# US 10,871,711 B2 · Resist composition and patterning process

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- Number: US 10,871,711 B2
- Document ID: US10871711B2
- Status: Granted
- Kind: B2
- Application number: 16/130,271
- Filed: 2018-09-13
- Published: 2019-03-28
- Granted: 2020-12-22
- Earliest claimed: 2017-09-25
- Assignees: Shin-Etsu Chemical Co., Ltd.
- Applicants: Shin-Etsu Chemical Co., Ltd.
- Inventors: Jun Hatakeyama; Masaki Ohashi; Masahiro Fukushima; Takayuki Fujiwara
- Web page: https://patentgrep.com/patent/US10871711B2

## CPC

- G03F 7/0045: {with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors}
- C08K 5/0025: {Crosslinking or vulcanising agents; including accelerators}
- C08K 5/42: Sulfonic acids; Derivatives thereof
- C08L 33/14: of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
- C08L 41/00: Compositions of homopolymers or 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 bond to sulfur or by a heterocyclic ring containing sulfur; Compositions of derivatives of such polymers
- C09D 125/08: Copolymers of styrene (C09D129/08, C09D135/06, C09D155/02 take precedence)
- C09D 133/10: Homopolymers or copolymers of methacrylic acid esters
- G03F 7/0395: {the macromolecular compound having a backbone with alicyclic moieties}
- G03F 7/0397: {the macromolecular compound having an alicyclic moiety in a side chain}
- C08F 12/24: Phenols or alcohols
- C08F 212/16: {Halogens}
- C08F 212/24: {Phenols or alcohols}
- C08L 25/18: Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
- C08L 2312/00: Crosslinking
- 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)
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- 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)
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS

## Abstract

A resist composition is provided comprising a base polymer containing an iodized polymer, and an acid generator containing a sulfonium salt and/or iodonium salt of iodized benzene ring-containing fluorosulfonic acid. When processed by lithography, the resist composition exhibits a high sensitivity, low LWR and improved CDU independent of whether it is of positive tone or negative tone.

## Claims

### Claim 1

A resist composition comprising a base polymer containing an iodized polymer, and an acid generator containing a sulfonium salt and/or iodonium salt of iodized benzene ring-containing fluorosulfonic acid.

### Claim 2 (depends on 1)

The resist composition of claim 1 wherein the sulfonium salt and iodonium salt of iodized benzene ring-containing fluorosulfonic acid are a sulfonium salt having the formula (A-1) and an iodonium salt having the formula (A-2), respectively,
wherein L1 is a single bond, ether bond, ester bond, or a C1-C6 alkylene group which may contain an ether bond or ester bond,
R1 is a hydroxyl, carboxyl, fluorine, chlorine, bromine, or amino group, or a C1-C20 alkyl, C1-C20 alkoxy, C2-C10 alkoxycarbonyl, C2-C20 acyloxy or C1-C20 alkylsulfonyloxy group, which may contain fluorine, chlorine, bromine, hydroxyl, amino or C1-C10 alkoxy moiety, or —NR8—C(═O)—R9 or —NR8—C(═O)—O—R9, R8 is hydrogen, or a C1-C6 alkyl group which may contain halogen, hydroxyl, C1-C6 alkoxy, C2-C6 acyl or C2-C6 acyloxy moiety, R9 is a C1-C16 alkyl, C2-C16 alkenyl, or C6-C12 aryl group, which may contain a halogen, hydroxyl, C1-C6 alkoxy, C2-C6 acyl or C2-C6 acyloxy moiety,
R2 is a single bond or C1-C20 divalent linking group when p=1, or a C1-C20 tri- or tetravalent linking group when p=2 or 3, the linking group optionally containing an oxygen, sulfur or nitrogen atom,
Rf1 to Rf4 are each independently hydrogen, fluorine or trifluoromethyl, at least one of Rf1 to Rf4 being fluorine or trifluoromethyl, Rf1 and Rf2 taken together may form a carbonyl group,
R3, R4, R5, R6 and R7 are each independently a C1-C20 monovalent hydrocarbon group which may contain a heteroatom, any two of R3, R4, and R5 may bond together to form a ring with the sulfur atom to which they are attached,
p is an integer of 1 to 3, q is an integer of 1 to 5, r is an integer of 0 to 3, and 1≤q+r≤5.

### Claim 3 (depends on 1)

The resist composition of claim 1 wherein the iodized polymer comprises recurring units having the formula (a1) or (a2):
wherein RA is each independently hydrogen or methyl, R21 is a single bond or methylene, R22 is hydrogen or C1-C4 alkyl, X1 is a single bond, ether bond, ester bond, amide bond, —C(═O)—O—R23—, phenylene, -Ph-C(═O)—O—R24—, or -Ph-R25—O—C(═O)—R26—, Ph is phenylene, R23 is a C1-C10 alkylene group which may contain an ether bond or ester bond, R24, R25 and R26 are each independently a single bond or a C1-C6 straight or branched alkylene group, m is an integer of 1 to 5, n is an integer of 0 to 4, and 1≤m+n≤5.

### Claim 4 (depends on 3)

The resist composition of claim 3 wherein n is an integer of 1 to 3.

### Claim 5 (depends on 1)

The resist composition of claim 1, further comprising an organic solvent.

### Claim 6 (depends on 1)

The resist composition of claim 1 wherein the iodized polymer further comprises recurring units having the formula (b1) or (b2):
wherein RA is each independently hydrogen or methyl, Y1 is a single bond, phenylene group, naphthylene group, or a C1-C12 linking group containing an ester bond or lactone ring, Y2 is a single bond or ester bond, R31 and R32 are each independently an acid labile group, R33 is fluorine, trifluoromethyl, cyano, C1-C6 alkyl, C1-C6 alkoxy, C2-C7 acyl, C2-C7 acyloxy, or C2-C7 alkoxycarbonyl group, R34 is a single bond or a C1-C6 alkylene group in which at least one carbon may be substituted by an ether or ester bond, t is 1 or 2, s is an integer of 0 to 4, and 1≤t+s≤5.

### Claim 7 (depends on 6)

The resist composition of claim 6, further comprising a dissolution inhibitor.

### Claim 8 (depends on 6)

The resist composition of claim 6 which is a chemically amplified positive resist composition.

### Claim 9 (depends on 1)

The resist composition of claim 1 wherein the iodized polymer is free of an acid labile group.

### Claim 10 (depends on 9)

The resist composition of claim 9, further comprising a crosslinker.

### Claim 11 (depends on 9)

The resist composition of claim 9 which is a chemically amplified negative resist composition.

### Claim 12 (depends on 1)

The resist composition of claim 1, further comprising a quencher.

### Claim 13 (depends on 1)

The resist composition of claim 1, further comprising a surfactant.

### Claim 14 (depends on 1)

The resist composition of claim 1 wherein the iodized polymer further comprises recurring units of at least one type selected from recurring units having the formulae (g1), (g2) and (g3):
wherein RA is each independently hydrogen or methyl,
Z1 is a single bond, phenylene group, —O—Z12—, or —C(═O)—Z11—Z12—, Z11 is —O— or —NH—, Z12 is a C1-C6 alkylene, C2-C6 alkenylene or phenylene group, which may contain a carbonyl, 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 alkylene group which may contain a carbonyl moiety, ester bond or ether bond,
A is hydrogen or trifluoromethyl,
Z3 is a single bond, methylene, ethylene, phenylene or fluorinated phenylene group, —O—Z32—, or —C(═O)—Z31—Z32—, Z31 is —O— or —NH—, Z32 is a C1-C6 alkylene, phenylene, fluorinated phenylene, trifluoromethyl-substituted phenylene, or C2-C6 alkenylene group, which may contain a carbonyl, ester bond, ether bond or hydroxyl moiety,
R41 to R48 are each independently a C1-C20 monovalent hydrocarbon group which may contain a heteroatom, any two of R43, R44 and R45 or any two of R46, R47 and R48 may bond together to form a ring with the sulfur atom to which they are attached, and
Q− is a non-nucleophilic counter ion.

### Claim 15 (depends on 1)

A pattern forming process comprising the steps of coating the resist composition of claim 1 onto a substrate, baking to form a resist film, exposing the resist film to high-energy radiation, and developing the exposed resist film in a developer.

### Claim 16 (depends on 15)

The process of claim 15 wherein the high-energy radiation is ArF excimer laser of wavelength 193 nm or KrF excimer laser of wavelength 248 nm.

### Claim 17 (depends on 15)

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

### Claim 18 (depends on 1)

The resist composition of claim 1 wherein Rf1 is trifluoromethyl.

### Claim 19 (depends on 1)

The resist composition of claim 1 wherein both Rf3 and Rf4 are fluorine.