# US 12,222,654 B2 · Lithography method for positive tone development

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- Number: US 12,222,654 B2
- Document ID: US12222654B2
- Status: Granted
- Kind: B2
- Application number: 17/378,507
- Filed: 2021-07-16
- Published: 2021-11-04
- Granted: 2025-02-11
- Earliest claimed: 2018-11-21
- Assignees: Taiwan Semiconductor Manufacturing Company, Ltd.
- Applicants: Taiwan Semiconductor Manufacturing Co., Ltd.
- Inventors: Ming-Hui Weng; Chen-Yu Liu; Cheng-Han Wu; Ching-Yu Chang; Chin-Hsiang Lin
- Web page: https://patentgrep.com/patent/US12222654B2

## CPC

- G03F 7/40: Treatment after imagewise removal, e.g. baking
- G03F 1/82: Auxiliary processes, e.g. cleaning or inspecting
- G03F 7/30: Imagewise removal using liquid means
- G03F 7/322: {Aqueous alkaline compositions}
- G03F 7/38: Treatment before imagewise removal, e.g. prebaking {(G03F7/265 takes precedence)}
- G03F 7/70925: {Cleaning, i.e. actively freeing apparatus from pollutants, e.g. using plasma cleaning}
- 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 includes illuminating radiation to a resist layer over a substrate to pattern the resist layer. The patterned resist layer is developed by using a positive tone developer. The patterned resist layer is rinsed using a basic aqueous rinse solution. A pH value of the basic aqueous rinse solution is lower than a pH value of the developer, and a rinse temperature of rinsing the patterned resist layer is in a range of about 20° C. to about 40° C.

## Claims

### Claim 1

A method comprising:
illuminating radiation to a resist layer over a substrate to pattern the resist layer;
developing the patterned resist layer using a positive tone developer;
providing a basic aqueous developing solution during developing the patterned resist layer, wherein a pH value of the basic aqueous developing solution is different from a pH value of the positive tone developer; and
rinsing the patterned resist layer by using a basic aqueous rinse solution, wherein a pH value of the basic aqueous rinse solution is lower than a pH value of the positive tone developer, and a rinse temperature of rinsing the patterned resist layer is in a range of about 20° C. to about 40° C.

### Claim 2 (depends on 1)

The method of claim 1, wherein the basic aqueous rinse solution comprises a base comprising ammonia, methylamine, dimethylamine, trimethylamine, pyridine, imidazole, pyrrole, 4-methylimidazole, pyrazole, pyrazoline, pyrazolidine, methylethylamine, oxazole, thiazole, or combinations thereof.

### Claim 3 (depends on 1)

The method of claim 1, wherein the pH value of the basic aqueous rinse solution is in a range of about 8 to about 12.

### Claim 4 (depends on 1)

The method of claim 1, wherein a base concentration of the basic aqueous rinse solution is in a range of about 0.2 ppm to about 300 ppm.

### Claim 5 (depends on 1)

The method of claim 1, wherein the basic aqueous developing solution comprises a base the same as a base of the basic aqueous rinse solution.

### Claim 6 (depends on 1)

The method of claim 1, wherein a base concentration of the basic aqueous developing solution is lower than a base concentration of the positive tone developer.

### Claim 7 (depends on 1)

The method of claim 1, further comprising:
after rinsing the patterned resist layer, performing a spin drying process to substantially remove the basic aqueous rinse solution.

### Claim 8

A method comprising:
forming a resist layer over a substrate;
exposing the resist layer to radiation;
providing a basic aqueous wetting solution to the resist layer after exposing the resist layer to radiation, wherein a pH value of the basic aqueous wetting solution is greater than 7.5; and
developing the resist layer by using a developer after providing the basic aqueous wetting solution to the resist layer, wherein the pH value of the basic aqueous wetting solution is different from a pH value of the developer.

### Claim 9 (depends on 8)

The method of claim 8, wherein the basic aqueous wetting solution comprises a base comprising ammonia, methylamine, dimethylamine, trimethylamine, pyridine, imidazole, pyrrole, 4-methylimidazole, pyrazole, pyrazoline, pyrazolidine, methylethylamine, oxazole, thiazole, or combinations thereof.

### Claim 10 (depends on 8)

The method of claim 8, wherein the basic aqueous wetting solution is free of tetramethylammonium hydroxide.

### Claim 11 (depends on 8)

The method of claim 8, wherein a base concentration of the basic aqueous wetting solution is in a range of about 0.2 ppm to about 300 ppm.

### Claim 12 (depends on 8)

The method of claim 8, further comprising after developing the resist layer, rinsing the resist layer using a basic aqueous rinse solution.

### Claim 13 (depends on 12)

The method of claim 12, wherein the basic aqueous rinse solution comprises a base the same as a base of the basic aqueous wetting solution.

### Claim 14 (depends on 12)

The method of claim 12, wherein a base concentration of the basic aqueous rinse solution is in a range of about 0.2 ppm to about 300 ppm.

### Claim 15 (depends on 8)

The method of claim 8, wherein the pH value of the basic aqueous wetting solution is in a range from 7.5 to 12.

### Claim 16

A method comprising:
illuminating a patterned EUV radiation to a resist layer over a substrate;
developing the resist layer with a developer, wherein the developer comprises a first basic aqueous solution and a second basic aqueous solution having a pH value lower than the first basic aqueous solution, and a base concentration of the second basic aqueous solution is lower than a base concentration of the first basic aqueous solution, the base concentration of the second basic aqueous solution is in a range of about 0.2 ppm to about 300 ppm; and
rinsing the resist layer.

### Claim 17 (depends on 16)

The method of claim 16, wherein the first basic aqueous solution is tetramethylammonium hydroxide.

### Claim 18 (depends on 16)

The method of claim 16, wherein the second basic aqueous solution comprises a base comprising ammonia, methylamine, dimethylamine, trimethylamine, pyridine, imidazole, pyrrole, 4-methylimidazole, pyrazole, pyrazoline, pyrazolidine, methylethylamine, oxazole, thiazole, or combinations thereof.

### Claim 19 (depends on 16)

The method of claim 16, wherein rinsing the resist layer comprises providing a basic aqueous rinse solution on the resist layer.

### Claim 20 (depends on 19)

The method of claim 19, wherein the basic aqueous rinse solution comprises a base the same as a base of the second basic aqueous solution of the developer.