# US 12,601,975 B2 · Compositions for reducing resist consumption of extreme ultraviolet metallic type resist

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- Number: US 12,601,975 B2
- Document ID: US12601975B2
- Status: Granted
- Kind: B2
- Application number: 17/713,823
- Filed: 2022-04-05
- Published: 2022-12-22
- Granted: 2026-04-14
- Earliest claimed: 2021-06-17
- Assignees: Taiwan Semiconductor Manufacturing Company, Ltd.
- Applicants: Taiwan Semiconductor Manufacturing Co., Ltd.
- Inventors: An-Ren Zi; Ming-Hui Weng; Ching-Yu Chang
- Web page: https://patentgrep.com/patent/US12601975B2

## CPC

- G03F 7/36: Imagewise removal not covered by groups G03F7/30 - G03F7/34, e.g. using gas streams, using plasma
- 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 7/11: having cover layers or intermediate layers, e.g. subbing layers {(G03F7/091 - G03F7/093, B41N3/03 take precedence)}
- G03F 7/162: {Coating on a rotating support, e.g. using a whirler or a spinner}
- H10P 50/73: {using masks for insulating materials}
- H10P 76/20: of masks comprising organic materials
- H10P 76/2043: {using an anti-reflective coating}
- H10P 76/4085: {characterised by the processes involved to create the masks}
- 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 for reducing resist consumption (RRC) is provided. The method includes treating a surface of a substrate using a RRC composition and forming a photoresist layer comprising a metal-containing material on the RRC composition treated surface. The RRC composition includes a solvent and an acid or a base. The solvent has a dispersion parameter between 10 and 25. The acid has an acid dissociation constant between −20 and 6.8. The base having an acid dissociation constant between 7.2 and 45.

## Claims

### Claim 1

A method for reducing resist consumption (RRC), comprising:
treating a surface of a substrate using a RRC composition; and
forming a photoresist layer comprising a metal-containing material on the RRC composition treated surface,
wherein the RRC composition comprises:
a first solvent having a dispersion parameter between 10 and 25; and
an acid having an acid dissociation constant between −20 and 6.8, or a base having an acid dissociation constant between 7.2 and 45; and
wherein the RRC composition further comprises a chelating agent.

### Claim 2 (depends on 1)

The method of claim 1, wherein the first solvent comprises propylene glycol methyl ether (PGME), propylene glycol ethyl ether (PGEE), γ-butyrolactone, cyclohexanone, ethyl lactate, methyl isobutyl carbinol, propylene glycol monomethyl ether acetate, methanol, ethanol, propanol, n-butanol, acetone, dimethylfuran, acetonitrile, isopropyl alcohol, tetrahydrofuran, acetic acid, diacetone alcohol or combinations thereof.

### Claim 3 (depends on 1)

The method of claim 1, wherein the first solvent has a polarity parameter between 3 and 25 and a hydrogen bonding parameter between 4 and 30.

### Claim 4 (depends on 3)

The method of claim 3, wherein a concentration of the acid or base ranges from 0.1 wt. % to 20 wt. % based on a total weight of the RRC composition.

### Claim 5 (depends on 1)

The method of claim 1, wherein the acid is an organic acid comprising ethanedioic acid, methanoic acid, 2-hydroxypropanoic acid, 2-hydroxybutanedioic acid, citric acid, uric acid, trifluoromethanesulfonic acid, benzenesulfonic acid, ethanesulfonic acid, methanesulfonic acid, acetic acid, maleic acid or combinations thereof, or an inorganic acid including, but not limited to, nitric acid (HNO3), sulfuric acid (H2SO4), hydrochloric acid (HCl), hydrobromic acid (HBr), phosphoric acid (H3PO4) or combinations thereof.

### Claim 6 (depends on 1)

The method of claim 1, wherein the base is an organic base comprising monoethanolamine, monoisopropanolamine, 2-amino-2-methyl-1-propanol, 1H-benzotriazole, 1,2,4-triazole, 1,8-diazabicycloundec-7-ene, 1,5-diazabicyclo[4.3.0]non-5-ene or combinations thereof, or an inorganic base comprising ammonia (NH3), ammonium hydroxide, ammonium sulfamate, ammonium carbamate, sodium hydroxide (NaOH), potassium hydroxide (KOH) or combinations thereof.

### Claim 7 (depends on 1)

The method of claim 1, wherein the chelating agent comprises 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, ethylenediamine or combinations thereof.

### Claim 8 (depends on 1)

The method of claim 1, wherein the RRC composition further comprises a surfactant.

### Claim 9 (depends on 1)

The method of claim 1, wherein the RRC composition further comprises a second solvent having a boiling point greater than 150° C.

### Claim 10 (depends on 1)

The method of claim 1, wherein the RRC composition further comprises an aqueous solvent.

### Claim 11 (depends on 1)

The method of claim 1, wherein the RRC composition further comprises water.

### Claim 12

A method for forming a semiconductor structure, comprising:
depositing a material layer over a substrate;
forming a layer of a reducing resist consumption (RRC) composition on the material layer;
forming a photoresist layer comprising a metal-containing material on the RRC composition layer;
patterning the photoresist layer to form a patterned photoresist layer; and
etching the material layer using the patterned photoresist layer as an etch mask,
wherein the RRC composition comprises:
a solvent having the following Hansen solubility parameters:
a dispersion parameter between 10 and 25,
a polarity parameter between 3 and 25, and
a hydrogen bonding parameter between 4 and 30; and
an acid having an acid dissociation constant between −20 and 6.8, or a base having an acid dissociation constant between 7.2 and 45; and
wherein the RRC composition further comprises a chelating agent.

### Claim 13 (depends on 12)

The method of claim 12, wherein the solvent comprises propylene glycol methyl ether (PGME), propylene glycol ethyl ether (PGEE), γ-butyrolactone, cyclohexanone, ethyl lactate, methyl isobutyl carbinol, propylene glycol monomethyl ether acetate, methanol, ethanol, propanol, n-butanol, acetone, dimethylfuran, acetonitrile, isopropyl alcohol, tetrahydrofuran, acetic acid, diacetone alcohol or combinations thereof.

### Claim 14 (depends on 12)

The method of claim 12, wherein the acid is an organic acid comprising ethanedioic acid, methanoic acid, 2-hydroxypropanoic acid, 2-hydroxybutanedioic acid, citric acid, uric acid, trifluoromethanesulfonic acid, benzenesulfonic acid, ethanesulfonic acid, methanesulfonic acid, acetic acid, maleic acid or combinations thereof, or an aqueous acid comprising H2SO4, HNO3, HCl, H3PO4, CCl3COOH, HBr or combinations thereof.

### Claim 15 (depends on 12)

The method of claim 12, wherein the base is an organic base comprising monoethanolamine, monoisopropanolamine, 2-amino-2-methyl-1-propanol, 1H-benzotriazole, 1,2,4-triazole, 1,8-diazabicycloundec-7-ene, 1,5-diazabicyclo[4.3.0]non-5-ene or combinations thereof, or an aqueous base comprising NaOH, NH3, KOH, TMAH, TEAH or combinations thereof.

### Claim 16 (depends on 12)

The method of claim 12, wherein patterning the photoresist layer comprises:
exposing the photoresist layer to an extreme ultraviolet (EUV) radiation; and
developing the exposed photoresist layer.

### Claim 17

A method for forming a semiconductor structure, comprising:
depositing a material layer over a substrate;
forming a layer of a reducing resist consumption (RRC) composition on the material layer;
forming a photoresist layer comprising a metal-containing material on the RRC composition layer;
exposing the photoresist layer to an extreme ultraviolet (EUV) radiation to form a patterned photoresist layer; and
etching the material layer using the patterned photoresist layer as an etch mask,
wherein the RRC composition comprises:
a first solvent having a hydrogen bonding parameter between 4 and 30;
an acid having an acid dissociation constant between −20 and 6.8 or a base having an acid dissociation constant between 7.2 and 45;
a chelating agent;
a surfactant;
a second solvent having a boiling point greater than 150° C.; and
an aqueous solvent; or water.

### Claim 18 (depends on 17)

The method of claim 17, wherein the first solvent comprises propylene glycol methyl ether (PGME), propylene glycol ethyl ether (PGEE), γ-butyrolactone, cyclohexanone, ethyl lactate, methyl isobutyl carbinol, propylene glycol monomethyl ether acetate, methanol, ethanol, propanol, n-butanol, acetone, dimethylfuran, acetonitrile, isopropyl alcohol, tetrahydrofuran, acetic acid, diacetone alcohol or combinations thereof.

### Claim 19 (depends on 17)

The method of claim 17, wherein the second solvent comprises cyclohexyl acetate (CHAX), dipropylene glycol dimethyl ether (DPDME), propylene glycol diacetate (PGDA), dipropylene glycol methyl n-propyl ether (DPMNP), dipropylene glycol methyl ether acetate (DPMA), 1,4-butanediol diacrylate (1,4-BDDA), 1,3-butanediol diacetate (1,3-BGDA), 1,6-hexanediol diacrylate (1,6-HDDA), tripropylene glycol monomethyl ether (TPM), 1,3-propanediol, propylene glycol, 1-methoxy-2-(2-propoxypropoxy)propane, hexane-1,6-diyl diacetate, butane-1,4-diyl diacetate, propane-1,2-diyl diacetate, 2-methoxy-1-((1-methoxypropan-2-yl)oxy)propane, 1-((1-methoxypropan-2-yl)oxy)propan-2-yl acetate, butane-1,2,4-triol, 2-(2-(2-methoxypropoxy)propoxy)propan-1-ol, and combinations thereof.

### Claim 20 (depends on 1)

The method of claim 1, wherein a concentration of the chelating agent ranges from 0.001 wt. % to 30 wt. % based on a total weight of the RRC composition.