WO2018186217A1 - Iron-nickel alloy electroplating liquid for filling and method for filling opening using same, and method for manufacturing circuit substrate - Google Patents

Iron-nickel alloy electroplating liquid for filling and method for filling opening using same, and method for manufacturing circuit substrate Download PDF

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WO2018186217A1
WO2018186217A1 PCT/JP2018/012072 JP2018012072W WO2018186217A1 WO 2018186217 A1 WO2018186217 A1 WO 2018186217A1 JP 2018012072 W JP2018012072 W JP 2018012072W WO 2018186217 A1 WO2018186217 A1 WO 2018186217A1
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iron
nickel alloy
filling
electroplating solution
opening
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PCT/JP2018/012072
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French (fr)
Japanese (ja)
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真雄 堀
康男 橋本
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株式会社Ｊｃｕ
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Priority to KR1020197030775A priority Critical patent/KR20190133709A/en
Publication of WO2018186217A1 publication Critical patent/WO2018186217A1/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
    • C25D3/56—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
    • 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
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/11—Printed elements for providing electric connections to or between printed circuits
    • 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
    • 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
    • H05K3/424—Plated through-holes or plated via connections characterised by electroplating method by direct electroplating
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/11—Printed elements for providing electric connections to or between printed circuits
    • H05K1/115—Via connections; Lands around holes or via connections
    • 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
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
    • H05K2203/0703—Plating
    • H05K2203/0723—Electroplating, e.g. finish plating

Definitions

  • the present invention relates to an electroplating solution for iron-nickel alloy filling, an opening filling method using the same, and a circuit board manufacturing method.
  • An iron-nickel alloy particularly an invar composition, is generally used for photomasks, bimetals and the like because its coefficient of thermal expansion is low and its dimensions do not change with temperature.
  • Patent Document 1 An iron-nickel alloy was a molten alloy and could not be used for circuit formation itself.
  • Patent Document 1 a technique for depositing an iron-nickel alloy by electroplating has recently been reported. It was expected to be used for circuit formation.
  • the present invention provides a technique that can use an iron-nickel alloy for circuit formation itself by electroplating.
  • acetylene which is an effective component of a conventionally known etching agent for iron-nickel alloys (for example, JP-A-2001-11661). It has been found that by adding alcohol to an iron-nickel alloy electroplating solution, a circuit such as filling of openings such as vias can be formed, and the present invention has been completed.
  • the present invention is an electroplating solution for iron-nickel alloy filling, characterized by further containing acetylene alcohol in the iron-nickel alloy electroplating solution.
  • the present invention is a method for filling an opening, characterized in that the substrate having the opening is electroplated with the above-described electroplating solution for iron-nickel alloy filling.
  • the present invention is a method for manufacturing a circuit board, wherein the substrate having an opening is electroplated with the above electroplating solution for iron-nickel alloy filling.
  • the present invention is a circuit board characterized in that the opening is filled with an iron-nickel alloy.
  • the electroplating solution for iron-nickel alloy filling of the present invention can be filled on a substrate having openings such as vias.
  • the iron-nickel alloy filled as described above has a small variation in composition in the depth direction from the opening.
  • the iron-nickel alloy filled as described above does not require heat treatment.
  • the electroplating solution for iron-nickel alloy filling of the present invention is suitable for circuit formation such as filling of openings such as vias.
  • Example 3 is a cross-sectional photograph of a substrate obtained in Example 2. The measurement point of EDS of the board
  • the iron-nickel alloy filling electroplating solution of the present invention (hereinafter referred to as “the present invention plating solution”) is an iron-nickel alloy electroplating solution further containing acetylene alcohol.
  • the acetylene alcohol used in the plating solution of the present invention is not particularly limited as long as the structure has a triple bond between carbon and an OH group.
  • propargyl alcohol, butynediol, pentynediol, hexynediol, octynediol and the like Is mentioned.
  • These acetylene alcohols may have a substituent such as an alkyl group or a hydroxyethyl group.
  • acetylene alcohols having 5 or more carbon atoms are preferable, and hexynediol is particularly preferable in order to reduce variation in the internal composition of the iron-nickel alloy when filled.
  • These acetylene alcohols may be used alone or in combination of two or more.
  • the content of acetylene alcohol in the plating solution of the present invention is not particularly limited, but is, for example, 0.001 to 1% by mass (hereinafter simply referred to as “%”), preferably 0.005 to 0.5%.
  • the iron-nickel alloy electroplating solution used as the base of the plating solution of the present invention is not particularly limited.
  • metal ions such as iron ions and nickel ions
  • complexing agents such as gluconic acid, malic acid and citric acid, boric acid And those containing a buffer such as acetic acid.
  • More specific examples of the electroplating solution for iron-nickel alloy include chloride bath, sulfate bath, sulfate-chloride bath, cyan bath, citric acid bath, pyrophosphate bath, watt bath, sulfamic acid bath, and the like. It is done. Among these, Watt bath and sulfamic acid bath are preferable.
  • R is a vinyl group or an ethynyl group, preferably a vinyl group.
  • X is an optionally substituted alkylene group or phenylene group, preferably an unsubstituted alkylene group or phenylene group, and more preferably an unsubstituted alkylene group.
  • substituent include an alkyl group having 1 to 3 carbon atoms, a halogen, and a hydroxyl group.
  • the alkylene group has 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms, and more preferably 1 carbon atom.
  • Y is an alkali metal, preferably lithium, sodium or potassium, more preferably sodium.
  • More specific unsaturated sulfonic acid compounds include sodium allyl sulfonate, sodium vinyl sulfonate, sodium propyne sulfonate, and the like, and preferably sodium allyl sulfonate. These unsaturated sulfonic acid compounds may be used alone or in combination of two or more.
  • the content of the unsaturated sulfonic acid compound in the plating solution of the present invention is 1 to 10%, preferably 4 to 8%.
  • an unsaturated sulfonic acid compound represented by the above general formula (1) and iron of 4 to 12 g / L, preferably 6 are particularly preferable. ⁇ 10 g / L, nickel contained in the amount of 20-50 g / L, preferably 25-40 g / L.
  • the composition of the iron-nickel alloy when filling the opening is 100%, and iron is 55-64% and nickel is 36-45%. It becomes.
  • the plating solution of the present invention may further contain cobalt, molybdenum and tungsten.
  • the addition amount of cobalt, molybdenum and tungsten is not particularly limited, and is, for example, 1 to 100 g / L, preferably 1 to 50 g / L.
  • Examples of the cobalt, molybdenum, and tungsten sources include cobalt sulfate, cobalt sulfamate, sodium molybdate, and sodium tungstate.
  • a stress relaxation agent such as sodium saccharinate added to a conventionally known iron-nickel alloy electroplating solution may be further added.
  • Nickel sulfate 50 to 125 g / L, preferably 60 to 100 g / L Nickel chloride: 40 to 80 g / L, preferably 50 to 70 g / L Boric acid: 30-60g / L Ferrous sulfate: 20-60 g / L, preferably 35-50 g / L Sodium gluconate: 20-80 g / L, preferably 50-60 g / L Saccharin sodium: 1-5 g / L, preferably 2-4 g / L Sodium allyl sulfonate: 1.5 to 10 g / L, preferably 3.5 to 8. 5g / L
  • Nickel sulfamate 90 to 250 g / L, preferably 140 to 19 0g / L Boric acid: 30-60g / L Nickel bromide: 5 to 15 g / L, preferably 6 to 10 g / L Iron sulfamate: 25 to 75 g / L, preferably 40 to 60 g / L Sodium gluconate: 20-80 g / L, preferably 50-60 g / L Saccharin sodium: 1-5 g / L, preferably 2-4 g / L Sodium allyl sulfonate: 1.5 to 10 g / L, preferably 3.5 to 8. 5g / L
  • the plating solution of the present invention can fill the opening by electroplating the substrate having the opening.
  • the method of electroplating is not particularly limited, and examples thereof include a method in which a substrate having an opening is subjected to pretreatment such as alkali degreasing and acid activity and then immersed in the plating solution of the present invention.
  • the substrate that can be electroplated with the plating solution of the present invention is not particularly limited.
  • the opening means a via or the like.
  • the size of the opening is not particularly limited.
  • the diameter is about 5 to 150 ⁇ m
  • the depth is about 10 to 100 ⁇ m
  • the aspect ratio is about 0.1 to 2.
  • the conditions for electroplating are not particularly limited, and normal filling conditions for electroplating may be used.
  • the bath temperature is 30 to 60 ° C.
  • iron and nickel are used in combination with the anode
  • the cathode current density is 0.05 to It may be performed at 3 A / dm 2 until the opening is filled.
  • the opening of the substrate can be filled.
  • the filled iron-nickel alloy does not require heat treatment.
  • the opening is filled using the plating solution of the present invention, there is little variation in composition in the depth direction from the opening of the iron-nickel alloy filled in the opening.
  • the composition in the depth direction from the opening when the opening is filled with a acetylene alcohol having 5 or more carbon atoms, particularly a plating solution using hexynediol, the composition in the depth direction from the opening.
  • the difference between the composition from the bottom of the opening to the film thickness of 30% of the via depth and the surface composition of the opening is ⁇ 10% or less.
  • the composition in the depth direction from the opening of the filled iron-nickel alloy can be measured by energy dispersive X-ray analysis (EDS) or the like.
  • the opening of the substrate having the opening is filled with an iron-nickel alloy using the plating solution of the present invention, and further, chemical mechanical polishing, laminating process, filling plating, filling of conductive paste, bump formation, etc. By doing this, it is possible to manufacture a circuit board whose opening is filled with an iron-nickel alloy.
  • a multilayer printed wiring board is preferable, in which a stack via can be formed at the time of lamination on the upper part of the opening after filling and a pad for mounting an electronic component can be formed.
  • the circuit board manufactured in this way uses a low thermal expansion alloy as the wiring, it is possible to suppress deterioration such as cracks caused by the difference in thermal expansion coefficient between the metal and the resin.
  • Example 1 Preparation of electroplating solution for iron-nickel alloy: In water, nickel sulfamate tetrahydrate 156 g / L, boric acid 30 g / L, nickel bromide 7 g / L, iron sulfamate pentahydrate 47 g / L, sodium gluconate 60 g / L, saccharin sodium 3.
  • An electroplating solution for iron-nickel alloy was prepared by adding and mixing 2 g / L, sodium allylsulfonate (36%) 16 ml / L, and hexynediol 1.0 g.
  • the plating bath had a pH of 3.8 and nickel and iron contents of 30 g / L and 7.5 g / L, respectively.
  • Example 2 Filling a substrate with vias: Using the electroplating solution for iron-nickel alloy prepared in Example 1 and Comparative Example 1, the substrate having vias was filled under the conditions shown in Table 1 below. A cross-sectional photograph after filling is shown in FIG. Further, the measurement points of EDS of the substrate after electroplating under condition 2 are shown in FIG.
  • ⁇ Board> A circuit board having an opening of a blind via, a diameter of the blind via of 70 ⁇ m, a depth of 40 ⁇ m, and an aspect ratio of 0.57 was used.
  • the iron-nickel alloy electroplating solution of the present invention containing hexynediol was able to fill vias, but the iron-nickel alloy electroplating solution not containing hexynediol was not able to fill vias. . It was also found that the iron-nickel alloy filled according to the present invention has a small variation in composition in the depth direction from the opening.
  • Example 3 Preparation of electroplating solution for iron-nickel alloy: An electroplating solution for an iron-nickel alloy was prepared in the same manner as in Example 1 except that hexynediol was changed to 0.02 g of propargyl alcohol.
  • Example 4 Filling a substrate with vias: The same substrate as in Example 2 was filled under the same conditions as in Condition 1 of Example 2 except that the electroplating solution for iron-nickel alloy of Example 3 was used. A cross-sectional photograph after filling is shown in FIG. Further, the composition of iron and nickel measured by EDS as in Example 2 is shown in Table 3.
  • the iron-nickel alloy electroplating solution of the present invention containing propargyl alcohol was able to fill vias. It was also found that the iron-nickel alloy filled according to the present invention has a smaller variation in composition in the depth direction from the opening when hexynediol is used than when propargyl alcohol is used.
  • Example 5 Preparation of electroplating solution for iron-nickel alloy: An electroplating solution for iron-nickel alloy was prepared in the same manner as in Example 1 except that hexynediol was changed to 1.5 g / L of dimethyloctynediol.
  • Example 6 Preparation of electroplating solution for iron-nickel alloy: In water, nickel sulfate 75 g / L, boric acid 30 g / L, nickel chloride 55 g / L, ferrous sulfate 37.5 g / L, sodium gluconate 60 g / L, saccharin sodium 3.2 g / L and sodium allyl sulfonate ( 36%) 16 ml / L and 1.0 g of hexynediol were added and mixed to prepare an electroplating solution for iron-nickel alloy. The pH of this plating bath was 3.0, and the contents of nickel and iron were 30 g / L and 7.5 g / L, respectively.
  • Example 7 Preparation of electroplating solution for iron-nickel-cobalt alloy: In water, 126 g / L of nickel sulfamate tetrahydrate, 30 g / L of boric acid, 7 g / L of nickel bromide, 50 g / L of iron sulfamate pentahydrate, cobalt sulfamate tetrahydrate 3. 5 g / L, sodium gluconate 60 g / L, saccharin sodium 3.2 g / L, sodium allyl sulfonate (36%) 16 ml / L, hexynediol 1.0 g are added and mixed, and an electroplating solution for iron-nickel alloy Was prepared. The pH of this plating bath was 3.8, and the contents of nickel, iron and cobalt were 30 g / L, 7.5 g / L and 0.625 g / L, respectively.
  • the electroplating solution for iron-nickel alloy filling of the present invention can be used for circuit formation such as filling of openings such as vias. more than

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  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
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Abstract

Provided are: an iron-nickel alloy electroplating liquid for filling, characterized in that an acetylene alcohol is furthermore contained in the iron-nickel alloy electroplating liquid; a method for filling an opening using the iron-nickel alloy electroplating liquid for filling; and a technique whereby an iron-nickel alloy can be utilized in circuit formation by electroplating using a method for manufacturing a circuit substrate.

Description

鉄－ニッケル合金フィリング用電気めっき液およびこれを用いた開口部のフィリング方法、回路基板の製造方法Electroplating solution for iron-nickel alloy filling, opening filling method using the same, and circuit board manufacturing method
　本発明は、鉄－ニッケル合金フィリング用電気めっき液およびこれを用いた開口部のフィリング方法、回路基板の製造方法に関するものである。 The present invention relates to an electroplating solution for iron-nickel alloy filling, an opening filling method using the same, and a circuit board manufacturing method.
　鉄－ニッケル合金、特にインバー組成と呼ばれる組成の場合には、一般に熱膨張率が低く温度によって寸法が変化しないため、フォトマスク、バイメタル等に利用されている。 An iron-nickel alloy, particularly an invar composition, is generally used for photomasks, bimetals and the like because its coefficient of thermal expansion is low and its dimensions do not change with temperature.
　これまで鉄－ニッケル合金は、溶製合金のため、回路形成自体に用いることができなかったが、近年電気めっきにより鉄－ニッケル合金を析出させる技術が報告されたため（特許文献１）、ビアフィリング等の回路形成への利用が期待された。 Until now, an iron-nickel alloy was a molten alloy and could not be used for circuit formation itself. However, a technique for depositing an iron-nickel alloy by electroplating has recently been reported (Patent Document 1). It was expected to be used for circuit formation.
　しかしながら、特許文献１の技術を用いて鉄－ニッケル合金でビアフィリング等を行おうとすると、コンフォーマル析出となるためフィリングが十分に行えないという問題があった。 However, when via filling or the like is performed with an iron-nickel alloy using the technique of Patent Document 1, there is a problem that filling cannot be performed sufficiently because of conformal precipitation.
特許第６０８４８９９号Japanese Patent No. 6084899
　従って、本発明は、鉄－ニッケル合金を電気めっきにより回路形成自体に利用できる技術を提供する。 Therefore, the present invention provides a technique that can use an iron-nickel alloy for circuit formation itself by electroplating.
　本発明者らは、上記課題を解決するために鋭意研究した結果、意外にも、従来公知の鉄－ニッケル合金用のエッチング剤（例えば、特開２００１－１１６６１号公報）の有効成分であるアセチレンアルコールを、鉄－ニッケル合金電気めっき液中に添加することにより、ビア等の開口部のフィリング等の回路形成が行えることを見出し、本発明を完成させた。 As a result of diligent research to solve the above problems, the present inventors have surprisingly found that acetylene, which is an effective component of a conventionally known etching agent for iron-nickel alloys (for example, JP-A-2001-11661). It has been found that by adding alcohol to an iron-nickel alloy electroplating solution, a circuit such as filling of openings such as vias can be formed, and the present invention has been completed.
　すなわち、本発明は、鉄－ニッケル合金電気めっき液に、更に、アセチレンアルコールを含有させたことを特徴とする鉄－ニッケル合金フィリング用電気めっき液である。 That is, the present invention is an electroplating solution for iron-nickel alloy filling, characterized by further containing acetylene alcohol in the iron-nickel alloy electroplating solution.
　また、本発明は、開口部を有する基板を、上記鉄－ニッケル合金フィリング用電気めっき液で電気めっきを行うことを特徴とする開口部のフィリング方法である。 Further, the present invention is a method for filling an opening, characterized in that the substrate having the opening is electroplated with the above-described electroplating solution for iron-nickel alloy filling.
　更に、本発明は、開口部を有する基板を、上記鉄－ニッケル合金フィリング用電気めっき液で電気めっきを行うことを特徴とする回路基板の製造方法である。 Furthermore, the present invention is a method for manufacturing a circuit board, wherein the substrate having an opening is electroplated with the above electroplating solution for iron-nickel alloy filling.
　また更に、本発明は、開口部が、鉄－ニッケル合金でフィリングされていることを特徴とする回路基板である。 Furthermore, the present invention is a circuit board characterized in that the opening is filled with an iron-nickel alloy.
　本発明の鉄－ニッケル合金フィリング用電気めっき液は、ビア等の開口部を有する基板にフィリングすることができる。また、前記のようにしてフィリングされた鉄－ニッケル合金は開口部から深さ方向への組成のばらつきが小さい。更に、前記のようにしてフィリングされた鉄－ニッケル合金は熱処理の必要もない。 The electroplating solution for iron-nickel alloy filling of the present invention can be filled on a substrate having openings such as vias. In addition, the iron-nickel alloy filled as described above has a small variation in composition in the depth direction from the opening. Furthermore, the iron-nickel alloy filled as described above does not require heat treatment.
　そのため、本発明の鉄－ニッケル合金フィリング用電気めっき液は、ビア等の開口部のフィリング等の回路形成に好適である。 Therefore, the electroplating solution for iron-nickel alloy filling of the present invention is suitable for circuit formation such as filling of openings such as vias.
実施例２で得られた基板の断面写真である。3 is a cross-sectional photograph of a substrate obtained in Example 2. 実施例２の条件２で得られた基板のＥＤＳの測定地点を示す。The measurement point of EDS of the board | substrate obtained on the conditions 2 of Example 2 is shown. 実施例４で得られた基板の断面写真である。6 is a cross-sectional photograph of the substrate obtained in Example 4.
　本発明の鉄－ニッケル合金フィリング用電気めっき液（以下、「本発明めっき液」という）は、鉄－ニッケル合金電気めっき液に、更に、アセチレンアルコールを含有させたものである。 The iron-nickel alloy filling electroplating solution of the present invention (hereinafter referred to as “the present invention plating solution”) is an iron-nickel alloy electroplating solution further containing acetylene alcohol.
　本発明めっき液に用いられるアセチレンアルコールは、構造中に炭素間３重結合と、ＯＨ基があれば特に限定されず、例えば、プロパルギルアルコール、ブチンジオール、ペンチンジオール、ヘキシンジオール、オクチンジオール等が挙げられる。また、これらアセチレンアルコールはアルキル基やヒドロキシエチル基などの置換基を有してもよい。これらアセチレンアルコールの中でも、フィリングされた際の鉄－ニッケル合金の内部の組成のばらつきを小さくするためには炭素数が５以上のアセチレンアルコールが好ましく、特にヘキシンジオールが好ましい。これらアセチレンアルコールは１種または２種以上を組み合わせてもよい。 The acetylene alcohol used in the plating solution of the present invention is not particularly limited as long as the structure has a triple bond between carbon and an OH group. For example, propargyl alcohol, butynediol, pentynediol, hexynediol, octynediol and the like Is mentioned. These acetylene alcohols may have a substituent such as an alkyl group or a hydroxyethyl group. Among these acetylene alcohols, acetylene alcohols having 5 or more carbon atoms are preferable, and hexynediol is particularly preferable in order to reduce variation in the internal composition of the iron-nickel alloy when filled. These acetylene alcohols may be used alone or in combination of two or more.
　本発明めっき液におけるアセチレンアルコールの含有量は特に限定されないが、例えば、０.００１～１質量％（以下、単に「％」という）、好ましくは０.００５～０.５％である。 The content of acetylene alcohol in the plating solution of the present invention is not particularly limited, but is, for example, 0.001 to 1% by mass (hereinafter simply referred to as “%”), preferably 0.005 to 0.5%.
　本発明めっき液のベースとなる鉄－ニッケル合金電気めっき液は、特に限定されないが、例えば、鉄イオン、ニッケルイオンなどの金属イオン、グルコン酸、リンゴ酸、クエン酸等の錯化剤、ホウ酸、酢酸等の緩衝剤を含有するものが挙げられる。より具体的な鉄－ニッケル合金用電気めっき液としては、塩化物浴、硫酸塩浴、硫酸塩－塩化物浴、シアン浴、クエン酸浴、ピロリン酸浴、ワット浴、スルファミン酸浴等が挙げられる。これらの中でもワット浴、スルファミン酸浴が好ましい。 The iron-nickel alloy electroplating solution used as the base of the plating solution of the present invention is not particularly limited. For example, metal ions such as iron ions and nickel ions, complexing agents such as gluconic acid, malic acid and citric acid, boric acid And those containing a buffer such as acetic acid. More specific examples of the electroplating solution for iron-nickel alloy include chloride bath, sulfate bath, sulfate-chloride bath, cyan bath, citric acid bath, pyrophosphate bath, watt bath, sulfamic acid bath, and the like. It is done. Among these, Watt bath and sulfamic acid bath are preferable.
　本発明めっき液のベースとなる鉄－ニッケル合金電気めっき液として、より好ましいのは、上記鉄－ニッケル合金電気めっき液に、以下の一般式（１）
Figure JPOXMLDOC01-appb-C000002
 で表される不飽和スルホン酸化合物を含有させたものである。 As the iron-nickel alloy electroplating solution used as the base of the plating solution of the present invention, the following general formula (1) is more preferable.
Figure JPOXMLDOC01-appb-C000002
 An unsaturated sulfonic acid compound represented by the formula:
　上記不飽和スルホン酸化合物において、Ｒはビニル基またはエチニル基であり、好ましくはビニル基である。また、Ｘは置換されていてもよい、アルキレン基またはフェニレン基であり、好ましくは置換されていないアルキレン基またはフェニレン基であり、より好ましくは置換されていないアルキレン基である。置換基としては炭素数１～３のアルキル基、ハロゲン、ヒドロキシル基等が挙げられ、アルキレン基としては炭素数１～１０のもの、好ましくは炭素数１～３のもの、より好ましくは炭素数１のものが挙げられる。更に、Ｙはアルカリ金属であり、好ましくはリチウム、ナトリウム、カリウムであり、より好ましくはナトリウムである。 In the unsaturated sulfonic acid compound, R is a vinyl group or an ethynyl group, preferably a vinyl group. X is an optionally substituted alkylene group or phenylene group, preferably an unsubstituted alkylene group or phenylene group, and more preferably an unsubstituted alkylene group. Examples of the substituent include an alkyl group having 1 to 3 carbon atoms, a halogen, and a hydroxyl group. The alkylene group has 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms, and more preferably 1 carbon atom. Can be mentioned. Furthermore, Y is an alkali metal, preferably lithium, sodium or potassium, more preferably sodium.
　より具体的な不飽和スルホン酸化合物としては、アリルスルホン酸ナトリウム、ビニルスルホン酸ナトリウム、プロピンスルホン酸ナトリウム等が挙げられ、好ましくはアリルスルホン酸ナトリウムである。これらの不飽和スルホン酸化合物は、１種または２種以上を組み合わせて用いても良い。 More specific unsaturated sulfonic acid compounds include sodium allyl sulfonate, sodium vinyl sulfonate, sodium propyne sulfonate, and the like, and preferably sodium allyl sulfonate. These unsaturated sulfonic acid compounds may be used alone or in combination of two or more.
　本発明めっき液における、不飽和スルホン酸化合物の含有量は１～１０％、好ましくは４～８％である。 The content of the unsaturated sulfonic acid compound in the plating solution of the present invention is 1 to 10%, preferably 4 to 8%.
　本発明めっき液のベースとなる鉄－ニッケル合金電気めっき液として、特に好ましいのは、上記一般式（１）で表される不飽和スルホン酸化合物と、鉄を４～１２ｇ／Ｌ、好ましくは６～１０ｇ／Ｌ、ニッケルを２０～５０ｇ／Ｌ、好ましくは２５～４０ｇ／Ｌ含有させたものである。このような鉄－ニッケル合金電気めっき液であれば、開口部にフィリングした場合の鉄－ニッケル合金の組成が両者の合計量を１００％として、鉄が５５～６４％およびニッケルが３６～４５％となる。 As the iron-nickel alloy electroplating solution used as the base of the plating solution of the present invention, an unsaturated sulfonic acid compound represented by the above general formula (1) and iron of 4 to 12 g / L, preferably 6 are particularly preferable. ˜10 g / L, nickel contained in the amount of 20-50 g / L, preferably 25-40 g / L. With such an iron-nickel alloy electroplating solution, the composition of the iron-nickel alloy when filling the opening is 100%, and iron is 55-64% and nickel is 36-45%. It becomes.
　本発明めっき液には、更に、コバルト、モリブデン、タングステンを含有させてもよい。この場合のコバルト、モリブデン、タングステンの添加量は特に限定されず、例えば１～１００ｇ／Ｌ、好ましくは１～５０ｇ／Ｌである。また、コバルト、モリブデン、タングステン源としては、硫酸コバルト、スルファミン酸コバルト、モリブデン酸ナトリウム、タングステン酸ナトリウム等が挙げられる。 The plating solution of the present invention may further contain cobalt, molybdenum and tungsten. In this case, the addition amount of cobalt, molybdenum and tungsten is not particularly limited, and is, for example, 1 to 100 g / L, preferably 1 to 50 g / L. Examples of the cobalt, molybdenum, and tungsten sources include cobalt sulfate, cobalt sulfamate, sodium molybdate, and sodium tungstate.
　本発明めっき液には、更に、従来公知の鉄－ニッケル合金電気めっき液に添加されるサッカリン酸ナトリウム等の応力緩和剤等を添加してもよい。 In the plating solution of the present invention, a stress relaxation agent such as sodium saccharinate added to a conventionally known iron-nickel alloy electroplating solution may be further added.
　以下に、本発明めっき液のベースとなる鉄－ニッケル合金電気めっき液の好ましい態様として、ワット浴、スルファミン酸浴の組成を記載する。 Hereinafter, as preferred embodiments of the iron-nickel alloy electroplating solution used as the base of the plating solution of the present invention, the composition of the watt bath and the sulfamic acid bath will be described.
＜ワット浴＞
　硫酸ニッケル：５０～１２５ｇ／Ｌ、好ましくは６０～１００ｇ／Ｌ
　塩化ニッケル：４０～８０ｇ／Ｌ、好ましくは５０～７０ｇ／Ｌ
　ホウ酸：３０～６０ｇ／Ｌ
　硫酸第一鉄：２０～６０ｇ／Ｌ、好ましくは３５～５０ｇ／Ｌ
　グルコン酸ナトリウム：２０～８０ｇ／Ｌ、好ましくは５０～６０ｇ／Ｌ
　サッカリンナトリウム：１～５ｇ／Ｌ、好ましくは２～４ｇ／Ｌ
　アリルスルホン酸ナトリウム：１.５～１０ｇ／Ｌ、好ましくは３.５～８.
　５ｇ／Ｌ <Watt bath>
Nickel sulfate: 50 to 125 g / L, preferably 60 to 100 g / L
Nickel chloride: 40 to 80 g / L, preferably 50 to 70 g / L
Boric acid: 30-60g / L
Ferrous sulfate: 20-60 g / L, preferably 35-50 g / L
Sodium gluconate: 20-80 g / L, preferably 50-60 g / L
Saccharin sodium: 1-5 g / L, preferably 2-4 g / L
Sodium allyl sulfonate: 1.5 to 10 g / L, preferably 3.5 to 8.
5g / L
＜スルファミン酸浴＞
　スルファミン酸ニッケル：９０～２５０ｇ／Ｌ、好ましくは１４０～１９
　０ｇ／Ｌ
　ホウ酸：３０～６０ｇ／Ｌ
　臭化ニッケル：５～１５ｇ／Ｌ、好ましくは６～１０ｇ／Ｌ
　スルファミン酸鉄：２５～７５ｇ／Ｌ、好ましくは４０～６０ｇ／Ｌ
　グルコン酸ナトリウム：２０～８０ｇ／Ｌ、好ましくは５０～６０ｇ／Ｌ
　サッカリンナトリウム：１～５ｇ／Ｌ、好ましくは２～４ｇ／Ｌ
　アリルスルホン酸ナトリウム：１.５～１０ｇ／Ｌ、好ましくは３.５～８.
　５ｇ／Ｌ <Sulphamic acid bath>
Nickel sulfamate: 90 to 250 g / L, preferably 140 to 19
0g / L
Boric acid: 30-60g / L
Nickel bromide: 5 to 15 g / L, preferably 6 to 10 g / L
Iron sulfamate: 25 to 75 g / L, preferably 40 to 60 g / L
Sodium gluconate: 20-80 g / L, preferably 50-60 g / L
Saccharin sodium: 1-5 g / L, preferably 2-4 g / L
Sodium allyl sulfonate: 1.5 to 10 g / L, preferably 3.5 to 8.
5g / L
　本発明めっき液は、開口部を有する基板に電気めっきすることで開口部をフィリングすることができる。電気めっきする方法は、特に限定されず、例えば、開口部を有する基板に、アルカリ脱脂、酸活性等の前処理を行った後、これを本発明めっき液に浸漬する方法等が挙げられる。 The plating solution of the present invention can fill the opening by electroplating the substrate having the opening. The method of electroplating is not particularly limited, and examples thereof include a method in which a substrate having an opening is subjected to pretreatment such as alkali degreasing and acid activity and then immersed in the plating solution of the present invention.
　本発明めっき液で電気めっきすることができる基板は、特に限定されず、例えば、予め無電解めっき、ＰＶＤ、ＣＶＤ処理などの導電化処理を施した樹脂、セラミックス、ガラス等で形成されたもの等が挙げられる。本発明において開口部とは、ビア等のことをいう。また、開口部の大きさは特に限定されないが、例えば、ビアであれば直径が、５～１５０μｍ程度、深さが、１０～１００μｍ程度、アスペクト比が、０.１～２程度である。 The substrate that can be electroplated with the plating solution of the present invention is not particularly limited. For example, a substrate formed of a resin, ceramics, glass or the like that has been previously subjected to a conductive treatment such as electroless plating, PVD, or CVD. Is mentioned. In the present invention, the opening means a via or the like. The size of the opening is not particularly limited. For example, in the case of a via, the diameter is about 5 to 150 μm, the depth is about 10 to 100 μm, and the aspect ratio is about 0.1 to 2.
　電気めっきの条件は、特に限定されず、通常の電気めっきによるフィリングの条件を用いればよく、例えば、浴温３０～６０℃で、アノードに鉄、ニッケルを併用し、陰極電流密度０.０５～３Ａ／ｄｍ２で、開口部が充填されるまで行えばよい。また、電気めっきの際にはパドル等で撹拌することが好ましい。 The conditions for electroplating are not particularly limited, and normal filling conditions for electroplating may be used. For example, the bath temperature is 30 to 60 ° C., iron and nickel are used in combination with the anode, and the cathode current density is 0.05 to It may be performed at 3 A / dm 2 until the opening is filled. Moreover, it is preferable to stir with a paddle or the like during electroplating.
　上記のように本発明のめっき液を用いて開口部を有する基板に電気めっきを行えば、基板の開口部をフィリングすることができる。なお、本発明の場合、フィリングされた鉄－ニッケル合金は熱処理の必要もない。 As described above, when electroplating is performed on a substrate having an opening using the plating solution of the present invention, the opening of the substrate can be filled. In the present invention, the filled iron-nickel alloy does not require heat treatment.
　また、本発明のめっき液を用いて開口部をフィリングすれば、開口部にフィリングされた鉄－ニッケル合金の開口部から深さ方向への組成のばらつきが少ない。 Further, if the opening is filled using the plating solution of the present invention, there is little variation in composition in the depth direction from the opening of the iron-nickel alloy filled in the opening.
　更に、本発明のめっき液のうち、アセチレンアルコールとして炭素数５以上のもの、特にヘキシンジオールを用いためっき液を用いて開口部をフィリングした場合には、開口部から深さ方向への組成のばらつきが少なく、例えば、開口部の底からビア深さの３０％の膜厚までの組成と開口部の表面組成との差が±１０％以下となる。なお、フィリングされた鉄－ニッケル合金の開口部から深さ方向への組成は、エネルギー分散型Ｘ線分析（ＥＤＳ）等により測定することができる。 Further, among the plating solutions of the present invention, when the opening is filled with a acetylene alcohol having 5 or more carbon atoms, particularly a plating solution using hexynediol, the composition in the depth direction from the opening. For example, the difference between the composition from the bottom of the opening to the film thickness of 30% of the via depth and the surface composition of the opening is ± 10% or less. The composition in the depth direction from the opening of the filled iron-nickel alloy can be measured by energy dispersive X-ray analysis (EDS) or the like.
　以上のように開口部を有する基板の開口部を本発明のめっき液を用いて鉄－ニッケル合金でフィリングし、更に、化学機械研磨や積層工程、再度フィリングめっき、導電ペーストの充填およびバンプ形成等をすることにより、開口部が、鉄－ニッケル合金でフィリングされた回路基板を製造することができる。 As described above, the opening of the substrate having the opening is filled with an iron-nickel alloy using the plating solution of the present invention, and further, chemical mechanical polishing, laminating process, filling plating, filling of conductive paste, bump formation, etc. By doing this, it is possible to manufacture a circuit board whose opening is filled with an iron-nickel alloy.
　なお、上記回路基板の中でも、フィリングした後の開口部の上部に積層時にスタックビアを形成することが可能および電子部品を搭載するためのパッドを形成することが可能な多層プリント配線板が好ましい。 Of the above circuit boards, a multilayer printed wiring board is preferable, in which a stack via can be formed at the time of lamination on the upper part of the opening after filling and a pad for mounting an electronic component can be formed.
　このようにして製造される回路基板は、低熱膨張合金を配線としているため、金属と樹脂間における熱膨張率の差が原因で生じるクラックなどの劣化を抑制できる。 Since the circuit board manufactured in this way uses a low thermal expansion alloy as the wiring, it is possible to suppress deterioration such as cracks caused by the difference in thermal expansion coefficient between the metal and the resin.
　以下、実施例を挙げて本発明を詳細に説明するが、本発明はこれら実施例に何ら限定されるものではない。 Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.
実　施　例　１
　　　鉄－ニッケル合金用電気めっき液の調製：
　水に、スルファミン酸ニッケル・４水和物１５６ｇ／Ｌ、ホウ酸３０ｇ／Ｌ、臭化ニッケル７ｇ／Ｌ、スルファミン酸鉄・５水和物４７ｇ／Ｌ、グルコン酸ナトリウム６０ｇ／Ｌ、サッカリンナトリウム３.２ｇ／Ｌおよびアリルスルホン酸ナトリウム（３６％）１６ｍｌ／Ｌ、ヘキシンジオール１.０ｇを添加、混合し、鉄－ニッケル合金用電気めっき液を調製した。このめっき浴のｐＨは３.８であり、ニッケルと鉄の含有量はそれぞれ３０ｇ／Ｌおよび７.５ｇ／Ｌであった。 Example 1
Preparation of electroplating solution for iron-nickel alloy:
In water, nickel sulfamate tetrahydrate 156 g / L, boric acid 30 g / L, nickel bromide 7 g / L, iron sulfamate pentahydrate 47 g / L, sodium gluconate 60 g / L, saccharin sodium 3. An electroplating solution for iron-nickel alloy was prepared by adding and mixing 2 g / L, sodium allylsulfonate (36%) 16 ml / L, and hexynediol 1.0 g. The plating bath had a pH of 3.8 and nickel and iron contents of 30 g / L and 7.5 g / L, respectively.
比　較　例　１
　　　鉄－ニッケル合金用電気めっき液の調製：
　ヘキシンジオールを含有しない以外は実施例１と同様にして鉄－ニッケル合金用電気めっき液を調製した。 Comparative Example 1
Preparation of electroplating solution for iron-nickel alloy:
An electroplating solution for iron-nickel alloy was prepared in the same manner as in Example 1 except that it did not contain hexynediol.
実　施　例　２
　　　ビアを有する基板のフィリング：
　実施例１および比較例１で調製した鉄－ニッケル合金用電気めっき液を用い、以下の表１に記載の条件でビアを有する基板のフィリングを行った。フィリング後の断面写真を図１に示した。また、条件２で電気めっきした後の基板のＥＤＳの測定地点を図２に、その測定地点における鉄とニッケルの組成を表２に示した。 Example 2
Filling a substrate with vias:
Using the electroplating solution for iron-nickel alloy prepared in Example 1 and Comparative Example 1, the substrate having vias was filled under the conditions shown in Table 1 below. A cross-sectional photograph after filling is shown in FIG. Further, the measurement points of EDS of the substrate after electroplating under condition 2 are shown in FIG.
＜基板＞
　開口部がブラインドビアであり、ブラインドビアの直径が７０μｍ、深さが４０μｍ、アスペクト比０.５７の回路基板に無電解銅めっきを施したものを用いた。　　 <Board>
A circuit board having an opening of a blind via, a diameter of the blind via of 70 μm, a depth of 40 μm, and an aspect ratio of 0.57 was used.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　ヘキシンジオールを含有する本発明の鉄－ニッケル合金電気めっき液はビアをフィリングすることができたが、ヘキシンジオールを含有しない鉄－ニッケル合金電気めっき液はビアをフィリングすることができなかった。また、本発明によりフィリングされた鉄－ニッケル合金は開口部から深さ方向への組成のばらつきが小さいことも分かった。 The iron-nickel alloy electroplating solution of the present invention containing hexynediol was able to fill vias, but the iron-nickel alloy electroplating solution not containing hexynediol was not able to fill vias. . It was also found that the iron-nickel alloy filled according to the present invention has a small variation in composition in the depth direction from the opening.
実　施　例　３
　　　鉄－ニッケル合金用電気めっき液の調製：
　ヘキシンジオールをプロパルギルアルコール０.０２ｇとする以外は実施例１と同様にして鉄－ニッケル合金用電気めっき液を調製した。 Example 3
Preparation of electroplating solution for iron-nickel alloy:
An electroplating solution for an iron-nickel alloy was prepared in the same manner as in Example 1 except that hexynediol was changed to 0.02 g of propargyl alcohol.
実　施　例　４
　　　ビアを有する基板のフィリング：
　実施例３の鉄－ニッケル合金用電気めっき液を用いる以外は、実施例２の条件１と同様の条件で実施例２と同様の基板にフィリングを行った。フィリング後の断面写真を図３に示した。また、実施例２と同様にＥＤＳにより測定した鉄とニッケルの組成を表３に示した。 Example 4
Filling a substrate with vias:
The same substrate as in Example 2 was filled under the same conditions as in Condition 1 of Example 2 except that the electroplating solution for iron-nickel alloy of Example 3 was used. A cross-sectional photograph after filling is shown in FIG. Further, the composition of iron and nickel measured by EDS as in Example 2 is shown in Table 3.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　プロパルギルアルコールを含有する本発明の鉄－ニッケル合金電気めっき液はビアをフィリングすることができた。また、本発明によりフィリングされた鉄－ニッケル合金は開口部から深さ方向への組成のばらつきは、プロパルギルアルコールを用いた場合よりもヘキシンジオールを用いた場合の方が小さいことも分かった。 The iron-nickel alloy electroplating solution of the present invention containing propargyl alcohol was able to fill vias. It was also found that the iron-nickel alloy filled according to the present invention has a smaller variation in composition in the depth direction from the opening when hexynediol is used than when propargyl alcohol is used.
実　施　例　５
　　　鉄－ニッケル合金用電気めっき液の調製：
　ヘキシンジオールをジメチルオクチンジオール１.５ｇ／Ｌにする以外は実施例１と同様にして鉄－ニッケル合金用電気めっき液を調製した。 Example 5
Preparation of electroplating solution for iron-nickel alloy:
An electroplating solution for iron-nickel alloy was prepared in the same manner as in Example 1 except that hexynediol was changed to 1.5 g / L of dimethyloctynediol.
実　施　例　６
　　　鉄－ニッケル合金用電気めっき液の調製：
　水に、硫酸ニッケル７５ｇ／Ｌ、ホウ酸３０ｇ／Ｌ、塩化ニッケル５５ｇ／Ｌ、硫酸第一鉄３７.５ｇ／Ｌ、グルコン酸ナトリウム６０ｇ／Ｌ、サッカリンナトリウム３.２ｇ／Ｌおよびアリルスルホン酸ナトリウム（３６％）１６ｍｌ／Ｌ、ヘキシンジオール１.０ｇを添加、混合し、鉄－ニッケル合金用電気めっき液を調製した。このめっき浴のｐＨは３.０であり、ニッケルと鉄の含有量はそれぞれ３０ｇ／Ｌおよび７.５ｇ／Ｌであった。 Example 6
Preparation of electroplating solution for iron-nickel alloy:
In water, nickel sulfate 75 g / L, boric acid 30 g / L, nickel chloride 55 g / L, ferrous sulfate 37.5 g / L, sodium gluconate 60 g / L, saccharin sodium 3.2 g / L and sodium allyl sulfonate ( 36%) 16 ml / L and 1.0 g of hexynediol were added and mixed to prepare an electroplating solution for iron-nickel alloy. The pH of this plating bath was 3.0, and the contents of nickel and iron were 30 g / L and 7.5 g / L, respectively.
実　施　例　７
　　　鉄－ニッケル－コバルト合金用電気めっき液の調製：
　水に、スルファミン酸ニッケル・４水和物１２６ｇ／Ｌ、ホウ酸３０ｇ／Ｌ、臭化ニッケル７ｇ／Ｌ、スルファミン酸鉄・５水和物５０ｇ／Ｌ、スルファミン酸コバルト・４水和物３.５ｇ／Ｌ、グルコン酸ナトリウム６０ｇ／Ｌ、サッカリンナトリウム３.２ｇ／Ｌおよびアリルスルホン酸ナトリウム（３６％）１６ｍｌ／Ｌ、ヘキシンジオール１.０ｇを添加、混合し、鉄－ニッケル合金用電気めっき液を調製した。このめっき浴のｐＨは３.８であり、ニッケル、鉄、コバルトの含有量はそれぞれ３０ｇ／Ｌ、７.５ｇ／Ｌおよび０.６２５ｇ／Ｌであった。 Example 7
Preparation of electroplating solution for iron-nickel-cobalt alloy:
In water, 126 g / L of nickel sulfamate tetrahydrate, 30 g / L of boric acid, 7 g / L of nickel bromide, 50 g / L of iron sulfamate pentahydrate, cobalt sulfamate tetrahydrate 3. 5 g / L, sodium gluconate 60 g / L, saccharin sodium 3.2 g / L, sodium allyl sulfonate (36%) 16 ml / L, hexynediol 1.0 g are added and mixed, and an electroplating solution for iron-nickel alloy Was prepared. The pH of this plating bath was 3.8, and the contents of nickel, iron and cobalt were 30 g / L, 7.5 g / L and 0.625 g / L, respectively.
　本発明の鉄－ニッケル合金フィリング用電気めっき液は、ビア等の開口部のフィリング等の回路形成に利用できる。
 
　　　　　　　　　　　　　　　　　　　　　　　　　　　以　　上 The electroplating solution for iron-nickel alloy filling of the present invention can be used for circuit formation such as filling of openings such as vias.

more than

Claims (9)

  1. 　鉄－ニッケル合金電気めっき液に、更に、アセチレンアルコールを含有させたことを特徴とする鉄－ニッケル合金フィリング用電気めっき液。 An iron-nickel alloy filling electroplating solution characterized by further containing acetylene alcohol in the iron-nickel alloy electroplating solution.
  2. 　アセチレンアルコールが、炭素数５以上のものである請求項１記載の鉄－ニッケル合金フィリング用電気めっき液。 2. The electroplating solution for iron-nickel alloy filling according to claim 1, wherein the acetylene alcohol has 5 or more carbon atoms.
  3. 　アセチレンアルコールが、ヘキシンジオールである請求項１記載の鉄－ニッケル合金フィリング用電気めっき液。 2. The electroplating solution for iron-nickel alloy filling according to claim 1, wherein the acetylene alcohol is hexynediol.
  4. 　鉄－ニッケル合金電気めっき液が、鉄を４～１２ｇ／Ｌ、ニッケルを２０～５０ｇ／Ｌおよび以下の一般式（１）
    Figure JPOXMLDOC01-appb-C000001
     （ただし、Ｒはビニル基またはエチニル基、Ｘは置換されていてもよい、アルキレン基またはフェニレン基、Ｙはアルカリ金属を示す。）
    で表される不飽和スルホン酸化合物を含有するものである請求項１～３の何れかに記載の鉄－ニッケル合金フィリング用電気めっき液。     The iron-nickel alloy electroplating solution contains 4 to 12 g / L of iron, 20 to 50 g / L of nickel, and the following general formula (1)
    Figure JPOXMLDOC01-appb-C000001
     (However, R represents a vinyl group or ethynyl group, X represents an optionally substituted alkylene group or phenylene group, and Y represents an alkali metal.)
    4. The electroplating solution for iron-nickel alloy filling according to claim 1, which contains an unsaturated sulfonic acid compound represented by the formula:
  5. 　開口部を有する基板を、請求項１～４の何れかに記載の鉄－ニッケル合金フィリング用電気めっき液で電気めっきを行うことを特徴とする開口部のフィリング方法。 A method of filling an opening, comprising: electroplating a substrate having an opening with the electroplating solution for iron-nickel alloy filling according to any one of claims 1 to 4.
  6. 　開口部を有する基板を、請求項１～４の何れかに記載の鉄－ニッケル合金フィリング用電気めっき液で電気めっきを行うことを特徴とする回路基板の製造方法。 A method for producing a circuit board, comprising: electroplating a substrate having an opening with the electroplating solution for iron-nickel alloy filling according to any one of claims 1 to 4.
  7. 　開口部が、鉄－ニッケル合金でフィリングされていることを特徴とする回路基板。 A circuit board characterized in that the opening is filled with an iron-nickel alloy.
  8. 　鉄－ニッケル合金が、鉄が５５～６４質量％およびニッケルが３６～４５質量％である請求項７記載の回路基板。 The circuit board according to claim 7, wherein the iron-nickel alloy contains 55 to 64% by mass of iron and 36 to 45% by mass of nickel.
  9. 　多層プリント配線板である請求項７または８記載の回路基板。 The circuit board according to claim 7, which is a multilayer printed wiring board.
PCT/JP2018/012072 2017-04-07 2018-03-26 Iron-nickel alloy electroplating liquid for filling and method for filling opening using same, and method for manufacturing circuit substrate WO2018186217A1 (en)

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WO2020160352A1 (en) 2019-01-31 2020-08-06 Macdermid Enthone Inc. Composition and method for fabrication of nickel interconnects
KR102680337B1 (en) * 2019-01-31 2024-07-03 맥더미드 엔쏜 인코포레이티드 Compositions and methods for making nickel interconnects

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WO2020160352A1 (en) 2019-01-31 2020-08-06 Macdermid Enthone Inc. Composition and method for fabrication of nickel interconnects
CN113366156A (en) * 2019-01-31 2021-09-07 麦克德米德乐思公司 Composition and method for fabricating nickel interconnects
EP3918115A4 (en) * 2019-01-31 2022-11-09 MacDermid Enthone Inc. Composition and method for fabrication of nickel interconnects
KR102680337B1 (en) * 2019-01-31 2024-07-03 맥더미드 엔쏜 인코포레이티드 Compositions and methods for making nickel interconnects

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