkyl group, R1 and R2 may bond together to form a ring with the carbon atom to which they are attached,
X1 is a single bond, phenylene, naphthalenediyl or —C(═O)—O—X11—, X11 is a C1-C10 saturated hydrocarbylene group or phenylene group.

### Claim 2

A fluorocarboxylic acid-containing polymer comprising recurring units having the formula (A1):
wherein RA is hydrogen or methyl,
R1 and R2 are each independently hydrogen, or a C1-C10 saturated hydrocarbyl group, C2-C8 unsaturated aliphatic hydrocarbyl group, optionally substituted C6-C10 aryl group, or C4-C10 monovalent group obtained by combining the foregoing, with the proviso that R2 is other than hydrogen when R1 is a C1-C4 alkyl group, R1 and R2 may bond together to form a ring with the carbon atom to which they are attached,
X1 is a single bond, phenylene, naphthalenediyl or —C(═O)—O—X11—, X11 is a C1-C10 saturated hydrocarbylene group or phenylene group,
the polymer being free of recurring units containing an acid labile group.

### Claim 3 (depends on 2)

The fluorocarboxylic acid-containing polymer of claim 2, further comprising recurring units of at least one type selected from recurring units having the formula (B) and recurring units having the formula (C):
wherein RA is hydrogen or methyl,
n is 1 or 2,
X2A is a single bond, —O—, —C(═O)—O—, or —C(═O)—NH—,
X2B is a C1-C12 (n+1)-valent saturated hydrocarbon group or (n+1)-valent aromatic hydrocarbon group, wherein some or all of the hydrogen atoms may be substituted by fluorine or hydroxyl, and some carbon may be replaced by an ester bond or ether bond,
X3 is a single bond, —O—, —C(═O)—O—X31—X32— or —C(═O)—NH—X31—X32—, X31 is a single bond or a C1-C4 alkanediyl group, X32 is a single bond ester bond ether bond or sulfonamide bond,
R3 is a single bond ester bond or C1-C12 saturated hydrocarbylene group wherein some or all of the hydrogen atoms may be substituted by fluorine, and some carbon may be replaced by an ester bond or ether bond,
R4 is hydrogen, fluorine, methyl, trifluoromethyl, or difluoromethyl, R3 and R4 may bond together to form a ring with the carbon atom to which they are attached, the ring may contain an ether bond, fluorine or trifluoromethyl, and
R5 is a C1-C20 hydrocarbyl group substituted with at least one fluorine, wherein some carbon may be replaced by an ester bond or ether bond.

### Claim 4 (depends on 2)

A resist composition comprising the fluorocarboxylic acid-containing polymer of claim 2 and a base polymer.

### Claim 5 (depends on 4)

The resist composition of claim 4 wherein 0.001 to 20 parts by weight of the fluorocarboxylic acid-containing polymer is present per 100 parts by weight of the base polymer.

### Claim 6 (depends on 4)

The resist composition of claim 4, further comprising an acid generator capable of generating a sulfonic acid, imide acid or methide acid.

### Claim 7 (depends on 4)

The resist composition of claim 4, further comprising an organic solvent.

### Claim 8 (depends on 4)

The resist composition of claim 4 wherein the base polymer comprises recurring units having the formula (a1) or recurring units having the formula (a2):
wherein RB is each independently hydrogen or methyl, R11 and R12 each are an acid labile group, R13 is fluorine, trifluoromethyl, a C1-C5 saturated hydrocarbyl group or C1-C5 saturated hydrocarbyloxy group, Y1 is a single bond, phenylene group, naphthylene group, or C1-C12 linking group containing at least one moiety selected from ester bond and lactone ring, Y2 is a single bond or ester bond, and a is an integer of 0 to 4.

### Claim 9 (depends on 8)

The resist composition of claim 8 which is a chemically amplified positive resist composition.

### Claim 10 (depends on 4)

The resist composition of claim 4 wherein the base polymer is free of an acid labile group.

### Claim 11 (depends on 10)

The resist composition of claim 10 which is a chemically amplified negative resist composition.

### Claim 12 (depends on 4)

The resist composition of claim 4 wherein the base polymer comprises recurring units of at least one type selected from recurring units having the formulae (f1) to (f3):
wherein RB is each independently hydrogen or methyl,
Z1 is a single bond, a C1-C6 aliphatic hydrocarbylene group, phenylene group, naphthylene group, or C7-C18 group obtained by combining the foregoing, or —O—Z11—, —C(═O)—O—Z11— or —C(═O)—NH—Z11—, Z11 is a C1-C6 aliphatic hydrocarbylene group, phenylene group, naphthylene group, or C7-C18 group obtained by combining the foregoing, which may contain a carbonyl moiety, ester bond, ether bond or hydroxyl moiety,
Z2 is a single bond, —Z21—C(═O)—O—, —Z21—O— or —Z21—O—C(═O)—, Z21 is a C1-C12 saturated hydrocarbylene group which may contain a carbonyl moiety, ester bond or ether bond,
Z3 is a single bond, methylene, ethylene, phenylene, fluorinated phenylene, —O—Z31—, —C(═O)—O—Z31—, or —C(═O)—NH—Z31—, Z31 is a C1-C6 aliphatic hydrocarbylene group, phenylene group, fluorinated phenylene group, or trifluoromethyl-substituted phenylene group, which may contain a carbonyl moiety, ester bond, ether bond or hydroxyl moiety,
R21 to R28 are each independently halogen or a C1-C20 hydrocarbyl group which may contain a heteroatom, a pair of R23 and R24 or R26 and R27 may bond together to form a ring with the sulfur atom to which they are attached,
RHF is hydrogen or trifluoromethyl, and
M− is a non-nucleophilic counter ion.

### Claim 13 (depends on 4)

The resist composition of claim 4, further comprising a surfactant.

### Claim 14 (depends on 4)

A process for forming a pattern comprising the steps of applying the resist composition of claim 4 onto a substrate to form a resist film thereon, exposing the resist film to high-energy radiation, and developing the exposed resist film in a developer.

### Claim 15 (depends on 14)

The process of claim 14 wherein the high-energy radiation is ArF excimer laser radiation of wavelength 193 nm or KrF excimer laser radiation of wavelength 248 nm.

### Claim 16 (depends on 14)

The process of claim 14 wherein the high-energy radiation is EB or EUV of wavelength 3 to 15 nm.