Electroplating process and composition

Abstract

A plating process employing an anode having a precious metal-based active material, and an electrolytic plating composition comprising a source of metal ions in an amount sufficient to electrolytically deposit a metal such as Cu onto the substrate, a source of chloride ions in an amount sufficient to provide at least 70 mg/L chloride ions into the composition, and a source of a d-block metal ions selected from the group consisting of molybdenum, vanadium, zirconium, tantalum, tungsten, hafnium, and titanium.

1 . An electrolytic plating composition for electrolytically plating a metal onto a substrate, the composition comprising: 
 a source of deposition metal ions in an amount sufficient to electrolytically deposit the metal onto the substrate;    a source of chloride ions in an amount sufficient to provide chloride ions in a concentration of at least 70 mg/L;    and a source of d-block metal ions selected from the group consisting of molybdenum, vanadium, zirconium, tantalum, tungsten, hafnium, and titanium in an amount sufficient to provide between about 5 mg/L and about 5000 mg/L of the d-block metal ions.    
   
   
       2 . The composition of  claim 1  wherein the amount of the source of the d-block metal ion is sufficient to provide between about 200 mg/L and 1200 mg/L of the d-block metal ions.  
   
   
       3 . The composition of  claim 1  wherein the amount of the source of chloride ions is sufficient to provide between about 90 mg/L and about 5000 mg/L chloride ions.  
   
   
       4 . The composition of  claim 1  wherein the amount of the source of chloride ions is sufficient to provide between about 100 mg/L and about 300 mg/L chloride ions.  
   
   
       5 . The composition of  claim 1  wherein the amount of the source of chloride ions is sufficient to provide between about 120 mg/L and about 250 mg/L chloride ions.  
   
   
       6 . The composition of  claim 1  wherein the composition is for Cu plating under acidic conditions and the source of deposition metal ions is a source of Cu ions which provides a Cu ion concentration in the range of about 4 to about 70 g/L.  
   
   
       7 . The composition of  claim 1  wherein the composition is for Cu plating under acidic conditions and the source of deposition metal ions is a source of Cu ions which provides a Cu ion concentration in the range of about 4 to about 30 g/L.  
   
   
       8 . The composition of  claim 1  wherein the composition is for Cu plating under acidic conditions and the source of deposition metal ions is a source of Cu ions which provides a Cu ion concentration in the range of about 35 to about 60 g/L.  
   
   
       9 . The composition of  claim 1  wherein: 
 the composition is for Cu plating under acidic conditions;    the source of deposition metal ions is a source of Cu ions which provides a Cu ion concentration in the range of about 4 to about 70 g/L;    the source of the d-block metal ion is sufficient to provide between about 200 mg/L and 1200 mg/L of the d-block metal ions; and    the source of chloride ions is sufficient to provide between about 100 mg/L and about 300 mg/L chloride ions.    
   
   
       10 . The composition of  claim 1  wherein: 
 the composition is for Cu plating under acidic conditions;    the source of deposition metal ions is a source of Cu ions which provides a Cu ion concentration in the range of about 4 to about 70 g/L;    the source of the d-block metal ion is a source of molybdenum ion sufficient to provide between about 200 mg/L and 1200 mg/L of molybdenum ions as the d-block metal ions; and    the source of chloride ions is sufficient to provide between about 100 mg/L and about 300 mg/L chloride ions.    
   
   
       11 . The composition of  claim 1  wherein: 
 the composition is for Cu plating under acidic conditions;    the source of deposition metal ions is a source of Cu sulfate pentahydrate to provide a Cu ion concentration in the range of about 4 to about 70 g/L;    the source of the d-block metal ion is sodium molybdate to provide between about 200 mg/L and 1200 mg/L of molybdenum ions as the d-block metal ions; and    the source of chloride ions is sufficient to provide between about 100 mg/L and about 300 mg/L chloride ions.    
   
   
       12 . A process for electrolytic plating a metal deposit onto a substrate, the process comprising: 
 immersing the substrate into an electrolytic plating bath comprising: 
 a cathode;  
 an anode; and  
 an electrolytic plating composition comprising a source of deposition metal ions in an amount sufficient to electrolytically deposit the metal onto the substrate, a source of chloride ions in an amount sufficient to provide at least 70 mg/L chloride ions into the composition, and a source of a d-block metal ions selected from the group consisting of molybdenum, vanadium, zirconium, tantalum, tungsten, hafnium, and titanium in an amount sufficient to provide between about 5 mg/L and about 5000 mg/L of the d-block metal; and  
   supplying electrical current to the electrolytic plating bath to deposit metal onto the substrate.    
   
   
       13 . The process of  claim 12  wherein the electrolytic plating composition is an acid Cu plating composition and the anode comprises an anode base body comprising a carrier material and a precious metal-based active material.  
   
   
       14 . The process of  claim 12  wherein the electrolytic plating composition is an acid Cu plating composition and the anode comprises an anode base body comprising a carrier material and an active material selected from the group consisting of platinum, iridium, ruthenium, other precious metals, mixed oxides thereof, and compounds thereof.  
   
   
       15 . The process of  claim 13  wherein the carrier material is a material is selected from the group consisting of titanium, niobium, zirconium, hafnium, lanthanum, tantalum, tungsten, nickel, alloys of the foregoing, stainless steel alloys, nickel-plated steel, and nickel/cobalt plated steel.  
   
   
       16 . The process of  claim 14  wherein the carrier material is a material is selected from the group consisting of titanium, niobium, zirconium, hafnium, lanthanum, tantalum, tungsten, nickel, alloys of the foregoing, stainless steel alloys, nickel-plated steel, and nickel/cobalt plated steel.  
   
   
       17 . The process of  claim 12  wherein the anode comprises a screen and an anode base body.  
   
   
       18 . The process of  claim 12  wherein the anode comprises a screen and an anode base body comprising a carrier metal and a precious metal-based active material.  
   
   
       19 . The process of  claim 12  wherein the anode comprises a screen disposed around an anode base body with spacing between the screen and the anode base body, wherein the anode base body comprises a carrier metal and a precious metal-based active material.  
   
   
       20 . The process of  claim 19  wherein the screen is the fabric comprising an interwoven network of fibers.  
   
   
       21 . The process of  claim 20  he acidic electrolytic plating bath of  claim 15  wherein the fabric is constructed from a polypropylene.  
   
   
       22 . The acidic electrolytic plating bath of  claim 20  wherein the fabric is constructed of material selected from the group consisting of fiberglass, glass wool, glass filament, and refractory ceramic fibers (RCF).  
   
   
       23 . A process for electrolytic plating a metal deposit onto a substrate, the process comprising: 
 immersing the substrate into an electrolytic plating bath comprising: 
 a cathode;  
 an anode comprising a fabric screen disposed around and spaced apart from an anode base body comprising a carrier material and a precious metal-based active material; and  
 an electrolytic plating composition for acid Cu plating comprising a source of Cu ions to provide between about 4 g/L and about 70 g/L Cu ions, a source of chloride ions in an amount sufficient to provide between about 100 mg/L and about 300 mg/L chloride ions, and a source of a molybdenum ions sufficient to provide between about 200 mg/L and 1200 mg/L of molybdenum ions; and  
   supplying electrical current to the electrolytic plating bath to deposit Cu onto the substrate.