# US 11,029,602 B2 · Photoresist composition and method of forming photoresist pattern

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- Number: US 11,029,602 B2
- Document ID: US11029602B2
- Status: Granted
- Kind: B2
- Application number: 15/994,615
- Filed: 2018-05-31
- Published: 2019-05-16
- Granted: 2021-06-08
- Earliest claimed: 2017-11-14
- Assignees: Taiwan Semiconductor Manufacturing Company, Ltd.
- Applicants: Taiwan Semiconductor Manufacturing Co., Ltd.
- Inventors: An-Ren Zi; Chin-Hsiang Lin; Ching-Yu Chang; Yahru Cheng
- Web page: https://patentgrep.com/patent/US11029602B2

## CPC

- G03F 7/11: having cover layers or intermediate layers, e.g. subbing layers {(G03F7/091 - G03F7/093, B41N3/03 take precedence)}
- 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 7/162: {Coating on a rotating support, e.g. using a whirler or a spinner}
- G03F 7/2002: {with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image}
- 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)

## Abstract

A method of forming a photoresist pattern includes forming a protective layer over a photoresist layer formed on a substrate, and selectively exposing the photoresist layer to actinic radiation. The photoresist layer is developed to form a pattern in the photoresist layer, and the protective layer is removed. The protective layer includes a polymer having fluorocarbon pendant groups.

## Claims

### Claim 1

A method of forming a photoresist pattern, comprising:
forming a protective layer over a photoresist layer formed on a substrate;
selectively exposing the photoresist layer to actinic radiation;
developing the photoresist layer to form a pattern in the photoresist layer; and
removing the protective layer,
wherein the protective layer comprises a polymer having fluorocarbon pendant groups, and
wherein the forming the protective layer over the photoresist layer comprises:
mixing material forming the protective layer and photoresist material to form a mixture;
disposing the mixture over the substrate; and
rotating the substrate with the mixture disposed thereon, wherein the protective layer separates from the mixture during the rotating and forms the protective layer over the photoresist layer.

### Claim 2 (depends on 1)

The method according to claim 1, wherein the photoresist layer includes metal oxide nanoparticles.

### Claim 3 (depends on 1)

The method according to claim 1, wherein the actinic radiation is extreme ultraviolet radiation.

### Claim 4 (depends on 1)

The method according to claim 1, further comprising heating the photoresist layer and protective layer after selectively exposing the photoresist layer.

### Claim 5 (depends on 1)

The method according to claim 1, wherein the protective layer has a thickness ranging from 0.1 nm to 20 nm.

### Claim 6 (depends on 1)

The method according to claim 1, wherein the contact angle of the protective layer to water is greater than 75°.

### Claim 7 (depends on 1)

The method according to claim 1, wherein the protective layer has a thickness ranging from 1 nm to 15 nm.

### Claim 8 (depends on 1)

The method according to claim 1, wherein the fluorocarbon pendant groups are selected from the group consisting of CxFy, where 1≤x≤9 and 3≤y≤12; and —(C(CF3)2OH)—.

### Claim 9

A method of fabricating a semiconductor device, comprising:
supplying a photoresist composition to a substrate surface to form a photoresist layer over the substrate;
forming a protective layer over the photoresist layer;
patternwise exposing the photoresist layer to extreme ultraviolet radiation to form a latent pattern in the photoresist layer;
heating the photoresist layer after the patternwise exposing;
developing the photoresist layer and removing the protective layer substantially simultaneously,
wherein the photoresist layer comprises a metal oxide,
wherein the protective layer comprises a polymer having fluorocarbon pendant groups, and
wherein the supplying the photoresist composition to the substrate surface to form the photoresist layer over the substrate, comprises:
mixing the polymer having fluorocarbon pendant groups with the photoresist composition to form a mixture;
supplying the mixture to the substrate surface; and
the protective layer is formed by spinning the substrate with the mixture disposed thereon, thereby causing the polymer having fluorocarbon pendant groups to separate from the mixture and form the protective layer over the photoresist layer.

### Claim 10 (depends on 9)

The method according to claim 9, wherein the protective layer has a thickness ranging from 1 nm to 15 nm.

### Claim 11 (depends on 9)

The method according to claim 9, wherein a contact angle of the protective layer to water is greater than 75°.

### Claim 12

A method of forming a photoresist pattern, comprising:
forming a layer of a photoresist composition including a polymer having fluorocarbon pendant groups over a substrate,
rotating the substrate with the layer of the photoresist composition disposed thereon to separate the layer of the photoresist composition into a photoresist layer and a layer of the polymer having fluorocarbon pendant groups disposed over the photoresist layer;
patternwise exposing the photoresist layer to actinic radiation; and
developing the photoresist layer to form a pattern in the photoresist layer.

### Claim 13 (depends on 12)

The method according to claim 12, wherein the photoresist composition includes metal oxide nanoparticles.

### Claim 14 (depends on 12)

The method according to claim 12, wherein the actinic radiation is extreme ultraviolet radiation.

### Claim 15 (depends on 12)

The method according to claim 12, further comprising heating the photoresist layer and the layer of the polymer having fluorocarbon pendant groups after selectively exposing the photoresist layer.

### Claim 16 (depends on 12)

The method according to claim 12, wherein the layer of the polymer having fluorocarbon pendant groups has a thickness ranging from 0.1 nm to 20 nm.

### Claim 17 (depends on 12)

The method according to claim 12, wherein the contact angle of the layer of the polymer having fluorocarbon pendant groups to water is greater than 75°.

### Claim 18 (depends on 12)

The method according to claim 12, wherein the polymer having fluorocarbon pendant groups comprises from 0.1 wt. % to 10 wt. % of the fluorocarbon pendant groups based on the total weight of the polymer having fluorocarbon groups.

### Claim 19 (depends on 12)

The method according to claim 12, wherein fluorocarbon pendant groups are selected from the group consisting of CxFy, where 1≤x≤9 and 3≤y≤12; and —(C(CF3)2OH)—.

### Claim 20 (depends on 12)

The method according to claim 12, wherein a contact angle of the layer of the polymer having fluorocarbon pendant groups to water is greater than 75°.