# US 11,441,109 B2 · Cleaning solution for removing dry etching residue and method for manufacturing semiconductor substrate using same

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- Number: US 11,441,109 B2
- Document ID: US11441109B2
- Status: Granted
- Kind: B2
- Application number: 16/980,287
- Filed: 2019-03-05
- Published: 2021-02-18
- Granted: 2022-09-13
- Earliest claimed: 2018-03-14
- Assignees: Mitsubishi Gas Chemical Company, Inc.
- Applicants: Mitsubishi Gas Chemical Company, Inc.
- Inventors: Takahiro Kikunaga; Hiroaki Horie; Kimihiro Aoyama; Nobuo Tajima
- Web page: https://patentgrep.com/patent/US11441109B2

## CPC

- C11D 17/08: Liquid soap, {e.g. for dispensers}; capsuled
- C11D 7/26: containing oxygen
- C11D 7/32: containing nitrogen
- C11D 7/3209: {Amines or imines with one to four nitrogen atoms; Quaternized amines}
- C11D 7/3218: {Alkanolamines or alkanolimines}
- C11D 7/50: Solvents
- C11D 7/5022: {containing oxygen}
- H10D 64/011: {of electrodes ohmically coupled to a semiconductor}
- H10P 14/69391: {the material containing aluminium, e.g. Al2O3}
- H10P 50/269: {pre- or post-treatments, e.g. anti-corrosion processes}
- H10P 70/23: {during, before or after processing of insulating materials}
- H10P 70/273: {the processing being a delineation of conductive layers, e.g. by RIE}
- H10W 20/01: {Manufacture or treatment}
- C11D 2111/22: Electronic devices, e.g. PCBs or semiconductors
- C11D: DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- H10D: INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
- H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
- H10W: GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10

## Abstract

The present invention can provide a cleaning solution containing 0.2-20 mass % of an amine compound (A), 40-70 mass % of a water-soluble organic solvent (B), and water, wherein the amine compound (A) contains at least one selected from the group consisting of n-butylamine, hexylamine, octylamine, 1,4-butanediamine, dibutylamine, 3-amino-1-propanol, N,N-diethyl-1,3-diaminopropane, and bis(hexamethylene)triamine, and the water-soluble organic solvent (B) has a viscosity of 10 mPa·s or less at 20° C. and a pH of 9.0-14.

## Claims

### Claim 1

A cleaning solution, comprising:
water:
an amine compound in a range of from 0.2 to 4.0 mass %; and
a water-soluble organic solvent in a range of from 40 to 70 mass %,
wherein the amine compound comprises at least one amine compound selected from the group consisting of n-butylamine, hexylamine, octylamine, 1,4-butanediamine, dibutylamine, N,N diethyl-1,3-diaminopropane and bis(hexamethylene)triamine, the water-soluble organic solvent has a viscosity of 10 mPa·s or less at 20° C., and pH of the cleaning solution is in a range of from 9.0 to 14.

### Claim 2 (depends on 1)

The cleaning solution according to claim 1, wherein a content of the amine compound is in a range of from 0.5 to 4.0 mass %.

### Claim 3 (depends on 1)

The cleaning solution according to claim 1, wherein a content of water is in a range of from 28 to 59 mass %.

### Claim 4 (depends on 1)

The cleaning solution according to claim 1, wherein the water-soluble organic solvent comprises at least one solvent selected from the group consisting of diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, dipropylene glycol monomethyl ether and N,N-dimethyl isobutylamide.

### Claim 5 (depends on 1)

The cleaning solution according to claim 1, wherein the amine compound comprises at least one of N,N-diethyl-1,3-diaminopropane and bis(hexamethylene)triamine.

### Claim 6 (depends on 1)

The cleaning solution according to claim 1, wherein the cleaning solution is suitable for removing dry etching residue.

### Claim 7 (depends on 1)

A method for manufacturing a semiconductor substrate, comprising:
cleaning a cobalt-containing semiconductor substrate with the cleaning solution of claim 1.

### Claim 8 (depends on 7)

The method according to claim 7, wherein the cobalt-containing semiconductor substrate comprises a cobalt-containing metal wiring layer, an interlayer dielectric film and a dry etching-stopper layer containing aluminum oxide.

### Claim 9

A method for manufacturing a semiconductor substrate, comprising:
cleaning a cobalt-containing semiconductor substrate with a cleaning solution,
wherein the cobalt-containing semiconductor substrate comprises a cobalt-containing metal wiring layer, an interlayer dielectric film and a dry etching-stopper layer containing aluminum oxide, the cleaning solution comprises water, an amine compound in a range of from 0.2 to 20 mass %, and a water-soluble organic solvent in a range of from 40 to 70 mass %, and the amine compound in the cleaning solution comprises at least one amine compound selected from the group consisting of n-butylamine, hexylamine, octylamine, 1,4-butanediamine, dibutylamine, 3-amino-1-propanol, N,N-diethyl-1,3-diaminopropane and bis(hexamethylene)triamine, the water-soluble organic solvent in the cleaning solution has a viscosity of 10 mPa·s or less at 20° C., and pH of the cleaning solution is in a range of from 9.0 to 14.

### Claim 10 (depends on 2)

The cleaning solution according to claim 2, wherein a content of water is in a range of from 28 to 59 mass %.

### Claim 11 (depends on 2)

The cleaning solution according to claim 2, wherein the water-soluble organic solvent comprises at least one solvent selected from the group consisting of diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, dipropylene glycol monomethyl ether and N,N-dimethyl isobutylamide.

### Claim 12 (depends on 2)

The cleaning solution according to claim 2, wherein the amine compound comprises at least one of N,N-diethyl-1,3-diaminopropane and bis(hexamethylene)triamine.

### Claim 13 (depends on 3)

The cleaning solution according to claim 3, wherein the water-soluble organic solvent comprises at least one solvent selected from the group consisting of diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, dipropylene glycol monomethyl ether and N,N-dimethyl isobutylamide.

### Claim 14 (depends on 3)

The cleaning solution according to claim 3, wherein the amine compound comprises at least one of N,N-diethyl-1,3-diaminopropane and bis(hexamethylene)triamine.

### Claim 15 (depends on 4)

The cleaning solution according to claim 4, wherein the amine compound comprises at least one of N,N-diethyl-1,3-diaminopropane and bis(hexamethylene)triamine.

### Claim 16 (depends on 1)

The cleaning solution according to claim 1, wherein a content of the water-soluble organic solvent is in a range of from 45 to 65 mass %.

### Claim 17 (depends on 1)

The cleaning solution according to claim 1, wherein a content of water is in a range of from 34 to 54 mass %.

### Claim 18 (depends on 1)

The cleaning solution according to claim 1, wherein the pH of the cleaning solution is in a range of from 11 to 13.

### Claim 19 (depends on 13)

The cleaning solution according to claim 13, wherein the amine compound comprises at least one of N,N-diethyl-1,3-diaminopropane and bis(hexamethylene)triamine.

### Claim 20 (depends on 9)

The method according to claim 9, wherein a content of water is in a range of from 28 to 59 mass %, and the water-soluble organic solvent comprises at least one solvent selected from the group consisting of diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, dipropylene glycol monomethyl ether and N,N-dimethyl isobutylamide.