Electric copper plating liquid and process for manufacturing semiconductor integrated circuit device using same

Abstract

An object of the present invention is to improve the reliability and the yield of production of semiconductor integrated circuit devices by filling copper in the inside of features having a high aspect ratio for forming multi-layer interconnections composed of a plurality of interconnection layers which are connected to one another and to a copper electroplating bath suitable therefor. In the present invention, when the features are filled with copper, the use of a copper electroplating bath with an addition of cyanine dyes, for example, indolium compounds allows the copper plating to proceed preferentially from the bottoms of the features.

1 . A copper electroplating solution containing copper ions, at least one electrolyte, and at least one cyanine dye, wherein said at least one cyanine dye suppresses an electroplating reaction during use of the copper electroplating solution for electroplating, and said at least one cyanine dye is present in the solution in a concentration of 1-15 mg/L.  
     
     
         2 . A copper electroplating solution containing copper ions, at least one electrolyte, and at least one indolium compound, wherein said at least one indolium compound suppresses an electroplating reaction during use of the copper electroplating solution for electroplating, and said at least one indolium compound is present in the solution in a concentration of 1-15 mg/L.  
     
     
         3 . A copper electroplating solution containing copper ions, at least one electrolyte and at least one of the compounds represented by the following general formula  
       
         
           
           
               
               
           
         
       
       where X −  is an anion, and n is 0, 1, 2, or 3, wherein said at least one of the compounds represented by the general formula (I) suppresses an electroplating reaction during use of the copper electroplating solution for electroplating, and is present in the solution in a concentration of 1-15 mg/L.  
     
     
         4 . The copper electroplating bath according to  claim 1 , further including at least one selected from the group consisting of polyether, organic sulfur compound, and halide ion, wherein the bath includes a polyether when it includes said halide ion.  
     
     
         5 . The copper electroplating bath according to  claim 2 , further including at least one selected from the group consisting of polyether, organic sulfur compound, and halide ion, wherein the bath includes a polyether when it includes said halide ion.  
     
     
         6 . The copper electroplating bath according to  claim 3 , further including at least one selected from the group consisting of polyether, organic sulfur compound, and halide ion, wherein the bath includes a polyether when it includes said halide ion.  
     
     
         7 . A process for producing a semiconductor integrated circuit device comprising providing an insulating layer having features on the top of the major surface of a semiconductor wafer which has a plurality of circuit element areas formed, depositing a barrier metal layer and a seed metal layer on the bottoms and the side surfaces of said features and on the top surface of said insulating layer, and filling the inside of said features with copper by electroplating with the copper electroplating solution according to  claim 1 .  
     
     
         8 . A process for producing a semiconductor integrated circuit device comprising providing an insulating layer having features on the top of the major surface of a semiconductor wafer which has a plurality of circuit element areas formed, depositing a barrier metal layer and a seed metal layer on the bottoms and the side surfaces of said features and on the top surface of said insulating layer, and filling the inside of said features with copper by electroplating with the copper electroplating solution according to  claim 2 .  
     
     
         9 . A process for producing a semiconductor integrated circuit device comprising providing an insulating layer having features on the top of the major surface of a semiconductor wafer which has a plurality of circuit element areas formed, depositing a barrier metal layer and a seed metal layer on the bottoms and the side surfaces of said features and on the top surface of said insulating layer, and filling the inside of said features with copper by electroplating with the copper electroplating solution according to  claim 3 .  
     
     
         10 . A copper electroplating solution containing copper ions, at least one electrolyte, and an additive selected from the group consisting of (a) cyanine dyes, (b) indolium compounds, and (c) compounds represented by the following general formula (I):  
       
         
           
           
               
               
           
         
       
       where X −  is an anion, and n is 0, 1, 2 or 3, wherein said additive suppresses an electroplating reaction during use of the copper electroplating solution for electroplating, and is present in the solution in a concentration of 1-15 mg/L.  
     
     
         11 . The copper electroplating bath according to  claim 10 , further including a least one selected from the group consisting of polyether, organic sulfur compound, and halide ion, wherein the bath includes a polyether when it includes said halide ion.  
     
     
         12 . A process for producing a semiconductor integrated circuit device comprising providing an insulating layer having features on the top of the major surface of a semiconductor wafer which has a plurality of circuit element areas formed, depositing a barrier metal layer and a seed metal layer on the bottoms and the side surfaces of said features and on the top surface of said insulating layer, and filling the inside of said features with copper by electroplating with the copper electroplating solution according to  claim 10 .  
     
     
         13 . The copper electroplating solution according to  claim 10 , wherein said additive is consumed as the electroplating reaction proceeds, and a diffusion rate thereof is lower than a rate of reaction of the additives during the use of the copper electroplating solution for electroplating.  
     
     
         14 . The copper electroplating solution according to  claim 3 , wherein said at least one of the compounds represented by the general formula (I) is consumed as the electroplating reaction proceeds, and a diffusion rate thereof is lower than the rate of reaction thereof during the use of the copper electroplating solution for electroplating.  
     
     
         15 . The copper electroplating solution according to  claim 6 , further containing said polyether.  
     
     
         16 . The copper electroplating solution according to  claim 15 , wherein said polyether is selected from the group consisting of polyethylene glycols, polypropylene glycols and polyoxypropylene glycols, having an average molecular weight of 1000 to 10,000.  
     
     
         17 . The copper electroplating solution according to  claim 6 , further containing said organic sulfur compound.  
     
     
         18 . The copper electroplating solution according to  claim 17 , wherein said organic sulfur compound is selected from the group consisting of 3-mercapto-1-propanesulfonic acid, 2-mercapto ethane sulfonic acid, bis (4-sulfobutyl) disulfide, bis (3-sulfopropyl) disulfide, bis (2-sulfaethyl) disulfide and bis (p-sulfophenyl) disulfide.  
     
     
         19 . A process for producing a semiconductor integrated circuit device comprising providing an insulating layer having features on the top of the major surface of a semiconductor wafer which has a plurality of circuit element areas formed, depositing a barrier metal layer and a seed metal layer on the bottoms and the side surfaces of said features and on the top surface of said insulating layer, and filling the inside of said features with copper by electroplating with the copper electroplating solution according to  claim 3 , wherein said at least one of the compounds represented by the general formula (I) is consumed as the electroplating reaction proceeds, and has a diffusion rate lower than a rate of reaction thereof during the process.  
     
     
         20 . A process for producing a semiconductor integrated circuit device comprising providing an insulating layer having features on the top of the major surface of a semiconductor wafer which has a plurality of circuit element areas formed, depositing a barrier metal layer and a seed metal layer on the bottoms and the side surfaces of said features and on the top surface of said insulating layer, and filling the inside of said features with copper by electroplating with the copper electroplating solution according to  claim 10 , wherein said additive is consumed as the electroplating reaction proceeds, and has a diffusion rate lower than a rate of reaction thereof during the process.  
     
     
         21 . The process according to  claim 9 , wherein concentration of said at least one of the compounds represented by the general formula (I) in the electroplating solution, at said bottoms of said features, during the process, is less than that at a top of said features.  
     
     
         22 . The process according to  claim 12 , wherein concentration of said additive in the electroplating solution, at said bottoms of said features, during the process, is less than that at a top of said features.  
     
     
         23 . The copper electroplating solution according to  claim 2 , wherein said at least one indolium compound is consumed as the electroplating reaction proceeds, and a diffusion rate thereof is lower than a rate of reaction thereof during use of the copper electroplating solution for electroplating.  
     
     
         24 . The copper electroplating solution according to  claim 1 , wherein said at least one cyanine dye is consumed as the electroplating reaction proceeds, and a diffusion rate thereof is lower than a rate of reaction thereof during use of the copper electroplating solution for electroplating.