Composition and method for removing photoresist and/or resist residue using supercritical fluids

Abstract

A method of removing photoresist and/or resist residue from a substrate includes exposing the substrate to a supercritical fluid in combination with a co-solvent mixture comprising an organic solvent and an oxidizer. In one embodiment, the supercritical fluid is supercritical carbon dioxide and the co-solvent mixture includes 1,2-Butylene Carbonate, Dimethyl Sulfoxide and hydrogen peroxide. If desired, supercritical carbon dioxide in combination with a second co-solvent mixture may be subsequently applied to the substrate to rinse and dry the substrate. In one embodiment, the second co-solvent mixture includes isopropyl alcohol.

What is claimed is:  
     
         1 . A method of removing photoresist and/or resist residue from a substrate, comprising the steps of: 
 (a) providing a substrate having photoresist material formed thereon;    (b) exposing the substrate to a supercritical fluid in combination with a co-solvent mixture comprising an organic solvent and an oxidizer.    
     
     
         2 . The method of  claim 1  wherein the supercritical fluid is supercritical carbon dioxide.  
     
     
         3 . The method of  claim 1  wherein the co-solvent mixture include an aqueous fluoride.  
     
     
         4 . The method of  claim 3  wherein the aqueous fluoride is selected from the group consisting of ammonium fluoride and hydrofluoric acid.  
     
     
         5 . The method of  claim 1  in which the organic solvent is selected from the group consisting of 1,2-Butylene Carbonate, Benzyl Alcohol, Ethylene and Propylene Carbonate and mixtures thereof, Dimethyl Sulfoxide, N-Methyl Pyrrolidone, Dimethyl Acetamide, Dimethyl Formamide, Propylene Glycol and Propylene Glycol n-Butyl Ether.  
     
     
         6 . The method of  claim 5 , wherein the organic solvent includes 1,2-Butylene Carbonate.  
     
     
         7 . The method of  claim 5 , wherein the organic solvent includes Dimethyl Sulfoxide.  
     
     
         8 . The method of  claim 5 , wherein the organic solvent includes Benzyl Alcohol.  
     
     
         9 . The method of  claim 5 , wherein the organic solvent includes Propylene Carbonate, 1,2-Butylene Carbonate and Dimethyl Sulfoxide.  
     
     
         10 . The method of  claim 5 , wherein the organic solvent includes Propylene Carbonate.  
     
     
         11 . The method of  claim 5 , wherein the organic solvent includes Propylene Carbonate and Dimethyl Sulfoxide.  
     
     
         12 . The method of  claim 5 , wherein the organic solvent includes Propylene Carbonate and Benzyl Alcohol.  
     
     
         13 . The method of  claim 5 , wherein the organic solvent includes 1,2-Butylene Carbonate and Dimethyl Sulfoxide.  
     
     
         14 . The method of  claim 5 , wherein the organic solvent includes 1,2-Butylene Carbonate and Benzyl Alcohol.  
     
     
         15 . The method of  claim 1  wherein the oxidizer is selected from the group consisting of hydrogen peroxide, benzoyl peroxide, urea peroxide and mixtures thereof.  
     
     
         16 . The method of  claim 15  wherein the oxidizer is 10 to 80% hydrogen peroxide.  
     
     
         17 . The method of  claim 1  wherein the exposing step causes stripping of photoresist material from the substrate.  
     
     
         18 . The method of  claim 1  wherein the exposing step cleans resist residue from the substrate.  
     
     
         19 . The method of  claim 17 , wherein the co-solvent mixture is a first co-solvent mixture and wherein the method further includes the step of, after step (b), exposing the substrate to a second mixture comprising a supercritical fluid in combination with isopropyl alcohol.  
     
     
         20 . The method of  claim 19  wherein the second co-solvent mixture includes supercritical fluid in combination with isopropyl alcohol and water.  
     
     
         21 . The method of  claim 19  wherein the step of exposing the substrate to the second co-solvent mixture removes the first co-solvent mixture from the substrate and dries the substrate.  
     
     
         22 . The method of  claim 1  wherein the substrate includes I-line photoresist and wherein the method is for removing the I-line photoresist.  
     
     
         23 . The method of  claim 1  wherein the substrate is a substrate previously exposed to ion implantation.  
     
     
         24 . The method of  claim 1  wherein the substrate includes aluminum lines formed thereon.  
     
     
         25 . The method of  claim 1  wherein the substrate includes at least one integrated circuit device including low-dielectric constant materials.  
     
     
         26 . The method of  claim 1  wherein the substrate includes at least one integrated circuit device having high dielectric constant gate materials.  
     
     
         27 . The method of  claim 1  wherein the substrate includes back anti-reflective coating and wherein the method removes the back anti-reflective coating from the substrate.  
     
     
         28 . The method of  claim 1  wherein the substrate includes deep UV photoresist and wherein the method removes the DUV photoresist from the substrate.  
     
     
         29 . The method of  claim 1  wherein the substrate includes post-ash residues, and wherein the method includes removing the post-ash residues from the substrate.  
     
     
         30 . A composition for removing photoresist and/or resist residues from a substrate, the composition comprising: 
 a supercritical fluid in combination with a co-solvent mixture comprising an organic solvent and an oxidizer.    
     
     
         31 . The composition of  claim 30  wherein the supercritical fluid is supercritical carbon dioxide.  
     
     
         32 . The composition of  claim 30  wherein the co-solvent mixture include an aqueous fluoride.  
     
     
         33 . The composition of  claim 32  wherein the aqueous fluoride is selected from the group consisting of ammonium fluoride and hydrofluoric acid.  
     
     
         34 . The composition of  claim 30  in which the organic solvent is selected from the group consisting of 1,2-Butylene Carbonate, Benzyl Alcohol, Ethylene and Propylene Carbonate and mixtures thereof, Dimethyl Sulfoxide, N-Methyl Pyrrolidone, Dimethyl Acetamide, Dimethyl Formamide, Propylene Glycol and Propylene Glycol n-Butyl Ether.  
     
     
         35 . The composition of  claim 34 , wherein the organic solvent includes 1,2-Butylene Carbonate.  
     
     
         36 . The composition of  claim 34 , wherein the organic solvent includes Dimethyl Sulfoxide.  
     
     
         37 . The composition of  claim 34 , wherein the organic solvent includes Benzyl Alcohol.  
     
     
         38 . The composition of  claim 34 , wherein the organic solvent includes Propylene Carbonate.  
     
     
         39 . The composition of  claim 34 , wherein the organic solvent includes Propylene Carbonate and Dimethyl Sulfoxide.  
     
     
         40 . The composition of  claim 34  wherein the organic solvent includes Propylene Carbonate and Benzyl Alcohol.  
     
     
         41 . The composition of  claim 34 , wherein the organic solvent includes 1,2-Butylene Carbonate and Dimethyl Sulfoxide.  
     
     
         42 . The composition of  claim 34 , wherein the organic solvent includes 1,2-Butylene Carbonate and Benzyl Alcohol.  
     
     
         43 . The composition of  claim 34 , wherein the organic solvent includes Propylene Carbonate, 1,2-Butylene Carbonate and Dimethyl Sulfoxide.  
     
     
         44 . The composition of  claim 30  wherein the oxidizer is selected from the group consisting of hydrogen peroxide, benzoyl peroxide, urea peroxide and mixtures thereof.  
     
     
         45 . The composition of  claim 44  wherein the oxidizer is 10 to 80% hydrogen peroxide.  
     
     
         46 . A composition for removing photoresist and/or resist residue from a substrate, the comprising including supercritical carbon dioxide, 1,2-Butylene Carbonate, Dimethyl Sulfoxide and hydrogen peroxide.  
     
     
         47 . The composition of  claim 46 , further including ammonium fluoride.  
     
     
         48 . A composition for removing photoresist and/or resist residuel from a substrate, the comprising including supercritical carbon dioxide, Benzyl Alcohol, 1,2-Butylene Carbonate and hydrogen peroxide.  
     
     
         49 . The composition of  claim 48 , further including ammonium fluoride.  
     
     
         50 . A composition for removing photoresist and/or resist residue from a substrate, the comprising including supercritical carbon dioxide, Propylene Carbonate, Dimethyl Sulfoxide and hydrogen peroxide.  
     
     
         51 . The composition of  claim 50 , further including ammonium fluoride.  
     
     
         52 . A composition for removing photoresist and/or resist residue from a substrate, the comprising including supercritical carbon dioxide, Propylene Carbonate, Benzyl Alcohol and hydrogen peroxide.  
     
     
         53 . The composition of  claim 52 , further including ammonium fluoride.