Copper plating solution for pr pulse electrolysis and copper plating method by means of pr pulse electrolysis

Abstract

An object of the present invention is to newly provide a copper plating solution for PR pulse electrolysis and a copper plating method by a PR pulse electrolysis method. Provided is a copper plating solution for PR pulse electrolysis, comprising a copper (II) ion, a polyvalent metal ion (excluding copper (II) ions), and an unsaturated fatty acid.

1 . A copper plating solution for PR pulse electrolysis, comprising:
 a copper (II) ion;   a polyvalent metal ion (excluding copper (II) ions); and   an unsaturated fatty acid.   
     
     
         2 . The copper plating solution for PR pulse electrolysis according to  claim 1 , wherein the polyvalent metal ion is an ion of at least one polyvalent metal selected from the group consisting of cobalt, iron, and cerium. 
     
     
         3 . The copper plating solution for PR pulse electrolysis according to  claim 1 , wherein the polyvalent metal ion is at least one polyvalent metal ion selected from the group consisting of cobalt (II), iron (II), and cerium (III). 
     
     
         4 . The copper plating solution for PR pulse electrolysis according to  claim 1 , wherein the copper plating solution for PR pulse electrolysis comprises 0.3 g/L to 3.0 g/L of the polyvalent metal ion. 
     
     
         5 . The copper plating solution for PR pulse electrolysis according to  claim 1 , wherein the unsaturated fatty acid is at least one unsaturated fatty acid selected from the group consisting of alkenes and alkynes. 
     
     
         6 . The copper plating solution for PR pulse electrolysis according to  claim 1 , wherein the unsaturated fatty acid is at least one unsaturated fatty acid selected from the group consisting of alkenes and alkynes having two or three carboxyl groups. 
     
     
         7 . The copper plating solution for PR pulse electrolysis according to  claim 1 , wherein the copper plating solution for PR pulse electrolysis comprises 0.5 g/L to 10 g/L of the unsaturated fatty acid. 
     
     
         8 . The copper plating solution for PR pulse electrolysis according to  claim 1 , wherein the copper plating solution for PR pulse electrolysis further comprises an acid component and is an acidic aqueous solution. 
     
     
         9 . The copper plating solution for PR pulse electrolysis according to  claim 1 , further comprising a halide ion. 
     
     
         10 . The copper plating solution for PR pulse electrolysis according to  claim 1 , further comprising a sulfur-containing organic compound. 
     
     
         11 . The copper plating solution for PR pulse electrolysis according to  claim 1 , wherein the copper plating solution for PR pulse electrolysis has a total content of at least one amine compound selected from the group consisting of tertiary amine compounds and quaternary amine compounds of less than 1 mg/L. 
     
     
         12 . A copper plating method by a PR pulse electrolysis method, comprising:
 (1) allowing a PR pulse current to pass through a copper plating solution for PR pulse electrolysis to perform electrolytic copper plating by using an object to be plated as a cathode,   wherein the copper plating solution for PR pulse electrolysis comprises:   a copper (II) ion;   a polyvalent metal ion (excluding copper (II) ions); and   an unsaturated fatty acid.   
     
     
         13 . The copper plating method by a PR pulse electrolysis method according to  claim 12 , wherein step (1) is performed under PR pulse electrolysis conditions of a current density ratio of anode to cathode (anode current density/cathode current density) of 0.2 to 0.85. 
     
     
         14 . The copper plating method by a PR pulse electrolysis method according to  claim 12 , wherein step (1) is performed under PR pulse electrolysis conditions of a positive current application time of 5 milliseconds to 200 milliseconds, and an application time ratio of positive to negative currents (positive current application time/negative current application time) of 5 or more and less than 50.