# US 2025/0093775 A1 · Photoresist composition and method of forming photoresist pattern

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 2025/0093775 A1
- Document ID: US20250093775A1
- Status: Published application
- Kind: A1
- Application number: 18/964,266
- Filed: 2024-11-29
- Published: 2025-03-20
- Earliest claimed: 2020-06-18
- Assignees: Taiwan Semiconductor Manufacturing Company, Ltd.
- Applicants: Taiwan Semiconductor Manufacturing Company, Ltd.
- Inventors: Li-Po YANG; Wei-Han LAI; Ching-Yu CHANG
- Web page: https://patentgrep.com/patent/US20250093775A1

## CPC

- G03F 7/0045: {with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors}
- C08F 212/24: {Phenols or alcohols}
- C08F 220/382: {and containing oxygen, e.g. 2-sulfoethyl (meth)acrylate}
- C09D 125/18: Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
- G03F 7/0042: {with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists (G03F7/075 takes precedence)}
- G03F 7/0043: {Chalcogenides; Silicon, germanium, arsenic or derivatives thereof; Metals, oxides or alloys thereof (G03F7/0044 takes precedence)}
- 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 7/168: {Finishing the coated layer, e.g. drying, baking, soaking}
- G03F 7/20: Exposure; Apparatus therefor (photographic printing apparatus for making copies G03B27/00)
- G03F 7/322: {Aqueous alkaline compositions}
- G03F 7/325: {Non-aqueous compositions}
- G03F 7/36: Imagewise removal not covered by groups G03F7/30 - G03F7/34, e.g. using gas streams, using plasma
- G03F 7/38: Treatment before imagewise removal, e.g. prebaking {(G03F7/265 takes precedence)}
- 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)
- 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

Method of forming pattern in photoresist layer includes forming photoresist layer over substrate, selectively exposing photoresist layer to actinic radiation forming latent pattern. Latent pattern is developed by applying developer to form pattern. Photoresist layer includes photoresist composition including polymer: A1, A2, L are direct bond, C4-C30 aromatic, C4-C30 alkyl, C4-C30 cycloalkyl, C4-C30 hydroxylalkyl, C4-C30 alkoxy, C4-C30 alkoxyl alkyl, C4-C30 acetyl, C4-C30 acetylalkyl, C4-C30 alkyl carboxyl, C4-C30 cycloalkyl carboxyl, C4-C30 hydrocarbon ring, C4-C30 heterocyclic, —COO—, A1 and A2 are not both direct bonds, and are unsubstituted or substituted with a halogen, carbonyl, or hydroxyl; A3 is C6-C14 aromatic, wherein A3 is unsubstituted or substituted with halogen, carbonyl, or hydroxyl; R1 is acid labile group; Ra, Rb are H or C1-C3 alkyl; Rf is direct bond or C1-C5 fluorocarbon; PAG is photoacid generator; 0<x/(x+y+z)<1, 0<y/(x+y+z)<1, and 0<z/(x+y+z)<1.

## Claims

### Claim 1

A method of manufacturing a semiconductor device, comprising:
depositing a photoresist layer over a semiconductor substrate,
wherein the photoresist layer comprises a composition, comprising:
a polymer having a formula:
where A1, A2, and L are independently-a direct bond, a C4-C30 aromatic group, a C4-C30 alkyl group, a C4-C30 cycloalkyl group, a C4-C30 hydroxylalkyl group, a C4-C30 alkoxy group, a C4-C30 alkoxyl alkyl group, a C4-C30 acetyl group, a C4-C30 acetylalkyl group, a C4-C30 alkyl carboxyl group, a C4-C30 cycloalkyl carboxyl group, a C4-C30 saturated or unsaturated hydrocarbon ring, or a C4-C30 heterocyclic group, wherein A1 and A2 are not both direct bonds, wherein A1 and A2 are unsubstituted or substituted with a halogen, carbonyl group, or hydroxyl group;
A3 is a phenol group, a hydroxynaphthalene group, or a naphthalenyl group;
wherein at least one of A1 and A2 is an adamantyl group, a norbornyl group, a hydroxyanthracene group, or a phenyl group;
R1 is an acid labile group;
Ra and Rb are independently H or a C1-C3 alkyl group;
Rf is a perfluorinated C1-C5 group; and
PAG includes a triphenylsulfonium group and a sulfonate group; and
0<x/(x+y+z)<1, 0<y/(x+y+z)<1, and 0<z/(x+y+z)<1;
selectively exposing the photoresist layer to actinic radiation; and
developing the photoresist layer exposed to the actinic radiation to form a pattern.

### Claim 2 (depends on 1)

The method according to claim 1, wherein A3 is substituted with a halogen, a carbonyl group, or a hydroxyl group.

### Claim 3 (depends on 1)

The method according to claim 1, wherein the composition further comprises a photoactive compound.

### Claim 4 (depends on 3)

The method according to claim 3, wherein the photoactive compound is a photoacid generator.

### Claim 5 (depends on 1)

The method according to claim 1, wherein L is a direct bond and A3 is a p-phenol group, and 0.2≤x/(x+y+z)≤0.5.

### Claim 6 (depends on 1)

The method according to claim 1, wherein A1 is not a direct bond and 0.2≤y/(x+y+z)≤0.7.

### Claim 7 (depends on 1)

The method according to claim 1, wherein 0.1≤x/(x+y+z)≤0.5.

### Claim 8 (depends on 1)

The method according to claim 1, wherein A1 and A2 are not direct bonds and 0.2≤y/(x+y+z)≤0.7 and 0.05≤z/(x+y+z)≤0.5.

### Claim 9 (depends on 1)

The method according to claim 1, wherein A1 is not a direct bond and 0.2≤y/(x+y+z)≤0.7 and 0.1≤x/(x+y+z)≤0.5.

### Claim 10 (depends on 1)

The method according to claim 1, wherein A1 and A2 are not direct bonds and 0.2≤y/(x+y+z)≤0.7, 0.05≤z/(x+y+z)≤0.5, and 0.1≤x/(x+y+z)≤0.5.

### Claim 11

A method of manufacturing a semiconductor device, comprising:
forming a photoresist layer over a semiconductor substrate;
selectively exposing the photoresist layer to actinic radiation; and
developing the selectively exposed photoresist layer to form a pattern,
wherein the photoresist layer includes a photoresist composition comprising a polymer,
wherein the polymer has a formula:
where A1, A2, and L are independently a direct bond, a C4-C30 aromatic group, a C4-C30 alkyl group, a C4-C30 cycloalkyl group, a C4-C30 hydroxylalkyl group, a C4-C30 alkoxy group, a C4-C30 alkoxyl alkyl group, a C4-C30 acetyl group, a C4-C30 acetylalkyl group, a C4-C30 alkyl carboxyl group, a C4-C30 cycloalkyl carboxyl group, a C4-C30 saturated or unsaturated hydrocarbon ring, or a C4-C30 heterocyclic group, wherein A1 and A2 are not both direct bonds;
wherein at least one of A1 and A2 is an adamantyl group, a norbornyl group, a hydroxyanthracene group, or a phenyl group;
A3 is a C6-C14 aromatic group;
R1 is an acid labile group;
Ra and Rb are independently H or a C1-C3 alkyl group;
Rf is a direct bond;
PAG is a photoacid generator; and
0<x/(x+y+z)<1, 0<y/(x+y+z)<1, and 0<z/(x+y+z)<1.

### Claim 12 (depends on 11)

The method according to claim 11, wherein at least one of A1, A2, and A3 are substituted with a halogen, carbonyl group, or hydroxyl group.

### Claim 13 (depends on 11)

The method according to claim 11, wherein the photoresist composition further comprises a solvent.

### Claim 14 (depends on 11)

The method according to claim 11, wherein the polymer has a weight average molecular weight ranging from 500 to 1,000,000.

### Claim 15 (depends on 11)

The method according to claim 11, wherein the photoresist composition further includes a metal oxide nanoparticle and one or more organic ligands.

### Claim 16 (depends on 11)

The method according to claim 11, wherein the photoresist composition further comprises a photoactive compound.

### Claim 17

A photoresist composition, comprising:
a polymer,
wherein the polymer has a formula:
where A1, A2, and L are independently a direct bond, a C4-C30 aromatic group, a C4-C30 alkyl group, a C4-C30 cycloalkyl group, a C4-C30 hydroxylalkyl group, a C4-C30 alkoxy group, a C4-C30 alkoxyl alkyl group, a C4-C30 acetyl group, a C4-C30 acetylalkyl group, a C4-C30 alkyl carboxyl group, a C4-C30 cycloalkyl carboxyl group, a C4-C30 saturated or unsaturated hydrocarbon ring, or a C4-C30 heterocyclic group, wherein A1 and A2 are not both direct bonds, wherein A1 and A2 are unsubstituted or substituted with a halogen, carbonyl group, or hydroxyl group;
wherein at least one of A1 and A2 is an adamantyl group, a norbornyl group, a phenol group, a hydroxynaphthalene group, a hydroxyanthracene group, a phenyl group, or a naphthalenyl group;
A3 is a C6-C14 aromatic group;
R1 is an acid labile group;
Ra and Rb are independently H or a C1-C3 alkyl group;
Rf is a perfluorinated C1-C5 group;
PAG is a photoacid generator; and
0<x/(x+y+z)<1, 0<y/(x+y+z)<1, and 0<z/(x+y+z)<1;
a metal oxide nanoparticle: and
one or more organic ligands.

### Claim 18 (depends on 17)

The photoresist composition of claim 17, wherein at least one of A1, A2, and A3 is unsubstituted or substituted with a halogen, carbonyl group, or hydroxyl group.

### Claim 19 (depends on 17)

The photoresist composition of claim 17, wherein the polymer has a weight average molecular weight ranging from 2,000 to 250,000.

### Claim 20 (depends on 17)

The photoresist composition of claim 17, wherein A3 is a phenol group, a hydroxynaphthalene group, or a hydroxyanthracene group.