Electroplating aqueous solution and method of making and using same

Abstract

In one embodiment of the invention, an electroplating aqueous solution is disclosed. The electroplating aqueous solution includes at least two acids, copper, at least one accelerator agent, and at least two suppressor agents. The at least one accelerator agent provides an acceleration strength of at least about 2.0 and the at least two suppressor agents, collectively, provide a suppression strength of at least about 5.0. Methods of making and using such an electroplating aqueous solution are also disclosed.

1 . An electroplating aqueous solution, comprising:
 at least two acids;   copper;   at least one accelerator agent that provides an acceleration strength of at least about 2.0; and   at least two suppressor agents that collectively provide a suppression strength of at least about 5.0.   
     
     
         2 . The electroplating aqueous solution of  claim 1  wherein the at least two acids comprise one or more of the following acids:
 sulfuric acid;   hydrochloric acid;   hydroiodic acid;   hydroboric acid; and   fluoroboric acid.   
     
     
         3 . The electroplating aqueous solution of  claim 1  wherein the at least two acids comprise:
 sulfuric acid present in a concentration from about 5 grams per liter to about 20 grams per liter; and   hydrochloric acid present in a concentration from about 20 milligrams per liter to about 100 milligrams per liter.   
     
     
         4 . The electroplating aqueous solution of  claim 1  wherein the copper is present in a concentration from about 50 grams per liter to about 100 grams per liter. 
     
     
         5 . The electroplating aqueous solution of  claim 1  wherein the concentration is at least about 85 grams per liter. 
     
     
         6 . The electroplating aqueous solution of  claim 1  wherein the at least one accelerator agent comprises at least one of:
 a sulfide compound;   a selenium-containing anion; and   a tellurium-containing anion.   
     
     
         7 . The electroplating aqueous solution of  claim 1  wherein the at least two suppressor agents comprise one or more of the following suppressor agents:
 a surfactant;   a chelating agent;   a leveler agent; and   a wetting agent.   
     
     
         8 . The electroplating aqueous solution of  claim 1  wherein the at least two suppressor agents comprise one or more of the following suppressor agents:
 a quaternized polyamine; a polyacrylamide; a cross-linked polyamide;   a phenazine azo-dye; an alkoxylated amine surfactant; a polyether surfactant; a non-ionic surfactant; a cationic surfactant;   an anionic surfactant; a block copolymer surfactant; polyacrylic acid; a polyamines; aminocarboxylic acid;   hydrocarboxylic acid; citric acid; entprol; edetic acid; and tartaric acid.   
     
     
         9 . The electroplating aqueous solution of  claim 1  wherein:
 the at least one accelerator agent is present in a concentration from about 10 milligrams per liter to about 1000 milligrams per liter; and   the at least two suppressor agents are collectively present in a concentration from about 10 milligrams per liter to about 1000 milligrams per liter.   
     
     
         10 . The electroplating aqueous solution of  claim 1  wherein:
 the at least two acids are, collectively, present in a concentration from about 5 grams per liter to about 20 grams per liter; and   the copper is present in a concentration from about 50 grams per liter to about 100 grams per liter.   
     
     
         11 . A method of electroplating, comprising:
 immersing a substrate in an electroplating aqueous solution, the electroplating aqueous solution comprising:
 at least two acids; 
 copper; 
 at least one accelerator agent that provides an acceleration strength of at least about 2.0; and 
 at least two suppressor agents that collectively provide a suppression strength of at least about 5.0; and 
   electroplating at least a portion of the copper from the electroplating aqueous solution onto the substrate.   
     
     
         12 . The method of  claim 11 , further comprising linearly oscillating the substrate in the electroplating aqueous solution during the act of electroplating. 
     
     
         13 . The method of  claim 12  wherein linearly oscillating the substrate in the electroplating aqueous solution comprises:
 linearly oscillating the substrate in the bath at a rate of about 10 millimeters per second to about 1000 millimeters per second.   
     
     
         14 . The method of  claim 11 , further comprising rotating the substrate in the electroplating aqueous solution during the act of electroplating. 
     
     
         15 . The method of  claim 14  wherein rotating the substrate in the electroplating aqueous solution comprises:
 rotating the substrate in the electroplating aqueous solution at a rate of about 150 revolutions per minute to about 300 revolutions per minute.   
     
     
         16 . The method of  claim 14 :
 wherein the substrate comprises a surface to be electroplated with the copper; and   further comprising orienting the surface in an upwardly facing direction or downwardly facing direction.   
     
     
         17 . The method of  claim 14 :
 wherein the substrate comprises a surface to be electroplated with the copper;   further comprising moving the substrate in a manner that maintains the surface substantially parallel to a longitudinal axis of an anode immersed in the electroplating aqueous solution.   
     
     
         18 . The method of  claim 11  wherein electroplating at least a portion of the copper from the electroplating aqueous solution onto the substrate comprises:
 depositing the copper on the substrate as a substantially dendrite-free film at a deposition rate of at least 10 micrometers per minute.   
     
     
         19 . The method of  claim 11 , further comprising adding additional copper to the electroplating aqueous solution provided from a consumable anode immersed in the electroplating aqueous solution. 
     
     
         20 . The method of  claim 11 , further comprising replenishing the electroplating aqueous solution with additional copper introduced into the electroplating aqueous solution. 
     
     
         21 . The method of  claim 11 , further comprising:
 prior to immersing the substrate in the electroplating aqueous solution, cleaning the substrate in a cleaning solution that includes at least one suppressor agent having the same composition as one of the at least two suppressor agents of the electroplating aqueous solution.   
     
     
         22 . The method of  claim 11 , further comprising maintaining the electroplating aqueous solution at a temperature between about 20° Celsius to about 60° Celsius. 
     
     
         23 . The method of  claim 11 :
 wherein the substrate comprises a surface to be electroplated with the copper; and   further comprising spacing the surface a distance of about 0.1 centimeter to about 10 centimeter from an anode immersed in the electroplating aqueous solution.   
     
     
         24 . The method of  claim 11  wherein the at least two acids of the electroplating aqueous solution comprise one or more of the following acids:
 sulfuric acid;   hydrochloric acid;   hydroiodic acid;   hydroboric acid; and   fluoroboric acid.   
     
     
         25 . The method of  claim 11  wherein the at least two acids of the electroplating aqueous solution comprise:
 sulfuric acid present in a concentration from about 5 grams per liter to about 20 grams per liter; and   hydrochloric acid present in a concentration from about 20 milligrams per liter to about 100 milligrams per liter.   
     
     
         26 . The method of  claim 11  wherein the copper of the electroplating aqueous solution is present in a concentration from about 50 grams per-liter to about 100 grams per liter. 
     
     
         27 . The method of  claim 11  wherein the at least one accelerator agent of the electroplating aqueous solution comprises at least one of:
 a sulfide compound;   a selenium-containing anion; and   a tellurium-containing anion.   
     
     
         28 . The method of  claim 11  wherein the at least two suppressor agents of the electroplating aqueous solution comprise one or more of the following suppressor agents:
 a surfactant;   a chelating agent;   a leveler agent; and   a wetting agent.   
     
     
         29 . The method of  claim 11  wherein the at least two suppressor agents of the electroplating aqueous solution comprise one or more of the following suppressor agents:
 a quaternized polyamine; a polyacrylamide; a cross-linked polyamide;   a phenazine azo-dye; an alkoxylated amine surfactant; a polyether surfactant; a non-ionic surfactant; a cationic surfactant;   an anionic surfactant; a block copolymer surfactant; polyacrylic acid; a polyamines; aminocarboxylic acid;   hydrocarboxylic acid; citric acid; entprol; edetic acid; and tartaric acid.   
     
     
         30 . The method of  claim 11  wherein:
 the at least one accelerator agent is present in a concentration from about 10 milligrams per liter to about 1000 milligrams per liter; and   the at least two suppressor agents are collectively present in a concentration from about 10 milligrams per liter to about 1000 milligrams per liter.   
     
     
         31 . The method of  claim 11  wherein:
 the at least two acids of the electroplating aqueous solution are, collectively, present in a concentration from about 5 grams per liter to about 20 grams per liter; and   the copper of the electroplating aqueous solution is present in a concentration from about 50 grams per liter to about 100 grams per liter.   
     
     
         32 . A method of making an electroplating aqueous solution, comprising:
 maintaining an electroplating aqueous solution at a first temperature, the electroplating aqueous solution including:
 at least two acids; 
 copper present in a concentration below a copper solubility limit, at the first temperature, of the at least two acids; 
   heating the electroplating aqueous solution to a second temperature that is greater than the first temperature; and   introducing additional copper from a copper source to the electroplating aqueous solution when the electroplating aqueous solution is at the second temperature so that the electroplating aqueous solution exhibits a copper concentration of at least about 50 grams per liter.   
     
     
         33 . The method of  claim 32  wherein introducing additional copper from a copper source comprises:
 introducing additional copper in a concentration that is less than a copper solubility limit of the at least two acids at the electroplating temperature.   
     
     
         34 . The method of  claim 32  wherein introducing additional copper comprises:
 introducing the additional copper into the electroplating aqueous solution in an amount so that the copper concentration is about 50 grams per liter to about 100 grams per liter at the second temperature.   
     
     
         35 . The method of  claim 32  wherein introducing additional copper from a copper source comprises:
 introducing the additional copper into the electroplating aqueous solution in an amount so that the copper concentration is about 85 grams per liter or more at the second temperature.   
     
     
         36 . The method of  claim 32  wherein the copper source comprises at least one of:
 a copper salt;   copper oxide; and   copper hydroxide.   
     
     
         37 . The method of  claim 31  wherein the electroplating aqueous solution comprises at least one accelerator agent that provides an acceleration strength of at least about 2.0 and at least two suppressor agents that collectively provides a suppression strength of at least about 5.0.