# US 2025/0093779 A1 · Method of manufacturing a semiconductor device

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- Number: US 2025/0093779 A1
- Document ID: US20250093779A1
- Status: Published application
- Kind: A1
- Application number: 18/961,391
- Filed: 2024-11-26
- Published: 2025-03-20
- Earliest claimed: 2021-08-27
- Assignees: Taiwan Semiconductor Manufacturing Company, Ltd.
- Applicants: Taiwan Semiconductor Manufacturing Company, Ltd.
- Inventors: Chieh-Hsin HSIEH; Wei-Han LAI; Ching-Yu CHANG
- Web page: https://patentgrep.com/patent/US20250093779A1

## CPC

- G03F 7/094: {Multilayer resist systems, e.g. planarising layers}
- H10P 50/71: {using masks for conductive or resistive materials}
- G03F 7/0045: {with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors}
- G03F 7/0752: {in non photosensitive layers or as additives, e.g. for dry lithography}
- G03F 7/091: {characterised by antireflection means or light filtering or absorbing means, e.g. anti-halation, contrast enhancement}
- G03F 7/105: having substances, e.g. indicators, for forming visible images
- H10P 50/73: {using masks for insulating materials}
- H10P 76/2043: {using an anti-reflective coating}
- H10D 64/01: Manufacture or treatment
- 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)
- H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
- H10D: INORGANIC ELECTRIC SEMICONDUCTOR DEVICES

## Abstract

A method of manufacturing a semiconductor device includes forming a first layer including an organic material over a substrate. A second layer including a reaction product of a silicon-containing material and a photoacid generator is formed over the first layer. A photosensitive layer is formed over the second layer, and the second layer is patterned.

## Claims

### Claim 1

A method of manufacturing a semiconductor device, comprising:
forming a first layer comprising an organic material over a substrate;
forming a second layer comprising a reaction product of a siloxane and a photoacid generator over the first layer,
forming a photosensitive layer over the second layer; and
patterning the photosensitive layer, and
wherein the reaction product of the siloxane and the photoacid generator comprises a cation having the following structure
where R3 includes I.

### Claim 2 (depends on 1)

The method according to claim 1, wherein R3 further comprises F.

### Claim 3 (depends on 1)

The method according to claim 1, wherein the reaction product of the siloxane and the photoacid generator further comprises
where A is a direct bond, a C1-C5 alkyl group, a C1-C5 cycloalkyl group, a C1-C5 hydroxy alkyl group, a C1-C5 alkoxy group, a C1-C5 alkoxyl alkyl group, a C1-C5 acetyl group, a C1-C5 acetyl alkyl group, a C1-C5 carboxyl group, or a C1-C5 alkyl carboxyl group; R1 and R2 are each independently a C6-C12 aryl group, a C6-C12 alkyl group, a C6-C12 cycloalkyl group, a C6-C12 hydroxy alkyl group, a C6-C12 alkoxy group, a C6-C12 alkoxyl alkyl group, a C6-C12 acetyl group, a C6-C12 acetyl alkyl group, a C6-C12 carboxyl group, a C6-C12 alkyl carboxyl group, a C6-C12 cycloalkyl carboxyl group, a C3-C15 saturated or unsaturated hydrocarbon ring or a C2-C15 heterocyclic group, and a, b, c, and d are each independently H or a C1-C6 alkyl group.

### Claim 4 (depends on 3)

The method of claim 3, wherein at least one of R1 and R2 includes I.

### Claim 5 (depends on 3)

The method of claim 3, wherein R1 and R2 include F and I.

### Claim 6 (depends on 1)

The method according to claim 1, wherein the forming the second layer comprises:
applying a mixture comprising the reaction product of the siloxane and the photoacid generator over the first layer; and
heating the mixture to polymerize or crosslink the reaction product of the photoacid generator and the silicon-containing material after applying the mixture over the first layer.

### Claim 7 (depends on 6)

The method according to claim 6, wherein the mixture is heated at a temperature ranging from 150° C. to 300° C.

### Claim 8

A method of manufacturing a semiconductor device, comprising:
forming a bottom anti-reflective coating layer over a substrate;
forming a middle layer comprising a polysiloxane with pendant photoacid generator groups over the bottom anti-reflective coating layer,
wherein the photoacid generator groups are bonded to a silicon in the polysiloxane through an oxygen;
forming a photosensitive layer over the middle layer;
selectively exposing the photosensitive layer to actinic radiation to form a latent pattern; and
developing the selectively exposed photosensitive layer to form a pattern in the photosensitive layer,
wherein a monomer of the polysiloxane with the pendant photoacid generator groups include a cation having the following structure
where R3 includes I.

### Claim 9 (depends on 8)

The method according to claim 8, wherein the bottom anti-reflective coating layer comprises a polymer selected from the group consisting of poly(4-hydroxystyrene), poly(4-vinylphenol-co-methyl-methacrylate, and poly(styrene)-b-poly(4-hydroxystyrene).

### Claim 10 (depends on 8)

The method according to claim 8, wherein forming the bottom anti-reflective coating layer comprises applying a compound to the substrate.

### Claim 11 (depends on 10)

The method according to claim 10, wherein the compound comprises a polymer consisting of at least one of the following groups:

### Claim 12 (depends on 10)

The method according to claim 10, wherein the compound comprises a polymer consisting of at least one of the following compounds 1-12:

### Claim 13

A method of manufacturing a semiconductor device, comprising:
forming a bottom layer of a trilayer resist over a substrate;
forming a middle layer of a trilayer resist over the bottom layer,
wherein the middle layer comprises a polysiloxane with pendant photoacid generator groups,
wherein the photoacid generator groups are bonded to a silicon in the polysiloxane through an oxygen;
forming a photosensitive layer over the middle layer;
wherein a monomer of the polysiloxane with the pendant photoacid generator groups includes a cation having the following structure
where R3 includes I.

### Claim 14 (depends on 13)

The method according to claim 13, further comprising:
selectively exposing the photosensitive layer and the middle layer to actinic radiation; and
diffusing acid released by the pendant photoacid generator groups in exposed portions of the middle layer into exposed portions of the photosensitive layer.

### Claim 15 (depends on 14)

The method according to claim 14, wherein the diffusing acid released by the pendant photoacid generator groups in exposed portions of the middle layer into exposed portions of the photosensitive layer comprises heating the photosensitive layer and the middle layer at a temperature ranging from 80° C. to 160° C. before the applying the developer.

### Claim 16 (depends on 13)

The method according to claim 13, further comprising
applying a developer composition to the selectively exposed photosensitive layer to form a pattern in the photosensitive layer.

### Claim 17 (depends on 16)

The method according to claim 16, wherein the photosensitive layer comprises a polymer having pendant acid labile groups and a photoacid generator compound.

### Claim 18 (depends on 13)

The method according to claim 13, wherein R3 further comprises F.

### Claim 19 (depends on 13)

The method according to claim 13, wherein the monomer of the polysiloxane with the pendant photoacid generator groups further includes a compound represented by
where A is a direct bond, a C1-C5 alkyl group, a C1-C5 cycloalkyl group, a C1-C5 hydroxy alkyl group, a C1-C5 alkoxy group, a C1-C5 alkoxyl alkyl group, a C1-C5 acetyl group, a C1-C5 acetyl alkyl group, a C1-C5 carboxyl group, or a C1-C5 alkyl carboxyl group; R1 and R2 are each independently a C6-C12 aryl group, a C6-C12 alkyl group, a C6-C12 cycloalkyl group, a C6-C12 hydroxy alkyl group, a C6-C12 alkoxy group, a C6-C12 alkoxyl alkyl group, a C6-C12 acetyl group, a C6-C12 acetyl alkyl group, a C6-C12 carboxyl group, a C6-C12 alkyl carboxyl group, a C6-C12 cycloalkyl carboxyl group, a C3-C15 saturated or unsaturated hydrocarbon ring or a C2-C15 heterocyclic group, and a, b, c, and d are each independently H or a C1-C6 alkyl group.

### Claim 20 (depends on 19)

The method of claim 19, wherein at least one of R1 and R2 includes I.