# US 12,181,798 B2 · Extreme ultraviolet photolithography method with developer composition

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- Number: US 12,181,798 B2
- Document ID: US12181798B2
- Status: Granted
- Kind: B2
- Application number: 18/446,702
- Filed: 2023-08-09
- Published: 2024-02-08
- Granted: 2024-12-31
- Earliest claimed: 2016-12-15
- Assignees: Taiwain Semiconductor Manufacturing Company, Ltd.
- Applicants: Taiwan Semiconductor Manufacturing Co., Ltd.
- Inventors: An-Ren Zi; Joy Cheng; Ching-Yu Chang; Chin-Hsiang Lin
- Web page: https://patentgrep.com/patent/US12181798B2

## CPC

- G03F 7/0042: {with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists (G03F7/075 takes precedence)}
- G03F 7/0047: {characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing}
- G03F 7/32: Liquid compositions therefor, e.g. developers
- G03F 7/325: {Non-aqueous compositions}
- G03F 7/30: Imagewise removal using liquid means
- G03F 7/36: Imagewise removal not covered by groups G03F7/30 - G03F7/34, e.g. using gas streams, using plasma
- 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

The present disclosure provides a method for lithography patterning in accordance with some embodiments. The method includes forming a photoresist layer over a substrate, wherein the photoresist layer includes a metal-containing chemical; performing an exposing process to the photoresist layer; and performing a first developing process to the photoresist layer using a first developer, thereby forming a patterned resist layer, wherein the first developer includes a first solvent and a chemical additive to remove metal residuals generated from the metal-containing chemical.

## Claims

### Claim 1

A method comprising:
forming a material layer on a substrate;
forming a photoresist layer directly on the material layer disposed on the substrate, wherein a composition of the photoresist layer includes a metal-containing chemical;
performing an exposing process to the photoresist layer;
prior to performing any etching of the material layer, performing a first developing process to the photoresist layer using a first developer to pattern the photoresist layer, wherein the first developer removes metal residuals generated from the metal-containing chemical, wherein the performing of the first developing process includes heating the first developer to a first temperature; and
after the performing of the first developing process, performing an ion implantation process on the material layer while using the patterned photoresist layer as a mask.

### Claim 2 (depends on 1)

The method of claim 1, further comprising performing a second developing process to the photoresist layer using a second developer to pattern the photoresist layer, wherein the second developer has a different material composition than the first developer.

### Claim 3 (depends on 2)

The method of claim 2, wherein the performing of the first developing process occurs prior to the performing of the second developing process.

### Claim 4 (depends on 2)

The method of claim 2, wherein the performing of the second developing process occurs prior to the performing of the first developing process.

### Claim 5 (depends on 2)

The method of claim 2, wherein the performing of the second developing process to the photoresist layer using the second developer to pattern the photoresist layer occurs without heating the second developer to the first temperature.

### Claim 6 (depends on 1)

The method of claim 1, wherein the first temperature is in a range greater than room temperature and less than 75° C.

### Claim 7 (depends on 1)

The method of claim 1, wherein the metal-containing chemical is selected from the group consisting of barium (Ba), indium (In), cerium (Ce), tin (Sn) and antimony (Sb).

### Claim 8 (depends on 1)

The method of claim 1, wherein the photoresist layer further includes a polymer, an acid liable group, a photoacid generator and a solvent.

### Claim 9

A method comprising
forming a material layer on a substrate;
forming a photoresist layer on the material layer, wherein a composition of the photoresist layer includes a metal-containing component;
performing an exposing process to the photoresist layer;
prior to etching the material layer, performing a first developing process to the photoresist layer using a first developer, the first developer including a first solvent and a chemical additive; and
performing a second developing process to the photoresist layer using a second developer that has a different material composition than the first developer, wherein the second developer is free of the chemical additive, wherein the performing of the first and second developing processes on the photoresist layer forms a patterned photoresist layer.

### Claim 10 (depends on 9)

The method of claim 9, wherein the chemical additive is selected from the group consisting of an organic acid, an organic base and a chelate.

### Claim 11 (depends on 10)

The method of claim 10, wherein the organic acid is selected from the group consisting of ethanedioic acid, methanoic acid, 2-hydroxypropanoic acid, 2-hydroxybutanedioic acid, Citric acid, Uric acid, Trifluoromethanesulfonic acid, Benzenesulfonic acid, ethanesulfonic acid, methanesulfonic acid, Oxalic acid dihydrate, and Maleic acid,
wherein the organic base is selected from the group consisting of Monoethanolamine, Monoisopropanolamine, 2-Amino-2-methyl-1-propanol, 1H-Benzotriazole, 1,2,4-Triazole, and 1,8-Diazabicycloundec-7-ene,
wherein the chelate is selected from the group consisting of Ethylenediaminetetraacetic acid (EDTA), Ethylenediamine-N,N′-disuccinic acid (EDDS), diethylenetriaminepentaacetic acid (DTPA), Polyaspartic acid, trans-1,2-Cyclohexanediamine-N,N,N′,N′-tetraacetic acid monohydrate, and ethylenediamine.

### Claim 12 (depends on 9)

The method of claim 9, further comprising etching the material layer while using the patterned photoresist layer as a mask after performing the first and second developing processes.

### Claim 13 (depends on 9)

The method of claim 9, further comprising performing an ion implantation process on the material layer while using the patterned photoresist layer as a mask after performing the first and second developing processes.

### Claim 14 (depends on 9)

The method of claim 9, wherein the first solvent has Hansen solubility parameters of delta D in a range between 3 and 18, delta P in a range between 1 and 7, and delta H in a range between 1 and 7, and
wherein the second developer includes a second solvent having Hansen solubility parameters of delta D in a range between 13 and 25, delta P in a range between 3 and 25, and delta H in a range between 4 and 30.

### Claim 15 (depends on 9)

The method of claim 9, wherein the material layer includes a conductive material layer.

### Claim 16

A method comprising:
forming a material layer on a substrate;
forming a photoresist layer on the material layer, wherein a composition of the photoresist layer includes a metal-containing component;
performing an exposing process to the photoresist layer; and
prior to performing any etching of the material layer, performing a development process on the photoresist layer that includes:
applying a first developer having a first temperature to the photoresist layer; and
applying a second developer having a second temperature to the photoresist layer, wherein the applying of the first and second developers forms a patterned photoresist layer that exposes a portion of the material layer, wherein the second developer has a different material composition than the first developer, wherein the second temperature is different than the first temperature.

### Claim 17 (depends on 16)

The method of claim 16, wherein the first developer includes a chemical additive selected from the group consisting of an organic acid, an organic base and a chelate, and
wherein the second developer is free of the selected chemical additive.

### Claim 18 (depends on 16)

The method of claim 16, wherein the second temperature is room temperature.

### Claim 19 (depends on 16)

The method of claim 16, further comprising performing a thermal treatment process on the photoresist layer after the performing of the exposing process such that the photoresist layer undergoes a chemical change.

### Claim 20 (depends on 16)

The method of claim 16, further comprising performing an ion implantation process on the exposed portion of the material layer while using the patterned photoresist layer as a mask.