# US 8,772,214 B2 · Aqueous cleaning composition for removing residues and method using same > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 8,772,214 B2 - Document ID: US8772214B2 - Status: Granted - Kind: B2 - Application number: 11/250,250 - Filed: 2005-10-14 - Published: 2007-04-19 - Granted: 2014-07-08 - Earliest claimed: 2005-10-14 - Assignees: Air Products and Chemicals, Inc. - Applicants: Aiping Wu; Roberto John Rovito - Inventors: Aiping Wu; Roberto John Rovito - Web page: https://patentgrep.com/patent/US8772214B2 ## CPC - C11D 3/0073: {Anticorrosion compositions} - C11D 7/08: Acids - C11D 7/3209: {Amines or imines with one to four nitrogen atoms; Quaternized amines} - C23G 1/18: Organic inhibitors - G03F 7/425: {containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen} - G03F 7/426: {containing organic halogen compounds; containing organic sulfonic acids or salts thereof; containing sulfoxides} - H10P 70/20: {Cleaning during device manufacture} - C11D 1/62: Quaternary ammonium compounds - C11D 3/245: {containing fluorine} - 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 - C23G: CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS - 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 composition and method for removing residues such as, without limitation, post etched and/or post ashed photoresist, plasma etching, ashing, and mixtures thereof from a substrate is described herein. In one aspect, there is provided a method for removing residues from a substrate comprising: contacting the substrate with a composition comprising: water; a quaternary ammonium hydroxide compound; a fluoride containing compound; and optionally a corrosion inhibitor wherein the composition is free of an added organic solvent and wherein the composition has a pH greater than 9. ## Claims ### Claim 1 A composition for removing residues from a substrate, the composition consisting of: water; a quaternary ammonium hydroxide compound comprising a compound having a general formula [N-R1R2R3R4]+OH−wherein R1, R2, R3, and R4 are each independently an alkyl group, a hydroxyalkyl group, and mixtures thereof; a fluoride containing compound comprising at least one selected from the group consisting of a compound having a general formula R5R6R7R8NF where R5, R6, R7 and R8 are each independently hydrogen, an alcohol group, an alkoxy group, an alkyl group, and mixtures thereof; hydrofluoric acid; choline fluoride; aluminum hexafluoride; fluoride salt of an amine; and mixtures thereof; optionally a corrosion inhibitor selected from the group consisting of an organic acid, an organic acid salt, catechol, resorcinol, a phenol, maleic anhydride, phthalic anhydride, pyrogallol, gallic acid or esters thereof, benzotriazole, carboxybenzotriazole, diethylhydroxlamine, fructose, ammonium thiosulfate, glycine, tetramethylguanidine, iminodiacetic acid, thioglycerol, triazole, dimethylacetamide, mercapto-group containing compound and combinations thereof; and optionally an additive selected from the group consisting of a surfactant, a chelating agent, a dye, a biocide, and combinations thereof, wherein the composition is free of an added organic solvent and wherein the composition has a pH greater than 9. ### Claim 2 (depends on 1) The composition of claim 1 comprising the corrosion inhibitor. ### Claim 3 (depends on 1) The composition of claim 1 wherein the quaternary ammonium hydroxide compound is selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, (2-hydroxyethyl)trimethylammonium hydroxide, (2-hydroxyethyl)triethylammonium hydroxide, (2-hydroxyethyl)tripropylammonium hydroxide, (1-hydroxypropyl)trimethylammonium hydroxide, and mixtures thereof. ### Claim 4 (depends on 1) The composition of claim 1 wherein the fluoride containing compound comprises the compound having the general formula R5R6R7R8NF where R5, R6, R7 and R8 are each independently hydrogen, an alcohol group, an alkoxy group, an alkyl group, and mixtures thereof. ### Claim 5 (depends on 4) The composition of claim 4 wherein the fluoride containing compound is selected from tetramethyl ammonium fluoride, tetraethyl ammonium fluoride, tetrabutyl ammonium fluoride, choline fluoride, and mixtures thereof. ### Claim 6 (depends on 1) The composition of claim 1 wherein the fluoride containing compound is selected from hydrofluoric acid, choline fluoride; aluminum hexafluoride; fluoride salt of an amine, and mixtures thereof. ### Claim 7 A method for defining a pattern comprising the steps of: coating a photoresist onto a substrate, lithographically defining a pattern on the photoresist; transferring the pattern onto at least a portion of the substrate; etching the pattern into the substrate to form a patterned substrate; exposing the patterned substrate to an activated reactive gas to remove at least a portion of the photoresist and provide a residue; removing the residue from the substrate by contacting the substrate with a composition consisting of: water; a quaternary ammonium hydroxide compound comprising a compound having a general formula [N-R1R2R3R4]+OH−wherein R1, R2, R3, and R4 are each independently an alkyl group, a hydroxyalkyl group, and mixtures thereof; a fluoride containing compound comprising at least one selected from the group consisting of a compound having a general formula R5R6R7R8NF where R5, R6, R7 and R8 are each independently hydrogen, an alcohol group, an alkoxy group, an alkyl group, and mixtures thereof; hydrofluoric acid; choline fluoride; aluminum hexafluoride; fluoride salt of an amine; and mixtures thereof; optionally a corrosion inhibitor selected from the group consisting of an organic acid, an organic acid salt, catechol, resorcinol, a phenol, maleic anhydride, phthalic anhydride, pyrogallol, gallic acid or esters thereof, benzotriazole, carboxybenzotriazole, diethylhydroxlamine, fructose, ammonium thiosulfate, glycine, tetramethylguanidine, iminodiacetic acid, thioglycerol, triazole, dimethylacetamide, mercapto-group containing compound and combinations thereof; and optionally an additive selected from the group consisting of a surfactant, a chelating agent, a dye, a biocide, and combinations thereof, wherein the composition is substantially free of an added organic solvent and wherein the composition has a pH greater than 9. ### Claim 8 A method for removing residues from a substrate comprising: contacting the substrate with a composition consisting of: from 65 to 99.9% by weight of water; from 0.5 to 15% by weight of a quaternary ammonium hydroxide compound comprising a compound having a general formula [N-R1R2R3R4]+OH−wherein R1, R2, R3, and R4 are each independently an alkyl group, a hydroxyalkyl group, and mixtures thereof; from 0.1 to 10% by weight of a fluoride-containing compound comprising at least one selected from the group consisting of a compound having a general formula R5R6R7R8NF where R5, R6, R7 and R8 are each independently hydrogen, an alcohol group, an alkoxy group, an alkyl group, and mixtures thereof; hydrofluoric acid; choline fluoride; aluminum hexafluoride; fluoride salt of an amine; and mixtures thereof; and optionally from 0 to 10% by weight a corrosion inhibitor selected from the group consisting of an organic acid, an organic acid salt, catechol, resorcinol, a phenol, maleic anhydride, phthalic anhydride, pyrogallol, gallic acid or esters thereof, benzotriazole, carboxybenzotriazole, diethylhydroxlamine, fructose, ammonium thiosulfate, glycine, tetramethylguanidine, iminodiacetic acid, thioglycerol, triazole, dimethylacetamide, mercapto-group containing compound and combinations thereof; and optionally from 0 to about 5% by weight of an additive selected from the group consisting of a surfactant, a chelating agent, a dye, a biocide, and combinations thereof, wherein the composition is substantially free of an added organic solvent and wherein the composition has a pH greater than 9. ### Claim 9 (depends on 1) The composition of claim 1 consisting of: from 65 to 99.9% by weight of the water; from 0.5 to 15% by weight of the quaternary ammonium hydroxide compound; from 0.1 to 10% by weight of the fluoride-containing compound; optionally from 0 to 10% by weight the corrosion inhibitor; and optionally from 0 to about 5% by weight of the additive. ### Claim 10 (depends on 9) The composition of claim 9 wherein the composition comprises the corrosion inhibitor. ### Claim 11 (depends on 9) The composition of claim 9 wherein the quaternary ammonium hydroxide compound is selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, (2-hydroxyethyl)trimethylammonium hydroxide, (2-hydroxyethyl)triethylammonium hydroxide, (2-hydroxyethyl)tripropylammonium hydroxide, (1-hydroxypropyl)trimethylammonium hydroxide, and mixtures thereof. ### Claim 12 (depends on 10) The composition of claim 10 wherein the quaternary ammonium hydroxide compound is selected from the group consisting of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, (2-hydroxyethyl)trimethylammonium hydroxide, (2-hydroxyethyl)triethylammonium hydroxide, (2-hydroxyethyl)tripropylammonium hydroxide, (1-hydroxypropyl)trimethylammonium hydroxide, and mixtures thereof. ### Claim 13 (depends on 11) The composition of claim 11 wherein the fluoride containing compound comprises the compound having the general formula R5R6R7R8NF where R5, R6, R7 and R8 are each independently hydrogen, an alcohol group, an alkoxy group, an alkyl group, and mixtures thereof. ### Claim 14 (depends on 12) The composition of claim 12 wherein the fluoride containing compound comprises the compound having the general formula R5R6R7R8NF where R5, R6, R7 and R8 are each independently hydrogen, an alcohol group, an alkoxy group, an alkyl group, and mixtures thereof. ### Claim 15 (depends on 13) The composition of claim 13 wherein the fluoride containing compound is selected from tetramethyl ammonium fluoride, tetraethyl ammonium fluoride, tetrabutyl ammonium fluoride, choline fluoride, and mixtures thereof. ### Claim 16 (depends on 14) The composition of claim 14 wherein the fluoride containing compound is selected from tetramethyl ammonium fluoride, tetraethyl ammonium fluoride, tetrabutyl ammonium fluoride, choline fluoride, and mixtures thereof. ### Claim 17 (depends on 11) The composition of claim 11 wherein the fluoride containing compound comprises hydrofluoric acid, choline fluoride, aluminum hexafluoride, fluroide salt of an amine, or mixtures thereof. ### Claim 18 (depends on 12) The composition of claim 12 wherein the fluoride containing compound comprises hydrofluoric acid, choline fluoride; aluminum hexafluoride, fluroide salt of an amine, or mixtures thereof. ### Claim 19 (depends on 9) The composition of claim 9 wherein the composition comprises the additive. ### Claim 20 (depends on 10) The composition of claim 10 wherein the composition comprises the additive.