Electroplating compositions and methods for electroplating

Abstract

Disclosed are electroplating compositions and methods for filling recessed microstructures of a microelectronic workpiece, such as a semiconductor wafer, with metallization. The electroplating compositions may comprise a mixture of copper and sulfuric acid wherein the ratio of copper concentration to sulfuric acid concentration is equal to from about 0.3 to about 0.8 g/L (grams per liter of solution). The disclosed electroplating compositions may also comprise a mixture of copper and sulfuric acid wherein the copper concentration is near its solubility limit when the sulfuric acid concentration is from about 65 to about 150 g/L. Such electroplating compositions may also include conventional additives, such as accelerators, suppressors, halides and/or levelers. Methods for electrochemically depositing conductive materials in features, such as trenches and/or contact holes formed on semiconductor workpieces are disclosed, including methods suited for use in multiple anode reactors using the disclosed electroplating solutions.

1 . An aqueous-based electroplating composition comprising: 
 about 35 to about 60 g/L copper;    about 65 to about 150 g/L sulfuric acid;    a glycol-based suppressor.    
     
     
         2 . The composition of  claim 1  wherein the glycol-based suppressor is present at a concentration of from about 2 to about 30 ml/L.  
     
     
         3 . The composition of  claim 1  further comprising a copper-deposition accelerator present at a concentration of from about 2 to about 30 ml/L.  
     
     
         4 . The composition of  claim 1  further comprising from about 10 to about 100 ppm halide ion.  
     
     
         5 . The composition of  claim 4  further comprising from about 30 to about 60 ppm HCl.  
     
     
         6 . An electroplating composition comprising: 
 about 35 to about 60 g/L copper;    about 65 to about 150 g/L sulfuric acid; and    about 2 to about 30 ml/L of a copper-deposition suppressor;    wherein the balance of the composition is water.    
     
     
         7 . The composition of  claim 6  further comprising a copper-deposition accelerator at a concentration of from about 2 to about 30 ml/L.  
     
     
         8 . The composition of  claim 6  wherein the copper-deposition suppressor is a random or block copolymer.  
     
     
         9 . The composition of  claim 6  wherein the copper-deposition suppressor is copper bath viaform suppressor or Shipley C-3100 suppressor.  
     
     
         10 . The composition of  claim 6  wherein the copper-deposition suppressor is glycol-based.  
     
     
         11 . The composition of  claim 6  further comprising a copper-deposition accelerator.  
     
     
         12 . The composition of  claim 11  wherein the copper-deposition accelerator is copper bath viaform accelerator or Shipley B-3100 accelerator.  
     
     
         13 . The composition of  claim 11  wherein the copper-deposition accelerator is SPS.  
     
     
         14 . The composition of  claim 6  further comprising from about 10 to about 100 ppm HCl.  
     
     
         15 . An aqueous electroplating composition comprising: 
 about 35 to about 60 g/L copper;    about 65 to about 150 g/L sulfuric acid;    about 2 to about 30 ml/L copper-deposition accelerator;    about 2 to about 30 ml/L copper-deposition suppressor; and    about 40 to about 60 ppm hydrogen chloride.    
     
     
         16 . The composition of  claim 15  wherein the copper-deposition suppressor is glycol-based.  
     
     
         17 . The composition of  claim 15  wherein the copper-deposition accelerator is a sulphur containing compound.  
     
     
         18 . The composition of  claim 1  further comprising about 50 ppm HCl.  
     
     
         19 . An electroplating composition comprising: 
 about 45 to about 55 g/L copper;    about 75 to about 120 g/L sulfuric acid;    a copper-deposition suppressor; and    a copper-deposition accelerator.    
     
     
         20 . The composition of  claim 19  wherein the glycol-based suppressor is at a concentration of from about 2 to about 10 ml/L.  
     
     
         21 . The composition of  claim 19  further comprising a copper-deposition accelerator present at a concentration of from about 2 to about 8 ml/L.  
     
     
         22 . The composition of  claim 19  further comprising from about 10 to about 100 ppm halide ion.  
     
     
         23 . The composition of  claim 19  further comprising from about 30 to about 60 ppm HCl.  
     
     
         24 . The composition of  claim 21  wherein the copper-deposition accelerator is a sulphur containing compound.  
     
     
         25 . The composition of  claim 19  further comprising a leveler.  
     
     
         26 . An electroplating composition comprising: 
 an aqueous mixture of copper and sulfuric acid wherein the ratio in g/L of solution of copper to acid is equal to about 0.4 to about 0.8;    a copper-deposition suppressor; and    a copper-deposition accelerator.    
     
     
         27 . The composition of  claim 26  wherein the copper-deposition suppressor is a random or block copolymer.  
     
     
         28 . The composition of  claim 26  wherein the copper-deposition suppressor is copper bath viaform suppressor or Shipley C-3 100 suppressor.  
     
     
         29 . The composition of  claim 26  wherein the copper-deposition suppressor is glycol-based.  
     
     
         30 . The composition of  claim 26  further comprising a copper-deposition accelerator present in a concentration of from about 2 to about 30 ml/L.  
     
     
         31 . The composition of  claim 26  wherein the copper-deposition accelerator is copper bath viaform accelerator or Shipley B-3100 accelerator.  
     
     
         32 . The composition of  claim 26  wherein the copper-deposition accelerator is SPS.  
     
     
         33 . The composition of  claim 26  further comprising from about 10 to about 100 ppm HCl.  
     
     
         34 . An electroplating composition comprising: 
 an aqueous-based mixture of copper and sulfuric acid wherein the ratio in g/L solution of copper to acid is equal to about 0.3 to about 0.8;    a copper-deposition suppressor;    a copper-deposition accelerator;    wherein only electroplating compositions comprising a mixture of copper and sulfuric acid wherein the ratio in g/L of copper to acid is equal to about 0.3 to about 0.8 are used to deposit copper on a workpiece.    
     
     
         35 . An electroplating composition comprising: 
 an aqueous mixture of copper and sulfuric acid wherein the copper concentration in the composition is within about 60% to about 90% of its solubility limit when the sulfuric acid concentration is from about 65 to about 150 g/L;    a copper-deposition suppressor; and    a copper-deposition accelerator.    
     
     
         36 . The composition of  claim 35  wherein the copper-deposition suppressor is present at a concentration of from about 2 to about 30 ml/L.  
     
     
         37 . The composition of  claim 35  further comprising a copper-deposition accelerator present at a concentration of from about 2 to about 30 ml/L.  
     
     
         38 . The composition of  claim 36  further comprising from about 10 to about 100 ppm halide ion.  
     
     
         39 . The composition of  claim 36  further comprising from about 30 to about 60 ppm HCl.  
     
     
         40 . The composition of  claim 36  wherein the copper-deposition suppressor is at a concentration of from about 2 to about 10 ml/L.  
     
     
         41 . The composition of  claim 36  further comprising a copper-deposition accelerator present at a concentration of from about 2 to about 8 ml/L.  
     
     
         42 . The composition of  claim 36  wherein the copper-deposition accelerator is a sulphur containing compound.  
     
     
         43 . The composition of  claim 36  wherein the copper-deposition suppressor is glycol-based.  
     
     
         44 . An electroplating composition comprising: 
 about 40 g/L copper;    about 100 g/L sulfuric acid;    a copper-deposition suppressor; and    a copper-deposition accelerator.    
     
     
         45 . The composition of  claim 44  wherein the copper-deposition suppressor is present at a concentration of from about 2 to about 30 ml/L.  
     
     
         46 . The composition of  claim 44  further comprising a copper-deposition accelerator present at a concentration of from about 2 to about 30 ml/L.  
     
     
         47 . The composition of  claim 44  further comprising from about 10 to about 100 ppm halide ion.  
     
     
         48 . The composition of  claim 44  further comprising from about 30 to about 60 ppm HCl.  
     
     
         49 . The composition of  claim 44  wherein the copper-deposition suppressor is at a concentration of from about 2 to about 10 ml/L.  
     
     
         50 . The composition of  claim 44  further comprising a copper-deposition accelerator present at a concentration of from about 2 to about 8 ml/L.  
     
     
         51 . The composition of  claim 44  wherein the copper-deposition accelerator is a sulphur containing compound.  
     
     
         52 . The composition of  claim 44  wherein the copper-deposition suppressor is glycol-based.  
     
     
         53 . An aqueous electroplating composition comprising: 
 about 50 g/L copper;    about 80 g/L sulfuric acid;    about 2 to about 10 ml/L copper-deposition suppressor; and    about 2 to about 8 ml/L copper-deposition accelerator.    
     
     
         54 . The composition of  claim 53  further comprising from about 10 to about 100 ppm halide ion.  
     
     
         55 . A method for plating a workpiece comprising: 
 providing a workpiece having a plurality of device features including a seed layer wherein the plurality of device features is to be metallized;    depositing copper within the plurality of device features utilizing an electroplating composition comprising about 35 to about 60 g/L copper, about 65 to about 150 g/L sulfuric acid, and a glycol-based suppressor.    
     
     
         56 . The method of  claim 55  further comprising a seed enhancement procedure.  
     
     
         57 . The method of  claim 55  further comprising rinsing and drying the workpiece during processing, wherein the rinsing and/or the drying occurs in a chamber in which the deposition of copper is performed.  
     
     
         58 . The method of  claim 55  further comprising selective etching of copper deposited on the workpiece.  
     
     
         59 . The method of  claim 55  further comprising cleaning the backside of the workpiece after copper is deposited on the workpiece.  
     
     
         60 . The method of  claim 55  further comprising annealing the workpiece at temperatures below about 100° C.  
     
     
         61 . The method of  claim 55  further comprising precleaning the workpiece prior to depositing copper wherein the precleaning of the workpiece is performed in the same plating tool in which the deposition is performed.  
     
     
         62 . The method of  claim 55  wherein the electroplating composition comprises from about 35 to about 60 g/L copper, from about 65 to about 150 g/L sulfuric acid, and from about 2 to about 30 ml/L of a copper-deposition suppressor.  
     
     
         63 . A method for plating a workpiece comprising: 
 providing a workpiece having a plurality of device features including a seed layer wherein the plurality of device features is to be metallized;    depositing copper within the plurality of device features utilizing an electroplating composition comprising from about 35 to about 60 g/L copper, from about 65 to about 150 g/L sulfuric acid, from about 2 to about 30 ml/L copper-deposition accelerator, from about 2 to about 30 ml/L copper-deposition suppressor; and from about 40 to about 60 ppm hydrogen chloride.    
     
     
         64 . The method of  claim 63  wherein the electroplating composition comprises a mixture of copper and sulfuric acid wherein the ratio in g/L of copper to acid is equal to about 0.4 to about 0.8, a copper-deposition suppressor, and a copper-deposition accelerator.  
     
     
         65 . The method of  claim 63  wherein the electroplating composition comprises a mixture of copper and sulfuric acid wherein the ratio in g/L of copper to acid is equal to about 0.3 to about 0.8, a copper-deposition suppressor, and a copper-deposition accelerator and wherein only electroplating compositions comprising a mixture of copper and sulfuric acid wherein the ratio in g/L of copper to acid is equal to about 0.3 to about 0.8 are used to deposit copper on the workpiece.  
     
     
         66 . A process for applying a metallization interconnect structure, comprising: 
 providing a workpiece on which a metal seed layer has been formed using a first deposition process;    repairing the seed layer by electrochemically depositing additional metal on the seed layer within a principal fluid chamber of a reactor to provide an enhanced seed layer using a deposition process comprising supplying electroplating power to a plurality of concentric anodes disposed at different positions within the principal fluid flow chamber relative to the workpiece; and    electrolytically depositing a metal on the enhanced seed layer utilizing an electroplating composition comprising about 35 to about 60 g/L copper, about 65 to about 150 g/L sulfuric acid, and a glycol-based suppressor.    
     
     
         67 . The process of  claim 66  wherein the electroplating composition comprises from about 35 to about 60 g/L copper, from about 65 to about 150 g/L sulfuric acid, and from about 2 to about 30 ml/L of a copper-deposition suppressor.  
     
     
         68 . A process for applying a metallization interconnect structure, comprising: 
 providing a workpiece on which a metal seed layer has been formed;    repairing the seed layer by electrochemically depositing additional metal on the seed layer within a principal fluid chamber of a reactor to provide an enhanced seed layer using a deposition process comprising supplying electroplating power to a plurality of electrodes within the principal fluid flow chamber,    independently controlling the supply of electrical power to the at least two electrodes during repair of the seed layer; and    electrolytically depositing copper on the enhanced seed layer under conditions in which the deposition rate of the electrolytic deposition process is substantially greater than the deposition rate of the process used to repair the metal seed utilizing an electroplating composition comprising a mixture of copper and sulfuric acid wherein the ratio in g/L of copper to acid is equal to about 0.4 to about 0.8, a copper-deposition suppressor, and a copper-deposition accelerator.    
     
     
         69 . The method of  claim 68  wherein the electroplating composition comprises a mixture of copper and sulfuric acid wherein the ratio in g/L of copper to acid is equal to about 0.3 to about 0.8.