# US 12,117,728 B2 · Resist composition and patterning process

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- Number: US 12,117,728 B2
- Document ID: US12117728B2
- Status: Granted
- Kind: B2
- Application number: 17/342,701
- Filed: 2021-06-09
- Published: 2021-12-30
- Granted: 2024-10-15
- Earliest claimed: 2020-06-18
- Assignees: Shin-Etsu Chemical Co., Ltd.
- Applicants: Shin-Etsu Chemical Co., Ltd.
- Inventors: Jun Hatakeyama
- Web page: https://patentgrep.com/patent/US12117728B2

## CPC

- G03F 7/0045: {with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors}
- C07C 381/12: Sulfonium compounds
- C08F 212/22: {Oxygen}
- C08F 212/24: {Phenols or alcohols}
- C08F 220/1802: {C2-(meth)acrylate, e.g. ethyl (meth)acrylate}
- C08F 220/1806: {C6-(meth)acrylate, e.g. (cyclo)hexyl (meth)acrylate or phenyl (meth)acrylate}
- C09D 125/18: Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
- C09D 133/08: Homopolymers or copolymers of acrylic acid esters
- 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 7/0392: {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: 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 resist composition is provided comprising a base polymer and a quencher comprising a salt compound obtained from a nitrogen-containing compound having an iodine or bromine-substituted hydrocarbyl group (exclusive of iodine or bromine-substituted aromatic ring) bonded to the nitrogen atom via an ester bond-containing group and a compound having a 1,1,1,3,3,3-hexafluoro-2-propanol group. The resist composition has a high sensitivity and forms a pattern with improved LWR or CDU, independent of whether it is of positive or negative tone.

## Claims

### Claim 1

A resist composition comprising a base polymer and a quencher,
said quencher comprising a salt compound obtained from a nitrogen-containing compound having an iodine or bromine-substituted hydrocarbyl group, exclusive of iodine or bromine-substituted aromatic ring, bonded to the nitrogen atom via an ester bond-containing group and a compound having a 1,1,1,3,3,3-hexafluoro-2-propanol group.

### Claim 2 (depends on 1)

The resist composition of claim 1 wherein said salt compound has the formula (A):
wherein k is an integer of 1 to 3, m1 is 1 or 2, m2 is an integer of 1 to 3, n is an integer of 1 to 4,
XBI is iodine or bromine,
Rah is a C1-C20 (k+1)-valent aliphatic hydrocarbon group which may contain at least one moiety selected from ether bond, carbonyl, ester bond, amide bond, sultone ring, lactam ring, carbonate, halogen exclusive of iodine, C6-C12 aryl, hydroxyl, and carboxyl,
X1 is a single bond, ether bond, ester bond, amide bond, carbonyl group, or carbonate group,
R1 is a single bond or a C1-C20 (m1+1)-valent hydrocarbon group which may contain an ether bond, ester bond or hydroxyl moiety,
R2 is a single bond or a C1-C20 (m2+1)-valent hydrocarbon group which may contain at least one moiety selected from ether bond, carbonyl, ester bond, amide bond, sultone ring, lactam ring, carbonate, halogen exclusive of iodine, hydroxyl, and carboxyl,
R3 is hydrogen, nitro, C1-C20 hydrocarbyl group or C2-C20 hydrocarbyloxycarbonyl group, the hydrocarbyl group or the hydrocarbyl moiety of the hydrocarbyloxycarbonyl group may contain at least one moiety selected from hydroxyl, carboxyl, thiol, ether bond, ester bond, sulfonyl, nitro, cyano, halogen, and amino, in case of n=1, two groups R3 may bond together to form a ring with the nitrogen atom to which they are attached, the ring optionally containing a double bond, oxygen, sulfur or nitrogen, or R3 and R1 may bond together to form a ring with the nitrogen atom to which they are attached, the ring optionally containing a double bond, oxygen, sulfur or nitrogen,
R4 is trifluoromethyl, a C2-C21 hydrocarbylcarbonyl group or C2-C21 hydrocarbyloxycarbonyl group, the hydrocarbyl moiety of the hydrocarbylcarbonyl group or hydrocarbyloxycarbonyl group may contain at least one moiety selected from ether bond, ester bond, thiol, cyano, nitro, hydroxyl, sultone, sulfonate bond, amide bond, and halogen.

### Claim 3 (depends on 1)

The resist composition of claim 1, further comprising an acid generator capable of generating a sulfonic acid, imide acid or methide acid.

### Claim 4 (depends on 1)

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

### Claim 5 (depends on 1)

The resist composition of claim 1 wherein the base polymer comprises recurring units having the formula (a1) or recurring units having the formula (a2):
wherein RA is each independently hydrogen or methyl, R11 and R12 are each independently an acid labile group, Y1 is a single bond, phenylene, naphthylene, or a C1-C12 linking group containing an ester bond and/or lactone ring, and Y2 is a single bond or ester bond.

### Claim 6 (depends on 5)

The resist composition of claim 5 which is a chemically amplified positive resist composition.

### Claim 7 (depends on 1)

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

### Claim 8 (depends on 7)

The resist composition of claim 7 which is a chemically amplified negative resist composition.

### Claim 9 (depends on 1)

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

### Claim 10 (depends on 1)

The resist composition of claim 1 wherein the base polymer comprises recurring to units of at least one type selected from recurring units having the formulae (f1) to (f3):
wherein RA 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 11 (depends on 1)

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

### Claim 12 (depends on 11)

The process of claim 11 wherein the high-energy radiation is ArF excimer laser of wavelength 193 nm or KrF excimer laser of wavelength 248 nm.

### Claim 13 (depends on 11)

The process of claim 11 wherein the high-energy radiation is EB or EUV of wavelength 3 to 15 nm.