Acid copper electroplating solutions

Abstract

Improved acid copper electroplating bath compositions are disclosed. The improved bath solutions contain at least one of a carrier; a water-soluble, mercapto-containing organic brightener; and a leveler which comprises an organic compound containing single or multiply charged centers in acidic bath solution. These electroplating bath compositions are used to copper plate advanced interconnects on semiconductor devices.

1 - 38  (cancelled)  
     
     
         39 . A method for copper plating of advanced interconnects comprising immersing said interconnects in a copper plating bath comprising an aqueous solution of an acid and a copper salt and at least one of a carrier compound; a water-soluble, mercapto-containing organic brightener compound; and a leveler compound containing single and multiply charged centers; wherein said leveler compound is selected from the group consisting of poly(allylamine); poly(allylamine hydrochloride); polyaniline, sulfonated, 5 wt. % in water, 75 mole % sulfonated; poly[bis(2-chloroethyl)ether-alt-1,3-bis[3-(dimethylamino)propyl]urea, quaternited; poly[N,N′-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine-co-2,4-dichloro-6-morpholino-1,3,5-triazine; polyacrylamide; poly(acrylamide-co-diallyldimethylammonium chloride); poly(diallyldimethylammonium chloride); poly(melamine-co-formaldehyde), partially methylated; poly(4-vinylpyridine), 25% cross-linked; and poly(1,2-dihydro-2,2,4-trimethylquinoline).  
     
     
         40 . The method as claimed in  claim 39  wherein said acid is sulfuric acid.  
     
     
         41 . The method as claimed in  claim 39  wherein said copper salt is selected from the group consisting of copper sulfate, copper acetate, copper fluoborate, cupric nitrate and copper pyrophosphate.  
     
     
         42 . The method as claimed in  claim 41  wherein said copper salt is copper sulfate.  
     
     
         43 . The method as claimed in  claim 39  wherein said carrier compound is selected from the group consisting of a polysaccharide compound, polyethylene glycol and poly(ethylene oxide).  
     
     
         44 . The method as claimed in  claim 43  wherein said polysaccharide carrier compound is selected from the group consisting of starch, cellulose, amylopectin and amylose.  
     
     
         45 . The method as claimed in  claim 39  wherein said water-soluble, mercapto-containing organic brightener is selected from the group consisting of N-methylallyl-N′-methylthiourea; tetramethylthiuram disulfide; ethylethylthiomethyl sulfoxide; ammonium diethyldithiocarbamate; dimethyl-2-thioxo-1,3-dithiole-4,5-dicarboxylate; 3-mercapto-1-propanesulfonic acid sodium salt; 3-mercapto-1-propanesulfonic acid; bis (2-mercaptoethyl) sulfide; ethylene trithio carbonate; ethanethiol; 2-mercaptoethanol; monothioglycerol (1-thioglycerol); 1,2-ethanedithiol; and thiodiethanol.  
     
     
         46 . The method as claimed in  claim 45  wherein said water-soluble, mercapto-containing organic brightener is selected from the group consisting of ammonium diethyldithiocarbamate, 3-mercapto-1-propanesulfonic acid sodium salt, and 3-mercapto-1-propanesulfonic acid.  
     
     
         47 - 48  (cancelled)  
     
     
         49 . The method as claimed in  claim 46  wherein said leveler compound is selected from the group consisting of poly[(bis(2-chloroethyl)ether-alt-1,2-bis[3(-dimethylamino)propyl]urea, quaternited, and poly(diallyl dimethylammonium chloride).  
     
     
         50 - 53  (cancelled)  
     
     
         54 . The method as claimed in  claim 39  further comprising a brightener/carrier molecule.  
     
     
         55 . The method as claimed in  claim 54  wherein said brightener/carrier molecule is polymeric protein.  
     
     
         56 . The method as claimed in  claim 39  further comprising a carrier/leveler molecule.  
     
     
         57 . The method as claimed in  claim 56  wherein said carrier/leveler molecule is selected from the group consisting of poly[bis(2-chloroethyl)ether-alt-1,3-bis[3-(dimethylamino)propyl] urea, quaternited, and poly(melamine-co-formaldehyde).  
     
     
         58 . The method as claimed in  claim 39  wherein said carrier is present in the composition in an amount ranging from about 2 to about 1000 parts per million parts water.  
     
     
         59 . The method as claimed in  claim 39  wherein said leveler is present in the composition in an amount ranging from about 2 to about 1000 parts per million parts water.  
     
     
         60 . The method as claimed in  claim 39  wherein said brightener is present in the composition in an amount ranging from about 5 to about 100 parts per million parts water.  
     
     
         61 . The method as claimed in  claim 39  wherein said carrier/brightener is present in an amount ranging from about 5 to about 1000 parts per million parts water and said carrier/leveler is present in an amount ranging from about 2 to about 1000 parts per million parts water.  
     
     
         62 . The method as claimed in  claim 39  wherein said compounds are added either individually or as combinations to said aqueous solution.  
     
     
         63 . The method as claimed in  claim 39  wherein a current between 3 mA/cm 2  and 40 mA/cm 2  is applied to said solution.  
     
     
         64 . The method as claimed in  claim 63  wherein the wave form of said current is selected from the group consisting of direct current, pulse current and pulse reverse current.