Nickel (alloy) electroplating solution

Abstract

The invention provides a nickel (alloy) electroplating solution which can fill minute holes or minute recesses 14 in the electronic circuit components 14 with the nickel or nickel alloy 18 without producing voids or seams, and can join two or more electronic components firmly together by filling minute gaps. The invention further provides a method of nickel or nickel alloy plating and filling using the aforesaid nickel (alloy) electroplating solution, a method of manufacturing a minute 3-dimensional structure, an electronic component assembly, and a method of manufacturing the same. The aforesaid problems in filling the minute holes or minute recesses 14 are overcome by using a nickel (alloy) electroplating solution containing a specific N-substituted pyridinium compound.

1 - 21 . (canceled) 
     
     
         22 . A nickel electroplating solution or nickel alloy electroplating solution containing a nickel salt, a pH buffer and an N-substituted pyridinium compound represented by the following general formula (A) or (B): 
       
         
           
           
               
               
           
         
         In the general formula (A), —R 1  is an alkyl group, alkylamino group or cyanoalkyl group, having 1-6 carbon atoms, an amino group (—NH 2 ) or a cyano group, —R 2  is a hydrogen atom, an alkyl group or hydroxyalkyl group having 1-6 carbon atoms, a vinyl group, a methoxycarbonyl group (—CO—O—CH 3 ), a carbamoyl group (—CO—NH 2 ), a dimethylcarbamoyloxy group (—O—CO—N(CH 3 ) 2 ), or an aldoxime group (—CH═NOH), and X −  is an arbitrary anion 
       
       
         
           
           
               
               
           
         
         In the general formula (B), —R 3  is a hydrogen atom or a hydroxyl group (—OH), —R 4  is a hydrogen atom, an alkyl group having 1-6 carbon atoms, a vinyl group, or a carbamoyl group (—CO—NH 2 ), and m is 0, 1, or 2. 
       
     
     
         23 . The nickel electroplating solution or nickel alloy electroplating solution according to  claim 22  where X −  is a halide ion. 
     
     
         24 . The nickel electroplating solution or nickel alloy electroplating solution according to  claim 22  wherein said nickel salt is one or more selected from the group consisting of nickel sulfate, nickel sulfamate, nickel chloride, nickel bromide, nickel carbonate, nickel nitrate, nickel formate, nickel acetate, nickel citrate, and nickel fluoroboride. 
     
     
         25 . The nickel electroplating solution or nickel alloy electroplating solution according to any of  claim 22 , wherein said pH buffer is one or more selected from the group consisting of boric acid, meta-boric acid, acetic acid, tartaric acid, citric acid, and salts thereof. 
     
     
         26 . The nickel electroplating solution or nickel alloy electroplating solution according to  claim 22 , wherein the N-substituted pyridinium compound represented by the general formula (A) is one or more compounds selected from the group consisting of halide of 1-methyl pyridinium, halide of 1-ethyl pyridinium, halide of 1-propyl pyridinium, halide of 1-butyl pyridinium, halide of 1-pentyl pyridinium, halide of 1-hexyl pyridinium, halide of 1-ethyl-3-(hydroxymethyl) pyridinium, halide of 1-ethyl 4-(methoxy carbonyl) pyridinium, halide of 1-butyl-4-methyl pyridinium, halide of 1-butyl-3-methyl pyridinium, halide of 1-methyl pyridinium 2-aldoxime, halide of 3-carbamoyl-1-methyl pyridinium, halide of 3-(dimethylcarbamoyloxy)-1-methyl pyridinium, and halide of 1-(cyanomethyl) pyridinium. 
     
     
         27 . The nickel electroplating solution or nickel alloy electroplating solution according to  claim 22 , wherein the N-substituted pyridinium compound represented by the general formula (B) is one or more compounds selected from the group consisting of 1-(3-sulfonate propyl) pyridinium, 1-(2-sulfonate ethyl) pyridinium, 1-(4-sulfonate butyl) pyridinium, 2-vinyl 1-(3-sulfonate propyl) pyridinium, 3-vinyl 1-(3-sulfonate propyl) pyridinium, 4-vinyl 1-(3-sulfonate propyl) pyridinium, 2-methyl 1-(3-sulfonate propyl) pyridinium, 3-methyl 1-(3-sulfonate propyl) pyridinium, 4-methyl 1-(3-sulfonate propyl) pyridinium, 2-ethyl 1-(3-sulfonate propyl) pyridinium, 3-ethyl 1-(3-sulfonate propyl) pyridinium, 4-ethyl 1-(3-sulfonate propyl) pyridinium, 2-vinyl 1-(4-sulfonate butyl) pyridinium, 3-vinyl 1-(4-sulfonate butyl) pyridinium, 4-vinyl 1-(4-sulfonate butyl) pyridinium, 2-methyl 1-(4-sulfonate butyl) pyridinium, 3-methyl 1-(4-sulfonate butyl) pyridinium, 4-methyl 1-(4-sulfonate butyl) pyridinium, 2-ethyl 1-(4-sulfonate butyl) pyridinium, 3-ethyl 1-(4-sulfonate butyl) pyridinium, 4-ethyl 1-(4-sulfonate butyl) pyridinium, 4-tert-butyl-1-(3-sulfonate propyl) pyridinium, 2,6-dimethyl-1-(3-sulfonate propyl) pyridinium, 3-(amino carbonyl)-1-(3-sulfonate propyl) pyridinium, 1-(2-hydroxy-3-sulfonate propyl) pyridinium, 1-(2-hydroxy-3-sulfonate propyl) pyridinium, 3-vinyl 1-(2-hydroxy-3-sulfonate propyl) pyridinium, 4-vinyl 1-(2-hydroxy-3-sulfonate propyl) pyridinium, 2-methyl 1-(2-hydroxy-3-sulfonate propyl) pyridinium, 3-methyl 1-(2-hydroxy-3-sulfonate propyl) pyridinium, 4-methyl 1-(2-hydroxy-3-sulfonate propyl) pyridinium, 2-ethyl 1-(2-hydroxy-3-sulfonate propyl) pyridinium, 3-ethyl 1-(2-hydroxy-3-sulfonate propyl) pyridinium, and 4-ethyl 1-(2-hydroxy-3-sulfonate propyl) pyridinium. 
     
     
         28 . The nickel electroplating solution or nickel alloy electroplating solution according to any of  claim 22 , used for filling a minute hole or a minute recess in an electronic component, or a minute gap formed when electronic components are superposed on one another. 
     
     
         29 . A method of manufacturing a nickel deposit or a nickel alloy deposit, wherein electroplating is performed using the nickel electroplating solution or nickel alloy electroplating solution according to  claim 22 . 
     
     
         30 . A method of manufacturing an electronic component in which a minute hole or minute recess is filled with a nickel deposit or a nickel alloy deposit, wherein electroplating is performed using the nickel electroplating solution or nickel alloy electroplating solution according to  claim 22 . 
     
     
         31 . A method of manufacturing an electronic component in which a minute hole or minute recess is filled with a nickel deposit or a nickel alloy deposit, wherein, after first performing electroplating on the surface of the minute hole or minute recess, said electronic component is immersed in a nickel electroplating solution or nickel alloy electroplating solution according to  claim 22 , and electroplating is performed using an external power supply. 
     
     
         32 . The method of manufacturing an electronic component in which the minute hole or minute recess is filled with a nickel deposit or a nickel alloy deposit according to  claim 31 , wherein when electroplating is performed using an external power supply the minimum plating cross section film thickness X 2  in the minute hole or minute recess is made to be larger than the maximum plating cross section film thickness X 1  of the peripheral part outside the minute hole or minute recess. 
     
     
         33 . A method of manufacturing a minute three-dimensional structure, comprising a step wherein a minute hole or a minute recess is electroplated and filled by the manufacturing method according to  claim 30 . 
     
     
         34 . A method of manufacturing a minute three-dimensional structure, comprising a step wherein a minute hole or a minute recess is electroplated and filled by the manufacturing method according to  claim 31 . 
     
     
         35 . A method of manufacturing an electronic component assembly, wherein, when two or more electronic components are superposed and a minute gap is formed therebetween, said two or more electronic components are immersed in a nickel electroplating solution or nickel alloy electroplating solution according to  claim 22 , and electroplating is performed using an external power supply. 
     
     
         36 . An electronic component assembly wherein two or more electronic components are joined together by nickel or a nickel alloy, and a larger amount of nickel or nickel alloy is deposited in the vicinity of the minute gap formed between the electronic components than in other parts. 
     
     
         37 . A one-sided electronic component assembly terminal formed of nickel or a nickel alloy, comprising a plug embedded in a material of thickness 1 mm or less in a substantially perpendicular direction relative to the material surface but not penetrating said material, and a cap having an outer diameter greater than the outer diameter of said plug such that it is in contact with said plug, wherein the outer diameter of said cap is 200 μm or less, and said cap projects from the surface of said material. 
     
     
         38 . A two-sided electronic component assembly terminal formed of nickel or a nickel alloy, comprising a plug embedded in a material of thickness 1 mm or less in a substantially perpendicular direction relative to the material surface and penetrating said material, and two caps having an outer diameter greater than the outer diameter of said plug such that they are respectively in contact with said plug, wherein the outer diameter of each of said two caps is 200 μm or less, and said two caps project from the respective surfaces of said material. 
     
     
         39 . A one-sided electronic component assembly terminal formed of nickel or a nickel alloy, comprising a plug embedded in a material of thickness 1 mm or less in a substantially perpendicular direction relative to the material surface but not penetrating said material, wherein the outer diameter of said plug is 100 μm or less. 
     
     
         40 . A two-sided electronic component assembly terminal formed of nickel or a nickel alloy, comprising a plug embedded in a material of thickness 1 mm or less in a substantially perpendicular direction relative to the material surface and penetrating said material, wherein the outer diameter of said plug is 100 μm or less. 
     
     
         41 . An electronic component assembly terminal according to any of  claim 37 , wherein there is no void in said plug having a maximum width greater than 10 μm. 
     
     
         42 . An electronic component assembly terminal according to any of  claim 38 , wherein there is no void in said plug having a maximum width greater than 10 μm. 
     
     
         43 . An electronic component assembly terminal according to any of  claim 39 , wherein there is no void in said plug having a maximum width greater than 10 μm. 
     
     
         44 . An electronic component assembly terminal according to any of  claim 40 , wherein there is no void in said plug having a maximum width greater than 10 μm. 
     
     
         45 . An electronic component assembly terminal according to  claim 37 , formed using a nickel electroplating solution or nickel alloy electroplating solution. 
     
     
         46 . An electronic component assembly terminal according to  claim 38 , formed using a nickel electroplating solution or nickel alloy electroplating solution. 
     
     
         47 . An electronic component assembly terminal according to  claim 39 , formed using a nickel electroplating solution or nickel alloy electroplating solution. 
     
     
         48 . An electronic component assembly terminal according to  claim 40 , formed using a nickel electroplating solution or nickel alloy electroplating solution.