Cyanide-Free Copper Preplating Electroplating Solution and Preparation Method Therefor

Abstract

The present invention relates to a cyanide-free copper-preplating electroplating solution, wherein the electroplating solution is prepared from following components in mass percent: 1-60% of complexing agent, 0.5-30% of copper salt and the balance of water, wherein the complexing agent has a general formula M x H y P n O 3n+1 R z , wherein M is any one or more of alkali metal ions and NH4+, R is acyl, the copper salt has a general formula Cu x/2 H y P n O 3n+1 R z , x, n and z are positive integers, y is 0 or a positive integer and x+y+z=n+2. A preparing method comprises: (1) preparing a complexing agent: mixing alkali, carbonate or bicarbonate containing M, phosphoric acid and an acidic salt of monoprotic organic acids or polybasic organic acids containing an R group for reacting according to a molar ratio, then carrying one step polymerization on a reaction solution at 100-800° C. for 0.5-10h to obtain a finished product of the complexing agent; (2) preparing a copper salt: uniformly mixing the complexing agent prepared in step (1) with a bivalent copper compound in a water phase system according to a molar ratio, reacting for 0.5-1.0h at 25-100° C., and centrifuging for separation and drying to obtain the copper salt after the reaction; (3) preparing an electroplating solution: uniformly and proportionally mixing respective components to obtain the electroplating solution.

1 . A cyanide-free copper preplating electroplating solution, wherein the electroplating solution is prepared from following components in mass percent: 1-60% of complexing agent, 0.3-20% of copper salt and the balance of water, wherein the complexing agent has a general formula M x H y P n O 3n+1 R z , wherein M is any one or more of alkali metal ions and NH 4   + , R is acyl, the copper salt has a general formula Cu x/2  H y P n O 3n+1 R z , x, n and z are positive integers, y is 0 or a positive integer, and x+y+z=n+2. 
     
     
         2 . A cyanide-free copper preplating electroplating solution, wherein the electroplating solution is prepared from following components in mass percent: 20-45% of complexing agent, 0.5-10% of copper salt and the balance of water, wherein the complexing agent has a general formula M x H y P n O 3n+1 R, wherein M is any one or more of Na + , K +  and NH 4   + , R is acyl, the copper salt has a general formula Cu x/2 H y P n O 3n+1 R, x and n are positive integers, y is 0 or a positive integer, and x+y=n+1. 
     
     
         3 . A method of preparing the cyanide-free copper preplating electroplating solution of  claim 1 , the method comprising:
 (1) preparing the complexing agent by a method that comprises mixing alkali, carbonate or bicarbonate containing M, phosphoric acid and an acidic salt of monoprotic organic acids or polybasic organic acids containing an R group according to a molar ratio to form a reaction solution, optionally drying the reaction solution, and performing one step polymerization of the reaction solution at 100-800° C. for 0.5-10 hours to obtain the complexing agent;   (2) preparing a copper salt by a method that comprises uniformly mixing the complexing agent prepared in step (1) with a bivalent copper compound in a water phase system according to a molar ratio, reacting for 0.5-1 hour at 25-100° C., and separating and drying the copper salt after the reaction; and   (3) preparing an electroplating solution by a method that comprises dissolving the complexing agent in step (1) in water, dissolving the copper salt in step (2) in the complexing agent water solution in proportion, supplementing the balance of water to form a solution, uniformly mixing the solution, and adjusting a pH value of the solution to 8.5-9.5 to obtain the cyanide-free copper preplating electroplating solution.   
     
     
         4 . The method of  claim 3 , wherein M is Na + , the complexing agent in step (1) is prepared by a method that comprises mixing sodium hydroxide, sodium carbonate or sodium bicarbonate, phosphoric acid and an acidic salt of monoprotic organic acids or polybasic organic acids containing an R group according to a molar ratio to form a reaction solution, and performing one step polymerization on a reaction solution at 200-400° C. for 0.5-10 hours to obtain the complexing agent. 
     
     
         5 . The method of  claim 3 , wherein M is K + , the complexing agent in step (1) is prepared by a method that comprises mixing potassium hydroxide, potassium carbonate or potassium bicarbonate, phosphoric acid and an acidic salt of monoprotic organic acids or polybasic organic acids containing an R group according to a molar ratio to form a reaction solution, and performing one step polymerization on a reaction solution at 250-800° C. for 0.5-10 hours to obtain the complexing agent. 
     
     
         6 . The method of  claim 3 , wherein M is NH 4   + , the complexing agent in step (1) is prepared by a method that comprises mixing ammonium hydroxide, ammonium carbonate or ammonium bicarbonate, phosphoric acid and an acidic salt of monoprotic organic acids or polybasic organic acids containing an R group according to a molar ratio to form a reaction solution, and performing one step polymerization on a reaction solution under 100-300° C. for 0.5-10 hours to obtain the complexing agent. 
     
     
         7 . The cyanide-free copper preplating electroplating solution of  claim 1 , wherein the copper salt is selected from the group consisting of copper sulfate, copper chloride, basic copper carbonate, and a mixture thereof. 
     
     
         8 . A method of preparing the cyanide-free copper preplating electroplating solution of  claim 7 , the method comprising:
 (1) preparing the complexing agent by a method that comprises mixing alkali, carbonate or bicarbonate containing M, phosphoric acid and an acidic salt of monoprotic organic acids or polybasic organic acids containing an R group according to a molar ratio to form a reaction solution, optionally drying the reaction solution, and performing one step polymerization of the reaction solution at 100-800° C. for 0.5-10 hours to obtain the complexing agent; and   (2) preparing an electroplating solution by a method that comprises dissolving the complexing agent in step (1) in water, dissolving the copper salt in the complexing agent water solution in proportion, supplementing the balance of water to form a solution, and adjusting a pH value of the solution to 8.5-9.5 to obtain the cyanide-free copper preplating electroplating solution.   
     
     
         9 . A method of preparing the cyanide-free copper preplating electroplating solution of  claim 2 , the method comprising:
 (1) preparing the complexing agent by a method that comprises mixing alkali, carbonate or bicarbonate containing M, phosphoric acid and an acidic salt of monoprotic organic acids or polybasic organic acids containing an R group according to a molar ratio to form a reaction solution, optionally drying the reaction solution, and performing one step polymerization of the reaction solution at 100-800° C. for 0.5-10 hours to obtain the complexing agent;   (2) preparing a copper salt by a method that comprises uniformly mixing the complexing agent prepared in step (1) with a bivalent copper compound in a water phase system according to a molar ratio, reacting for 0.5-1 hour at 25-100° C., and separating and drying the copper salt after the reaction; and   (3) preparing an electroplating solution by a method that comprises dissolving the complexing agent in step (1) in water, dissolving the copper salt in step (2) in the complexing agent water solution in proportion, supplementing the balance of water to form a solution, uniformly mixing the solution, and adjusting a pH value of the solution to 8.5-9.5 to obtain the cyanide-free copper preplating electroplating solution.   
     
     
         10 . The method of  claim 9 , wherein M is Na + , the complexing agent in step (1) is prepared by a method that comprises mixing sodium hydroxide, sodium carbonate or sodium bicarbonate, phosphoric acid and an acidic salt of monoprotic organic acids or polybasic organic acids containing an R group according to a molar ratio to form a reaction solution, and performing one step polymerization on a reaction solution at 200-400° C. for 0.5-10 hours to obtain the complexing agent. 
     
     
         11 . The method of  claim 9 , wherein M is K + , the complexing agent in step (1) is prepared by a method that comprises mixing potassium hydroxide, potassium carbonate or potassium bicarbonate, phosphoric acid and an acidic salt of monoprotic organic acids or polybasic organic acids containing an R group according to a molar ratio to form a reaction solution, and performing one step polymerization on a reaction solution at 250-800° C. for 0.5-10 hours to obtain the complexing agent. 
     
     
         12 . The method of  claim 9 , wherein M is NH 4   + , the complexing agent in step (1) is prepared by a method that comprises mixing ammonium hydroxide, ammonium carbonate or ammonium bicarbonate, phosphoric acid and an acidic salt of monoprotic organic acids or polybasic organic acids containing an R group according to a molar ratio to form a reaction solution, and performing one step polymerization on a reaction solution under 100-300° C. for 0.5-10 hours to obtain the complexing agent. 
     
     
         13 . The cyanide-free copper preplating electroplating solution of  claim 2 , wherein the copper salt is selected from the group consisting of copper sulfate, copper chloride, basic copper carbonate, and a mixture thereof. 
     
     
         14 . A method of preparing the cyanide-free copper preplating electroplating solution of  claim 13 , the method comprising:
 (1) preparing the complexing agent by a method that comprises mixing alkali, carbonate or bicarbonate containing M, phosphoric acid and an acidic salt of monoprotic organic acids or polybasic organic acids containing an R group according to a molar ratio to form a reaction solution, optionally drying the reaction solution, and performing one step polymerization of the reaction solution at 100-800° C. for 0.5-10 hours to obtain the complexing agent; and   (2) preparing an electroplating solution by a method that comprises dissolving the complexing agent in step (1) in water, dissolving the copper salt in the complexing agent water solution in proportion, supplementing the balance of water to form a solution, and adjusting a pH value of the solution to 8.5-9.5 to obtain the cyanide-free copper preplating electroplating solution.