# US 11,898,123 B2 · Cleaning compositions > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,898,123 B2 - Document ID: US11898123B2 - Status: Granted - Kind: B2 - Application number: 17/458,671 - Filed: 2021-08-27 - Published: 2022-03-03 - Granted: 2024-02-13 - Earliest claimed: 2020-08-27 - Assignees: Fujifilm Electronic Materials U.S.A., Inc. - Applicants: Fujifilm Electronic Materials U.S.A., Inc. - Inventors: Emil A. Kneer; Thomas Dory; Atsushi Mizutani - Web page: https://patentgrep.com/patent/US11898123B2 ## CPC - C11D 3/33: Amino carboxylic acids - C11D 3/0042: {Reducing agents} - C11D 3/0047: {pH regulated compositions} - C11D 3/0073: {Anticorrosion compositions} - C11D 3/28: Heterocyclic compounds containing nitrogen in the ring - C11D 3/3409: {Alkyl -, alkenyl -, cycloalkyl - or terpene sulfates or sulfonates} - C11D 3/43: Solvents - C11D 7/263: {Ethers} - C11D 7/3218: {Alkanolamines or alkanolimines} - C11D 7/3245: {Aminoacids} - C11D 7/3281: {Heterocyclic compounds} - C11D 7/34: containing sulfur - 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 ## Abstract This disclosure relates to a cleaning composition that contains 1) at least one redox agent; 2) at least one chelating agent, the chelating agent being a polyaminopolycarboxylic acid; 3) at least one corrosion inhibitor, the corrosion inhibitor being a substituted or unsubstituted benzotriazole; 4) at least one sulfonic acid; and 5) water. ## Claims ### Claim 1 A cleaning composition, comprising: 1) At least one redox agent; 2) At least one chelating agent, the chelating agent being a polyaminopolycarboxylic acid; 3) At least one corrosion inhibitor, wherein the at least one corrosion inhibitor comprises 5-methyl-1H-benzotriazole; 4) At least one sulfonic acid; and 5) water. ### Claim 2 (depends on 1) The composition of claim 1, wherein the at least one redox agent comprises hydroxylamine. ### Claim 3 (depends on 1) The composition of claim 1, wherein the at least one redox agent is from about 0.1% to about 5% by weight of the composition. ### Claim 4 (depends on 1) The composition of claim 1, wherein the polyaminopolycarboxylic acid is selected from the group consisting of mono- or polyalkylene polyamine polycarboxylic acids, polyaminoalkane polycarboxylic acids, polyaminoalkanol polycarboxylic acids, and hydroxyalkylether polyamine polycarboxylic acids. ### Claim 5 (depends on 4) The composition of claim 4, wherein the polyaminopolycarboxylic acid is diethylenetriamine pentaacetic acid. ### Claim 6 (depends on 1) The composition of claim 1, wherein the polyaminopolycarboxylic acid is from about 0.01% to about 0.5% by weight of the composition. ### Claim 7 (depends on 1) The composition of claim 1, wherein the at least one corrosion inhibitor is from about 0.05% to about 1% by weight of the composition. ### Claim 8 (depends on 1) The composition of claim 1, wherein the at least one sulfonic acid comprising a sulfonic acid of formula (I): R—SO3H (I), in which R is C1-C12 alkyl, C1-C12 cycloalkyl, or aryl, wherein the alkyl, cycloalkyl, or aryl is optionally substituted by at least one substituent selected from the group consisting of halo, OH, NH2, NO2, COOH, C1-C12 cycloalkyl, C1-C12 alkoxy optionally substituted by halo, and aryl optionally substituted by OH. ### Claim 9 (depends on 8) The composition of claim 8, wherein the at least one sulfonic acid comprises methanesulfonic acid. ### Claim 10 (depends on 1) The composition of claim 1, wherein the at least one sulfonic acid is from about 1% to about 10% by weight of the composition. ### Claim 11 (depends on 1) The composition of claim 1, further comprising at least one pH adjusting agent, the pH adjusting agent being a base free of a metal ion. ### Claim 12 (depends on 11) The composition of claim 11, wherein the at least one pH adjusting agent comprises a cyclic amine or an alkanolamine. ### Claim 13 (depends on 11) The composition of claim 11, wherein the at least one pH adjusting agent comprises 1,8-diazabicyclo[5.4.0]undec-7-ene or monoethanolamine. ### Claim 14 (depends on 11) The composition of claim 11, wherein the at least one pH adjusting agent is from about 0.1% to about 3% by weight of the composition. ### Claim 15 (depends on 1) The composition of claim 1, wherein the water is from about 55% to about 98% by weight of the composition. ### Claim 16 (depends on 1) The composition of claim 1, further comprising at least one organic solvent selected from the group consisting of water soluble alcohols, water soluble ketones, water soluble esters, and water soluble ethers. ### Claim 17 (depends on 16) The composition of claim 16, wherein the at least one organic solvent comprises ethylene glycol butyl ether. ### Claim 18 (depends on 16) The composition of claim 16, wherein the at least one organic solvent is from about 0.1% to about 40% by weight of the composition. ### Claim 19 (depends on 1) The composition of claim 1, wherein the composition has a pH of from about 4 to about 7. ### Claim 20 (depends on 1) The composition of claim 1, wherein the composition comprises hydroxylamine, diethylenetriamine pentaacetic acid, 5-methyl-1H-benzotriazole, 1,8-diazabicyclo[5.4.0]undec-7-ene, methanesulfonic acid, and water. ### Claim 21 (depends on 20) The composition of claim 20, wherein the composition comprises: hydroxylamine in an amount of from about 0.1% to about 5% by weight of the composition; diethylenetriamine pentaacetic acid in an amount of from about 0.01% to about 0.5% by weight of the composition; 5-methyl-1H-benzotriazole in an amount of from about 0.05% to about 1% by weight of the composition; methanesulfonic acid in an amount of from about 1% to about 10% by weight of the composition; 1,8-diazabicyclo[5.4.0]undec-7-ene in an amount of from about 0.1% to about 3% by weight of the composition; and water in an amount of from about 75% to about 98% by weight of the composition; wherein the composition has a pH of from about 4 to about 7. ### Claim 22 (depends on 21) The composition of claim 21, wherein the composition comprises: hydroxylamine in an amount of from about 0.5% to about 2% by weight of the composition; diethylenetriamine pentaacetic acid in an amount of from about 0.1% to about 0.5% by weight of the composition; 5-methyl-1H-benzotriazole in an amount of from about 0.1% to about 0.5% by weight of the composition; methanesulfonic acid in an amount of from about 2% to about 5% by weight of the composition; 1,8-diazabicyclo[5.4.0]undec-7-ene in an amount of from about 0.5% to about 2% by weight of the composition; and water in an amount of from about 85% to about 95% by weight of the composition; wherein the composition has a pH of from about 4.5 to about 6. ### Claim 23 (depends on 20) The composition of claim 20, further comprising ethylene glycol butyl ether. ### Claim 24 (depends on 23) The composition of claim 23, wherein the composition comprises: hydroxylamine in an amount of from about 0.1% to about 5% by weight of the composition; diethylenetriamine pentaacetic acid in an amount of from about 0.01% to about 0.5% by weight of the composition; 5-methyl-1H-benzotriazole in an amount of from about 0.05% to about 1% by weight of the composition; methanesulfonic acid in an amount of from about 1% to about 10% by weight of the composition; 1,8-diazabicyclo[5.4.0]undec-7-ene in an amount of from about 0.1% to about 3% by weight of the composition; ethylene glycol butyl ether in an amount of from about 0.5% to about 10% by weight of the composition; and water in an amount of from about 75% to about 98% by weight of the composition; wherein the composition has a pH of from about 4 to about 7. ### Claim 25 (depends on 24) The composition of claim 24, wherein the composition comprises: hydroxylamine in an amount of from about 0.5% to about 2% by weight of the composition; diethylenetriamine pentaacetic acid in an amount of from about 0.1% to about 0.5% by weight of the composition; 5-methyl-1H-benzotriazole in an amount of from about 0.1% to about 0.5% by weight of the composition; methanesulfonic acid in an amount of from about 2% to about 5% by weight of the composition; 1,8-diazabicyclo[5.4.0]undec-7-ene in an amount of from about 0.5% to about 2% by weight of the composition; ethylene glycol butyl ether in an amount of from about 1% to about 5% by weight of the composition; and water in an amount of from about 85% to about 95% by weight of the composition; wherein the composition has a pH of from about 4.5 to about 6. ### Claim 26 (depends on 1) The composition of claim 1, wherein the composition comprises hydroxylamine, diethylenetriamine pentaacetic acid, 5-methyl-1H-benzotriazole, monoethanolamine, methanesulfonic acid, and water. ### Claim 27 (depends on 26) The composition of claim 26, wherein the composition comprises: hydroxylamine in an amount of from about 0.1% to about 5% by weight of the composition; diethylenetriamine pentaacetic acid in an amount of from about 0.01% to about 0.5% by weight of the composition; 5-methyl-1H-benzotriazole in an amount of from about 0.05% to about 1% by weight of the composition; methanesulfonic acid in an amount of from about 1% to about 10% by weight of the composition; monoethanolamine in an amount of from about 0.1% to about 3% by weight of the composition; and water in an amount of from about 75% to about 98% by weight of the composition; wherein the composition has a pH of from about 4 to about 7. ### Claim 28 (depends on 27) The composition of claim 27, wherein the composition comprises: hydroxylamine in an amount of from about 0.5% to about 2% by weight of the composition; diethylenetriamine pentaacetic acid in an amount of from about 0.1% to about 0.5% by weight of the composition; 5-methyl-1H-benzotriazole in an amount of from about 0.1% to about 0.5% by weight of the composition; methanesulfonic acid in an amount of from about 2% to about 5% by weight of the composition; monoethanolamine in an amount of from about 0.5% to about 2% by weight of the composition; and water in an amount of from about 85% to about 95% by weight of the composition; wherein the composition has a pH of from about 4.5 to about 6. ### Claim 29 (depends on 26) The composition of claim 26, further comprising ethylene glycol butyl ether. ### Claim 30 (depends on 29) The composition of claim 29, wherein the composition comprises: hydroxylamine in an amount of from about 0.1% to about 5% by weight of the composition; diethylenetriamine pentaacetic acid in an amount of from about 0.01% to about 0.5% by weight of the composition; 5-methyl-1H-benzotriazole in an amount of from about 0.05% to about 1% by weight of the composition; methanesulfonic acid in an amount of from about 1% to about 10% by weight of the composition; monoethanolamine in an amount of from about 0.1% to about 3% by weight of the composition; ethylene glycol butyl ether in an amount of from about 0.5% to about 10% by weight of the composition; and water in an amount of from about 75% to about 98% by weight of the composition; wherein the composition has a pH of from about 4 to about 7. ### Claim 31 (depends on 30) The composition of claim 30, wherein the composition comprises: hydroxylamine in an amount of from about 0.5% to about 2% by weight of the composition; diethylenetriamine pentaacetic acid in an amount of from about 0.1% to about 0.5% by weight of the composition; 5-methyl-1H-benzotriazole in an amount of from about 0.1% to about 0.5% by weight of the composition; methanesulfonic acid in an amount of from about 2% to about 5% by weight of the composition; monoethanolamine in an amount of from about 0.5% to about 2% by weight of the composition; ethylene glycol butyl ether in an amount of from about 1% to about 5% by weight of the composition; and water in an amount of from about 85% to about 95% by weight of the composition; wherein the composition has a pH of from about 4.5 to about 6. ### Claim 32 (depends on 1) The composition of claim 1, wherein the composition comprises hydroxylamine, diethylenetriamine pentaacetic acid, 5-methyl-1H-benzotriazole, ethylene glycol butyl ether, methanesulfonic acid, and water. ### Claim 33 (depends on 32) The composition of claim 32, wherein the composition comprises: hydroxylamine in an amount of from about 0.1% to about 5% by weight of the composition; diethylenetriamine pentaacetic acid in an amount of from about 0.01% to about 0.5% by weight of the composition; 5-methyl-1H-benzotriazole in an amount of from about 0.05% to about 1% by weight of the composition; methanesulfonic acid in an amount of from about 1% to about 10% by weight of the composition; ethylene glycol butyl ether in an amount of from about 1% to about 40% by weight of the composition; and water in an amount of from about 55% to about 98% by weight of the composition; wherein the composition has a pH of from about 4 to about 7. ### Claim 34 (depends on 33) The composition of claim 33, wherein the composition comprises: hydroxylamine in an amount of from about 0.5% to about 2% by weight of the composition; diethylenetriamine pentaacetic acid in an amount of from about 0.1% to about 0.5% by weight of the composition; 5-methyl-1H-benzotriazole in an amount of from about 0.1% to about 0.5% by weight of the composition; methanesulfonic acid in an amount of from about 1% to about 5% by weight of the composition; ethylene glycol butyl ether in an amount of from about 3% to about 40% by weight of the composition; and water in an amount of from about 55% to about 95% by weight of the composition; wherein the composition has a pH of from about 4.5 to about 6.5. ### Claim 35 (depends on 1) A method of cleaning residues from a semiconductor substrate, comprising: contacting a semiconductor substrate containing post etch residues and/or post ash residues with the cleaning composition of claim 1. ### Claim 36 (depends on 1) A method of treating a semiconductor substrate having a metal layer on a surface, comprising: oxidizing the metal layer to form an oxidized metal layer, and removing the oxidized metal layer from the semiconductor substrate by contacting the cleaning composition of claim 1 with the oxidized metal layer. ### Claim 37 (depends on 36) The method of claim 36, wherein the metal layer comprises cobalt, ruthenium, molybdenum, copper, tungsten, titanium, aluminum, or an alloy thereof. ### Claim 38 (depends on 36) The method of claim 36, wherein the oxidizing step comprises contacting a chemical liquid with the metal layer on the semiconductor substrate, in which the chemical liquid is selected from the group consisting of water, a hydrogen peroxide aqueous solution, an aqueous solution of ammonia and hydrogen peroxide, an aqueous solution of hydrofluoric acid and hydrogen peroxide, an aqueous solution of sulfuric acid and hydrogen peroxide, an aqueous solution of hydrochloric acid and hydrogen peroxide, oxygen dissolved water, ozone dissolved water, a perchloric acid aqueous solution, and a sulfuric acid aqueous solution. ### Claim 39 (depends on 36) The method of claim 36, wherein the oxidizing step comprises contacting an oxidizing gas with the metal layer, heating the metal layer under an oxidizing atmosphere, or performing plasma treatment on the metal layer using an oxidizing gas.