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US20190330753A1 - Nickel (alloy) electroplating solution - Google Patents

Nickel (alloy) electroplating solution Download PDF

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Publication number
US20190330753A1
US20190330753A1 US16/349,740 US201716349740A US2019330753A1 US 20190330753 A1 US20190330753 A1 US 20190330753A1 US 201716349740 A US201716349740 A US 201716349740A US 2019330753 A1 US2019330753 A1 US 2019330753A1
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Prior art keywords
nickel
pyridinium
electroplating solution
sulfonate
minute
Prior art date
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US16/349,740
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English (en)
Inventor
Kazuya Shibata
Yuki Oohirabaru
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Japan Pure Chemical Co Ltd
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Japan Pure Chemical Co Ltd
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Assigned to JAPAN PURE CHEMICAL CO., LTD. reassignment JAPAN PURE CHEMICAL CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: OOHIRABARU, YUKI, SHIBATA, KAZUYA
Publication of US20190330753A1 publication Critical patent/US20190330753A1/en
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
    • C25D3/14—Electroplating: Baths therefor from solutions of nickel or cobalt from baths containing acetylenic or heterocyclic compounds
    • C25D3/18—Heterocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/02—Electroplating of selected surface areas
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/12—Semiconductors
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/12—Semiconductors
    • C25D7/123—Semiconductors first coated with a seed layer or a conductive layer
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
    • H05K3/42—Plated through-holes or plated via connections
    • H05K3/423—Plated through-holes or plated via connections characterised by electroplating method
    • H10P14/47—

Definitions

  • the present invention relates to a nickel electroplating solution and nickel alloy electroplating solution (hereafter, these are referred to generally as “nickel (alloy) electroplating solution”. Besides, “nickel or nickel alloy”, which is deposited by using a “nickel (alloy) electroplating solution”, is referred to as “nickel (alloy)”.), and more specifically, to a nickel (alloy) electroplating solution suitable for filling minute holes or minute recesses in electronic components, or minute gaps between two or more electronic components which are superposed.
  • the present invention further relates to a method of filling minute holes or minute recesses using this nickel (alloy) electroplating solution, a method of manufacturing a minute three-dimensional structure, an electronic component assembly, and a method of manufacturing the same.
  • Electronic circuit parts such as semiconductors and printed circuit boards have minute holes and minute recesses, such as via for forming wiring, throughholes, and trenches.
  • a staggered via structure is usually formed wherein, after performing conformal copper plating of the wall surface of the vias, they are connected to other layers in a staggered arrangement.
  • the copper electroplating solution contained two or more additives, and the vias were filled by controlling their optimal concentration balance, even if it were possible to fill so that there were no macrovoids of the order of several ⁇ m, a side effect of the additives was that microvoids of nm order remained.
  • Copper is a metal whereof the melting point is not very high (1083° C.), and it is well known that recrystallization occurs after copper electroplating even after standing at room temperature. Hence, there was a problem that, as a result of the condensation of microvoids of nm order in this recrystallization process, macroscopic voids were eventually formed.
  • non-patent document 1 it is reported that when polyethylene glycol (PEG) which is an additive is partly taken up by a copper film, microvoids of nm order are formed in the copper film, and in the copper recrystallization process, on standing at room temperature, large voids of diameter 70 nm are formed.
  • PEG polyethylene glycol
  • the copper filling method which uses a copper electroplating solution has this potential problem, and there is a risk that as the wiring becomes still finer, due to growth of voids and movement of voids resulting from the condensation of microvoids, the reliability of the wiring may be compromised.
  • the present invention was conceived in view of the problems inherent in the aforesaid prior art, and aims to provide a nickel (alloy) electroplating solution which can fill minute holes and minute recesses in electronic circuit components without generating defects such as voids and seams, to provide a nickel or nickel alloy filling method using said nickel (alloy) electroplating solution, and a method of manufacturing a minute three-dimensional structure.
  • the inventor has intensively studied to solve the above-mentioned problems, and as a result, the inventor has found that by using a nickel electroplating solution containing a specific N-substituted pyridinium compound, minute holes or minute recesses could be filled with nickel without generating defects such as voids, and thereby arrived at the present invention.
  • the present invention provides 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):
  • —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 2 ) 2 ), or an aldoxime group (—CH ⁇ NOH)
  • X ⁇ is an arbitrary anion.
  • the present invention further provides a nickel electroplating solution or nickel alloy electroplating solution containing a nickel salt, pH buffer, and an N-substituted pyridinium compound represented by the following 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 )
  • m is 0, 1, or 2.
  • the present invention further provides a method of manufacturing a nickel deposit or a nickel alloy deposit by performing nickel electroplating using said nickel electroplating solution or nickel alloy electroplating solution.
  • the present invention further provides a method of manufacturing electronic components wherein minute holes or minute recesses are filled with a nickel deposit or nickel alloy deposit by performing electroplating using said nickel electroplating solution or nickel alloy electroplating solution.
  • the present invention further provides a method of manufacturing electronic components wherein, after first forming an electroplating seed layer on the surface of minute holes or minute recesses in the electronic components, said minute holes or minute recesses are filled with a nickel deposit or nickel alloy deposit by immersing the electronic components in said nickel electroplating solution or nickel alloy electroplating solution, and performing electroplating using an external power supply.
  • the present invention further provides a method of manufacturing a minute three-dimensional structure including a step of filling minute holes or minute recesses by plating using the aforesaid manufacturing method.
  • the present invention further provides a method of manufacturing an electronic component assembly wherein, when two or more electronic components are superposed and minute gaps are formed therebetween, the gaps are filled by immersing the two or more electronic components in said nickel electroplating solution or nickel alloy electroplating solution, and performing electroplating using an external power supply.
  • the present invention further provides 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.
  • the present invention further provides a one-sided electronic component junction 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 the material, and a cap having an outer diameter greater than the outer diameter of the plug such that it is in contact therewith, wherein the outer diameter of this cap is 200 ⁇ m or less, and the cap projects from the surface of the material.
  • the present invention further provides a two-sided electronic component junction 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 the material, and two caps having an outer diameter greater than the outer diameter of the plug such that they are respectively in contact therewith, wherein the outer diameter of each of the two caps is 200 ⁇ m or less, and the two caps project from the respective surfaces of the material.
  • the present invention further provides a one-sided electronic component junction 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 the material, wherein the outer diameter of the plug is 100 ⁇ m or less.
  • the present invention further provides a two-sided electronic component junction 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 the material, wherein the outer diameter of the plug is 100 ⁇ m or less.
  • minute holes or minute recesses in electronic circuit components can be filled without generating defects such as voids and seams.
  • minute holes and minute recesses can be filled with nickel, which has a high melting point and does not easily recrystallize at room temperature, defects due to condensation of voids do not easily occur even as wiring becomes finer, so this can be widely applied to forming three-dimensional wiring or three-dimensional MEMS (Micro Electro Mechanical Systems) parts which are becoming increasingly miniaturized.
  • nickel which has a high melting point and does not easily recrystallize at room temperature, defects due to condensation of voids do not easily occur even as wiring becomes finer, so this can be widely applied to forming three-dimensional wiring or three-dimensional MEMS (Micro Electro Mechanical Systems) parts which are becoming increasingly miniaturized.
  • MEMS Micro Electro Mechanical Systems
  • the nickel deposit amount in the minute gaps formed when electronic components are superposed can be increased, and the electronic components can be firmly joined together.
  • FIG. 1 is a schematic diagram showing a cross section of the plating part periphery of a printed circuit board for evaluation used in the examples.
  • FIG. 2 is a photograph of a wiring pattern of the surface of the printed circuit board for evaluation used in the examples.
  • FIG. 3 is a schematic diagram showing a cross section before joining electronic components for evaluation (copper wire and copper plate) used in the examples.
  • FIG. 4 is a micrograph of a substrate cross section after plating and filling (Example 1).
  • FIG. 5 is a micrograph of a substrate cross section after plating and filling (Example 2).
  • FIG. 6 is a micrograph of a substrate cross section after plating and filling (Example 3).
  • FIG. 7 is a micrograph of a substrate cross section after plating and filling (Example 4).
  • FIG. 8 is a micrograph of a substrate cross section after plating and filling (Example 5).
  • FIG. 9 is a micrograph of a substrate cross section after plating and filling (Example 6).
  • FIG. 10 is a micrograph of a substrate cross section after plating and filling (Comparative Example 1).
  • FIG. 11 is a micrograph of a substrate cross section after plating and filling (Comparative Example 2).
  • FIG. 12 is a micrograph of a substrate cross section after plating and filling (Comparative Example 3).
  • FIG. 13 is a micrograph of cross sections of copper wire and copper plate after plating and filling (Example 7).
  • FIG. 14 is a micrograph of cross sections of copper wire and copper plate after plating and filling (Example 8).
  • FIG. 15 is a micrograph of cross sections of copper wire and copper plate after plating and filling (Comparative example 4).
  • FIG. 16 is a schematic diagram of a substrate cross section when minute holes or minute recesses are filled with nickel (alloy) deposits according to the method of the present invention.
  • FIG. 17 is a schematic diagram showing an example of a one-sided electronic component junction terminal according to the present invention.
  • FIG. 18 is a schematic diagram showing an example of a two-sided electronic-component junction terminal according to the present invention.
  • FIG. 19 is a schematic diagram showing an example of a one-sided electronic component junction terminal according to the present invention.
  • FIG. 20 is a schematic diagram showing an example of a two-sided electronic component junction terminal according to the present invention.
  • the nickel (alloy) electroplating solution of the present invention contains a nickel salt, a pH buffer and an N-substituted pyridinium compound represented by the following general formula (A) or the following general formula (B).
  • —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 methoxy carbonyl 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)
  • X ⁇ is an arbitrary anion.
  • —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 )
  • m is 0, 1, or 2.
  • the nickel salt contained in the plating solution of the present invention may be, for example, nickel sulfate, nickel sulfamate, nickel chloride, nickel bromide, nickel carbonate, nickel nitrate, nickel formate, nickel acetate, nickel citrate or nickel fluoroboride from the viewpoints of water solubility and filling properties, but the nickel salt is not limited thereto.
  • the sum total content of the nickel salt is preferably from 10 g/L to 180 g/L, but more preferably, from 50 g/L to 130 g/L, as nickel ions.
  • the nickel deposition rate is sufficient, and minute holes or minute recesses can be filled without generating voids.
  • the pH buffer contained in the plating solution of the present invention may be, for example, boric acid, meta-boric acid, acetic acid, tartaric acid, citric acid, and salts thereof, but the pH buffer is not limited thereto.
  • the sum total content of the pH buffer is preferably from 1 g/L to 100 g/L, but more preferably from 5 g/L to 50 g/L.
  • the pH buffer is not likely to interfere with the action of the N-substituted pyridinium compound represented by the aforesaid general formula (A) or general formula (B) (hereafter, may be referred to as “specific N-substituted pyridinium compound”), and the advantageous effect of the invention is maintained.
  • the plating solution of the present invention contains a specific N-substituted pyridinium compound. Due to the action of the specific N-substituted pyridinium compound, the plating solution of the present invention can fill minute holes or minute recesses without generating voids.
  • R 1 , R 2 and R 4 in the aforesaid general formula (A) and the aforesaid general formula (B) when R 1 , R 2 , R 4 is an alkyl group, alkylamino group, cyanoalkyl group, or hydroxyalkyl group having 1-6 carbon atoms, R 1 , R 2 , R 4 may be mutually different.
  • the number of carbon atoms in R 1 , R 2 , and R 4 is preferably 1-4, more preferably 1-3, but most preferably 1 or 2.
  • R 2 As examples of R 2 , —H, —CH 3 , —C 2 H 5 , —CH 2 OH, —CH ⁇ CH 2 , —CONH 2 and —CH ⁇ NOH may be mentioned.
  • halide ions chloride ion, bromide ion, iodide ion
  • halide chloride, bromide, iodide
  • N-substituted pyridinium compound denoted by the aforesaid general formula (B) 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
  • “1-(3-sulfonate propyl) pyridinium” is a compound wherein —R 3 is a hydrogen atom, —R 4 is a hydrogen atom and m is 1, and it is also known by other names such as “1-(3-sulfopropyl) pyridinium hydroxide intramolecular salt”, “1-(3-sulfopropyl) pyridinium”, and “PPS”.
  • “2-vinyl 1-(3-sulfonate propyl) pyridinium” is a compound wherein —R 3 is a hydrogen atom, —R 4 is vinyl group attached in the ortho position, and m is 1, and it is also known by other names such as “1-(3-sulfopropyl)-2-vinyl pyridinium hydroxide intramolecular salt, “1-(3-sulfo propyl)-2-vinyl pyridinium betaine”, and “PPV”.
  • “1-(2-hydroxy-3-sulfonate propyl) pyridinium” is a compound wherein —R 3 is a hydroxyl group, —R 4 is a hydrogen atom, and m is 1, and it is also known by other names such as “1-(2-hydroxy-3-sulfonate propyl) pyridinium hydroxide intramolecular salt”, “1-(2-hydrox-3-sulfo propyl) pyridinium betaine”, and “PPSOH”.
  • One type of the specific N-substituted pyridinium compound may be used alone, or two or more may be mixed and used together.
  • the sum total content of the specific N-substituted pyridinium compound in the plating solution of the present invention is preferably from 0.01 g/L to 100 g/L, but more preferably from 0.1 g/L to 10 g/L.
  • the plating solution of the present invention is a nickel alloy electroplating solution
  • metal ions that can be alloyed with nickel are tungsten, molybdenum, cobalt, manganese, iron, zinc, tin, copper, palladium and gold.
  • metals carbon, sulfur, nitrogen, phosphorus, boron, chlorine and bromine may be contained in the nickel or nickel alloy film.
  • a pit inhibitor, primary brightening agent, secondary brightening agent, surfactant or the like may be added within limits which do not impair the advantages of the present invention.
  • the plating solution of the present invention is particularly suitable for filling minute holes or filling minute recesses formed in electronic circuit components, it is applicable also to the manufacture of ordinary nickel (alloy) deposits. That is, the present invention relates also to a method of producing nickel deposits or nickel alloy deposits by performing electroplating using the aforesaid nickel electroplating solution or nickel alloy electroplating solution.
  • the deposit amount inside the minute holes or minute recesses is larger than the deposit amount exterior to the minute holes or minute recesses, so nickel (or nickel alloy) can be thoroughly embedded in the minute holes or minute recesses.
  • voids (holes) and seams (grooves) do not easily occur inside the minute holes or minute recesses. Consequently, also due to the high melting point of nickel, electronic circuit components wherein minute holes and minute recesses are filled with the plating solution of the present invention are expected to be highly reliable.
  • the invention further relates to a method of manufacturing electronic components wherein minute holes or minute recesses are filled with a nickel deposit or nickel alloy deposit by performing electroplating using said nickel electroplating solution or nickel alloy electroplating solution (That is, a method of filling nickel deposits or nickel alloy deposits).
  • the present invention is also a method of manufacturing electronic components wherein, after first forming an electroplating seed layer on the surface of the minute holes or minute recesses in the electronic components, the electronic components are immersed in the aforesaid nickel (alloy) electroplating solution, electroplating is performed using an external power supply, and the minute holes or minute recesses are filled with nickel deposits or nickel alloy deposits.
  • the present invention is also a method of manufacturing a minute three-dimensional structure including a step of filling minute holes or minute recesses by plating using the aforesaid manufacturing method.
  • Minute holes or minute recesses refer to minute hollow portions such as vias, through-holes and trenches formed in electronic circuit components such as semiconductors and printed circuit boards which, by filling them with metal by electro plating, function as wiring parts, and their configuration viewed from above is not limited.
  • minute holes may be penetrating or non-penetrating.
  • the substrate to be plated is not particularly limited, and as specific examples, glass epoxy, BT (Bismaleimide-Triazine) resin, polypropylene, polyimide, ceramics, silicon, metals and glass may be mentioned.
  • the method of forming minute holes and minute recesses in the plating substrate is not particularly limited, and methods known in the art may suitably be used.
  • a minute recess can be formed with an opening of 100 ⁇ m or less, and a depth with an aspect ratio of 0.5 or more.
  • a pattern is formed on the plating substrate surface by a photoresist or the like.
  • the electroplating seed layer is formed on the substrate surface and the inner surface of the minute recess.
  • the method of forming the seed layer is not particularly limited, but as examples, metal deposition by sputtering and electroless plating may specifically be mentioned.
  • the metal which constitutes the seed layer is not particularly limited, but as examples, copper, nickel, or palladium may be mentioned.
  • the substrate to be plated is immersed in the nickel (alloy) electroplating solution of the present invention, nickel (alloy) electroplating is performed using an external power supply, and minute holes and minute recesses are filled with nickel or a nickel alloy.
  • electroplating using the plating solution of the present invention may be performed.
  • filling of minute holes or minute recesses means filling minute holes and minute recesses without forming large voids (holes).
  • the term “filling” is also understood to include the case when the minute holes or minute recesses are not completely filled (for example, as shown in FIG. 16( b ) , FIG. 19( c ) , etc., when, although nickel (alloy) is deposited inside the minute holes or minute recesses, there is also a hollow part, or when nickel or a nickel alloy is deposited even to the peripheral part outside the minute holes or minute recesses (as in the case of FIG. 16( a ) , etc.).
  • the minimum plating cross section film thickness (X 2 in FIG. 16 ) in a minute hole or minute recess 30 may be made larger than the maximum plating cross section film thickness (X 1 in FIG. 16 ) of a peripheral part 31 outside the minute hole or minute recess 30 .
  • the filling method of the present invention it is possible to increase the nickel (alloy) deposit amount inside the minute hole or minute recess 30 .
  • the minute hole or minute recess 30 when filling the inside of the minute hole or minute recess 30 with nickel (alloy), the minute hole or minute recess 30 may be completely filled with nickel (alloy) as shown in FIG. 16( a ) , or part thereof need not be filled as shown in FIG. 16( b ) (i.e., it may have a reverse convex form).
  • Fine three-dimensional circuit wiring or a minute three-dimensional structure wherein minute holes and minute recesses are filled with nickel or a nickel alloy can be manufactured by including a step of plating and filling minute holes or minute recesses according to the nickel or nickel alloy filling and plating method of the present invention.
  • the plating temperature is preferably 30° C. or more, but more preferably 40° C. or more. Further, it preferably does not exceed 70° C., but more preferably does not exceed 60° C. Within this range, the ability to fill minute holes or minute recesses is superior, and it is also advantageous from the viewpoint of cost.
  • the current density for plating is preferably 0.1 A/dm 2 or more, but more preferably 1 A/dm 2 or more. Further, it preferably does not exceed 10 A/dm 2 , but more preferably does not exceed 5 A/dm 2 . Within this range, the ability to fill minute holes or minute recesses is superior, and it is also advantageous from the viewpoint of cost.
  • the current density during plating and filling may be constant, but need not be constant (for example, the initial current density may be low and then gradually increased; or pulsed current may be used; etc.).
  • filling can be performed easily without generating voids, and this is therefore preferred.
  • the plating time is preferably 5 minutes or more, but more preferably 10 minutes or more. Further, it preferably does not exceed 360 minutes, but more preferably does not exceed 60 minutes.
  • the present invention is also a method of manufacturing an electronic component assembly where two or more electronic components are superposed, and a minute gap is formed therebetween, wherein the two or more electronic components are immersed in the aforesaid nickel (alloy) electroplating solution, and electroplating is performed using an external power supply.
  • Electronic components means parts which are surface mounted on an electronic circuit.
  • Electrode assembly means two or more electronic components joined together to form one structure.
  • the nickel or nickel alloy deposit amount is large in the vicinity of these minute gaps.
  • an electronic component assembly where two or more electronic components are joined together by nickel or a nickel alloy
  • an electronic component assembly wherein more nickel or nickel alloy is deposited in the vicinity of the minute gaps formed between the electronic components than in other parts, can be obtained.
  • the nickel or nickel alloy deposit amount in the vicinity of the minute gaps is large, so sufficient strength is obtained in parts where the electronic components are joined together, and reliability is high.
  • the plating temperature when the electronic component assembly is manufactured is preferably 30° C. or more, but more preferably 40° C. or more. Further, it preferably does not exceed 70° C., and more preferably does not exceed 60° C.
  • the nickel or nickel alloy deposit amount in the vicinity of the minute gaps is sufficient, and join strength easily improves.
  • the current density when the electronic component assembly is manufactured is preferably 0.1 A/dm 2 or more, but more preferably 1 A/dm 2 or more. Further, it preferably does not exceed 10 A/dm 2 , but more preferably does not exceed 5 A/dm 2 .
  • the nickel or nickel alloy deposit amount in the vicinity of the minute gaps is sufficient, and join strength easily improves.
  • the current density during plating and filling may be constant, but need not be constant (for example, the initial current density may be set low and then gradually increased; or pulsed current may be used; etc.).
  • join strength easily improves, and this is therefore preferred.
  • the plating time is preferably 5 minutes or more, but more preferably 10 minutes or more.
  • join strength is superior, and it is also advantageous from the viewpoint of cost.
  • the present invention relates also to a terminal for joining electronic components with few voids (holes), embedded in a substantially perpendicular direction (60°-90° direction) relative to the surface of a substrate 11 in a substrate having minute holes and minute recesses.
  • a terminal 40 for joining electronic components according to the present invention comprises nickel or a nickel alloy.
  • the terminal for joining electronic components according to the present invention may be easily formed by using the aforesaid nickel (alloy) electroplating solution of the present invention.
  • the terminal 40 for joining electronic components according to the present invention is embedded in the substrate 11 having a thickness of 1 mm or less.
  • the terminal 40 for joining electronic components may be a one-sided terminal for joining electronic components (which does not penetrate the substrate 11 ) as shown in FIG. 17 or FIG. 19 , or may be a two-sided terminal for joining electronic components (which does penetrate the substrate 11 ) as shown in FIG. 18 or FIG. 20 .
  • the terminal shown in FIG. 17 is the one-sided terminal 40 for joining electronic components provided with a plug 41 embedded in a substantially perpendicular direction relative to the surface of the substrate 11 but not penetrating the substrate 11 , and a cap 42 which is in contact with this plug.
  • the cap 42 projects from the surface of the substrate 11 , its outer diameter is larger than the outer diameter of the plug 41 , and is 200 ⁇ m or less.
  • outer diameter means the outer diameter of a circle of equivalent surface area (hereafter, the same for the terminal 40 for joining electronic components shown in FIGS. 18-20 ).
  • the terminal shown in FIG. 18 is the two-sided terminal 40 for joining electronic components provided with the plug 41 embedded in a substantially perpendicular direction relative to the surface of the substrate 11 and penetrating the substrate 11 , and two caps 42 in contact with the ends of the plug 41 .
  • the two caps 42 respectively project from the surface of the substrate 11 , the outer diameters of the two caps 42 are larger than the outer diameter of the plug 41 , and are 200 ⁇ m or less.
  • the terminal shown in FIG. 19 is the one-sided terminal 40 for joining electronic components comprising the plug 41 embedded in a substantially perpendicular direction relative to the surface of the substrate 11 , but not penetrating the substrate 11 .
  • the outer diameter of the plug 41 is 100 ⁇ m or less.
  • the end of the plug 41 may project from the surface of the substrate 11 as shown in FIG. 19( a ) , may have the same height as the surface of the substrate 11 as shown in FIG. 19( b ) , or may be embedded relative to the surface of the substrate 11 as shown in FIG. 19( c ) .
  • the terminal shown in FIG. 20 is the two-sided terminal 40 for joining electronic components comprising a plug 41 embedded in a substantially perpendicular direction relative to the surface of the substrate 11 , and penetrating the substrate 11 .
  • the outer diameter of the plug 41 is 100 ⁇ m or less.
  • the ends of the plug 41 may project from the surface of the substrate 11 as shown in FIG. 20( a ) , may have the same height as the surface of the substrate 11 as shown in FIG. 20( b ) , or may be embedded relative to the surface of the substrate 11 as shown in FIG. 20( c ) .
  • a terminal for an electronic component junction of nickel (alloy) embedded in a substrate of thickness 1 mm or less comprising the plug 41 having an outer diameter of 100 ⁇ m or less, and a cap 42 having an outer diameter of 200 ⁇ m or less.
  • the terminal When manufacturing the terminal for an electronic component junction using the nickel (alloy) electroplating solution of the present invention, the terminal can be easily embedded in a thin substrate of 0.8 mm or less, or thinner substrate of 0.5 mm or less.
  • a terminal for an electronic component junction comprising a plug having a smaller outer diameter of 70 ⁇ m or less or even smaller outer diameter of 50 ⁇ m or less, and a cap having a smaller outer diameter of 150 ⁇ m or less or even smaller outer diameter of 100 ⁇ m or less.
  • the plug 41 of the terminal 40 for an electronic component junction does not contain voids having a larger maximum width than 10 ⁇ m.
  • the preferred conditions (plating temperature, current density, etc.) for manufacturing the aforesaid terminal for an electronic component junction by plating using the nickel (alloy) electroplating solution of the present invention are substantially identical to the conditions described in the aforesaid section, (Method of manufacturing nickel (alloy)-filled electronic components, and three-dimensional structure).
  • Examples 1-6, comparative examples 1-3 As a model of minute recesses, the printed circuit boards for evaluation (made by Japan Circuit Co. Ltd.) of 12 mm angle having laser vias of aspect ratio 0.88 ( ⁇ 45 ⁇ m ⁇ 40 ⁇ m D) were used.
  • FIG. 1 shows a cross-sectional view of a plating part periphery 10 .
  • a blind via hole (hereafter, may be referred to simply as “via hole” or “via”) 14 having ⁇ 45 ⁇ m ⁇ 40 ⁇ m D was made by a laser, and a seed layer 15 was formed to a thickness of approx. 1 ⁇ m by non-electrolytic copper plating on the substrate outer surface (surface of the buildup resin 12 ) and the inner wall of the via 14 .
  • a circuit pattern shown in FIG. 2 was then formed by a dry film resist (DFR) 16 of thickness 25 ⁇ m, and a pad (opening) 17
  • the white parts are copper plating parts, and the black parts are dry film resist parts.
  • the circular part with the largest size to which wiring is connected is equivalent to the circular pad 17 ( ⁇ 190 ⁇ m) of FIG. 1 .
  • the via hole 14 which is the minute recess shown in FIG. 1 was formed in all the circular pads 17 .
  • Nickel sulfamate at 600 g/L, nickel chloride at 10 g/L and boric acid at 30 g/L were dissolved in deionized water to prepare a nickel electroplating solution.
  • Example 1 1-propyl pyridinium (A) 0.5 chloride
  • Example 2 1-(cyanomethyl) pyridinium (A) 0.1 chloride
  • Example 3 3-carbamoyl-1-methyl (A) 0.5 pyridinium chloride
  • Example 4 1-methyl (A) 0.5 pyridinium-2-aldoxime chloride
  • Example 5 1-(3-sulfonate propyl) (B) 0.5 pyridinium
  • Example 6 2-vinyl-1-(3-sulfonatee (B) 0.5 propyl) pyridinium Comparative None — —
  • Example 1 Comparative Thiourea — 0.2
  • Example 2 Comparative Thiourea — 0.1
  • Example 3 Dodecyltrimethylammonium — 0.65 Chloride
  • Nickel electroplating was performed to the aforesaid printed circuit board 1 for evaluation in a step shown in Table 2.
  • the current density was adjusted to 1.0 A/dm 2 using an external power supply.
  • the plating area was calculated as the surface area including the sides of the via 14 .
  • the substrate was embedded and fixed in a polishing resin, its cross section was polished, and the filling condition of the via was observed with a metallurgical microscope.
  • FIGS. 4-12 show micrographs of the substrate cross section after plating and filling.
  • Table 3 shows the evaluation results.
  • Example 1 1-propyl pyridinium ⁇ No Good chloride
  • Example 2 1-(cyanomethyl) ⁇ No Good pyridinium chloride
  • Example 3 3-carbamoyl-1-methyl ⁇ No Good pyridinium chloride
  • Example 4 1-methyl ⁇ No Good pyridinium-2-aldoxime chloride
  • Example 5 1-(3-sulfonate propyl) ⁇ No Good pyridinium
  • Example 6 2-vinyl-1-(3-sulfonate ⁇ No Good propyl) pyridinium Comparative None X No Defective Example 1 Comparative Thiourea X No Defective Example 2 Comparative Thiourea ⁇ Yes Defective Example 3 Dodecyltrimethyl ammonium Chloride
  • the amount of deposited nickel 18 was larger inside the via holes which are minute recesses than outside the via holes, and the filling was good without voids or seams.
  • the plating was conformal plating with approximately the same amount of deposited nickel 18 inside and outside the via holes, and filling was poor.
  • Comparative Example 2 the inside of the vias had voids V of maximum width 14 ⁇ m, and filling was poor.
  • Comparative Example 3 Although there were no voids inside the vias and filling was good, the deposited part was very weak, cracks had occurred, and remarkable exfoliation of deposited nickel 18 was seen in the upper part of the via after polishing.
  • Nickel sulfamate at 600 g/L, nickel chloride at 10 g/L and boric acid at 30 g/L were dissolved in deionized water to prepare a nickel electroplating solution.
  • the aforesaid electronic component sample was immersed in the aforesaid nickel electroplating solution so that the linear directions of the copper wire 21 and the plating surface were substantially perpendicular, and nickel electroplating was performed in the step shown in Table 5.
  • the nickel anode was made to face the outside of the masking material 22 a every one sheet.
  • the current density was adjusted to 1.0 A/dm 2 in a nickel electroplating step using an external power supply.
  • the plating area was taken as the surface area of only the copper plate 22 .
  • the electronic component sample (assembly) was embedded and fixed in a polishing resin, its cross section was polished, and the join between the copper wire 21 and copper plate 22 was observed with a metallurgical microscope.
  • FIGS. 13-15 show micrographs of a cross section of the electronic components sample (assembly) after plating and filling.
  • Example 7 1-propyl pyridinium chloride ⁇
  • Example 8 2-(vinyl)-1-(3-sulfonate propyl) pyridinium ⁇ Comparative None X
  • Example 4
  • the amount of deposited nickel 18 in the minute gaps 24 where the copper wire 21 and copper plate 22 were in contact was larger than in other places, and they were joined more firmly together.
  • the nickel (alloy) electroplating solution containing an N-substituted pyridinium compound according to the present invention can fill minute holes or minute recesses in electronic circuit components reliably, and as the electronic components can be firmly joined together, the wiring can be made even finer, so the solution has wide application in forming 3-dimensional wiring or 3-dimensional MEMS components.

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