# US 10,768,527 B2 · Resist solvents for photolithography applications

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- Number: US 10,768,527 B2
- Document ID: US10768527B2
- Status: Granted
- Kind: B2
- Application number: 16/102,429
- Filed: 2018-08-13
- Published: 2020-02-13
- Granted: 2020-09-08
- Earliest claimed: 2018-08-13
- Assignees: Taiwan Semiconductor Manufacturing Company, Ltd.
- Applicants: Taiwan Semiconductor Manufacturing Co., Ltd.
- Inventors: Yu-Chung Su; Kuan-Hsin Lo; Yahru Cheng; Ching-Yu Chang; Chin-Hsiang Lin
- Web page: https://patentgrep.com/patent/US10768527B2

## CPC

- G03F 7/0048: {characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents}
- G03F 7/162: {Coating on a rotating support, e.g. using a whirler or a spinner}
- G03F 7/0392: {the macromolecular compound being present in a chemically amplified positive photoresist composition}
- G03F 7/091: {characterised by antireflection means or light filtering or absorbing means, e.g. anti-halation, contrast enhancement}
- G03F 7/70033: {by plasma extreme ultraviolet [EUV] sources}
- H10P 76/2043: {using an anti-reflective coating}
- 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

## Abstract

A method includes providing a photoresist solution that includes a first solvent having a first volume and a second solvent having a second volume, where the first solvent is different from the second solvent and where the first volume is less than the second volume; dispersing the photoresist solution over a substrate to form a film, where the dispersing evaporates a portion of the first solvent and a portion of the second solvent such that a remaining portion of the first solvent is greater than a remaining portion of the second solvent; baking the film; after baking the film, exposing the film to form an exposed film; and developing the exposed film.

## Claims

### Claim 1

A method, comprising:
providing a photoresist solution, wherein the photoresist solution includes a first solvent having a first volume and a second solvent having a second volume, wherein the first solvent and the second solvent differ in composition, and wherein the first volume is less than the second volume;
dispersing the photoresist solution over a substrate to form a film, wherein the dispersing evaporates a portion of the first solvent and a portion of the second solvent such that a remaining portion of the first solvent is greater than a remaining portion of the second solvent;
baking the film;
after baking the film, exposing the film, resulting in an exposed film; and
developing the exposed film.

### Claim 2 (depends on 1)

The method of claim 1, wherein the first solvent includes diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, dimethyl sulfoxide, ethylene glycol, glycerin, hexamethylphosphoramide, N-methyl-2-pyrrolidinone, benzonitrile, 1,2-dichlorobenzene, N,N dimethylacetamide, 2-ethoxyethyl ether, gamma-butyrolactone, 1,6-di-acetoxyhexane, tri(propylene glycol) methyl ether, propylene carbonate, tetra(ethylene glycol) monomethyl ether, or combinations thereof.

### Claim 3 (depends on 2)

The method of claim 2, wherein the second solvent includes propylene glycol methyl ether, propylene glycol monomethyl ether acetate, or combinations thereof.

### Claim 4 (depends on 1)

The method of claim 1, wherein the photoresist solution further includes a polymer, a photoacid generator (PAG), and a quencher.

### Claim 5 (depends on 4)

The method of claim 4, wherein a relative energy difference between the first solvent and each of the polymer, the PAG, and the quencher is less than 1.

### Claim 6 (depends on 1)

The method of claim 1, wherein the exposing of the film includes applying an extreme ultraviolet (EUV) source.

### Claim 7 (depends on 1)

The method of claim 1, wherein the baking of the film is implemented in a first baking process at a first temperature, further comprising baking the film in a second baking process at a second temperature after the exposing of the film, the first temperature and the second temperature being less than a boiling point of the first solvent.

### Claim 8 (depends on 7)

The method of claim 7, wherein the second temperature is lower than the first temperature.

### Claim 9

A method, comprising:
dispersing a resist layer on a substrate, wherein the resist layer includes a photosensitive unit, a first solvent having a first boiling point, and a second solvent having a second boiling point, the first boiling point being less than the second boiling point;
after dispersing the resist layer, performing a first heat treatment to the resist layer, wherein the first heat treatment is performed at a first temperature, and wherein the first temperature is greater than the first boiling point but lower than the second boiling point;
after performing the first heat treatment, exposing the resist layer to extreme ultraviolet (EUV) radiation;
performing a second heat treatment to the exposed resist layer, wherein the second heat treatment is performed at a second temperature; and
developing the exposed resist layer to form a patterned resist layer.

### Claim 10 (depends on 9)

The method of claim 9, the resist layer having a first thickness after the dispersing of the resist layer and before the performing of the first heat treatment, and the resist layer having a second thickness after the performing of the first heat treatment and before the exposing of the resist layer, wherein the second thickness is less than the first thickness.

### Claim 11 (depends on 9)

The method of claim 9, wherein the second temperature is less than the second boiling point.

### Claim 12 (depends on 9)

The method of claim 9, wherein after the dispersing of the resist layer, an amount of the second solvent is greater than an amount of the first solvent.

### Claim 13 (depends on 9)

The method of claim 9, wherein the second solvent includes 1, 6-di-acetoxyhexane, tri(propylene glycol) methyl ether, propylene carbonate, triethylene glycol dimethyl ether, tetra(ethylene glycol) monomethyl ether, or combinations thereof.

### Claim 14 (depends on 13)

The method of claim 13, wherein the first solvent includes propylene glycol methyl ether, propylene glycol monomethyl ether acetate, or combinations thereof.

### Claim 15 (depends on 9)

The method of claim 9, further comprising:
processing the substrate using the patterned resist layer as a mask; and
removing the patterned resist layer, wherein the removing includes applying a resist stripping solution, the resist stripping solution including the second solvent.

### Claim 16

A method, comprising:
providing an extreme ultraviolet (EUV) resist solution, wherein the EUV resist solution includes a first solvent and a second solvent, an amount of the first solvent being greater than an amount of the second solvent;
spin-coating the EUV resist solution over a substrate to form an EUV resist layer, wherein the spin-coating evaporates a portion of the first solvent and a portion of the second solvent such that a remaining amount of the second solvent is greater than a remaining amount of the first solvent;
performing a pre-exposure bake to the EUV resist layer;
after performing a pre-exposure bake to the EUV resist layer, exposing the EUV resist layer, resulting in an exposed EUV resist layer;
performing a post-exposure bake to the exposed EUV resist layer; and
after performing the post-exposure bake, developing the exposed EUV resist layer.

### Claim 17 (depends on 16)

The method of claim 16, the first solvent having a first vapor pressure and the second solvent having a second vapor pressure, wherein the second vapor pressure is lower than the first vapor pressure.

### Claim 18 (depends on 16)

The method of claim 16, wherein a ratio of the amount of the second solvent to the amount of the first solvent before the spin-coating of the EUV resist layer is no more than about 2:3.

### Claim 19 (depends on 16)

The method of claim 16, wherein the second solvent includes diethylene glycol dimethyl ether, hexamethylphosphoramide, N-methyl-2-pyrrolidinone, benzonitrile, 1,2-dichlorobenzene, N,N dimethylacetamide, 2-ethoxyethyl ether, gamma-butyrolactone, or combinations thereof.

### Claim 20 (depends on 16)

The method of claim 16, wherein the performing of the pre-exposure bake evaporates the first solvent completely without evaporating the second solvent completely.