JP2014055355A - Apparatus for copper electroplating - Google Patents

Apparatus for copper electroplating Download PDF

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JP2014055355A
JP2014055355A JP2013179274A JP2013179274A JP2014055355A JP 2014055355 A JP2014055355 A JP 2014055355A JP 2013179274 A JP2013179274 A JP 2013179274A JP 2013179274 A JP2013179274 A JP 2013179274A JP 2014055355 A JP2014055355 A JP 2014055355A
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copper
manganese oxide
plating
electrolytic copper
plating solution
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JP6026976B2 (en
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Hyo Seung Nam
ナム・ヒョ・スン
Mi Geum Kim
キム・ミ・グム
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Samsung Electro Mechanics Co Ltd
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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
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/10—Electrodes, e.g. composition, counter electrode
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/16—Regeneration of process solutions
    • C25D21/18—Regeneration of process solutions of electrolytes

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
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  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

PROBLEM TO BE SOLVED: To provide an apparatus for copper electroplating that can exhibit an excellent suppression effect of surface plating.SOLUTION: Provided is an apparatus for copper electroplating that comprises a single tank 120 comprising a cathode 121, an insoluble anode 122, copper balls 125 and a plating solution 123, in which the plating solution contains manganese oxide. Also provided is an apparatus for copper electroplating that comprises a main tank 123 comprising the cathode 121, the insoluble anode 122 and the plating solution 123, and a dissolving tank 120 comprising the copper balls 125 and a manganese oxide 126. The apparatus having this structure can exhibit an excellent suppression effect of surface plating, even applied under a low concentration, by utilizing the manganese oxide 126 having a higher redox potential, in stead of the conventional Fe, as a copper source in an apparatus for copper electroplating. The manganese oxide is selected from KMnOor NaMnOin a concentration of 0.1 to 10 g/L. The plating solution comprises copper sulfate of 50 to 350 g/L, sulfuric acid of 10 to 150 g/L, and chlorine of 10 to 200 mg/L.

Description

本発明は、電気銅めっき装置に関する。   The present invention relates to an electrolytic copper plating apparatus.

電気銅めっきにおいて、不溶性陽極は、銅を溶かして使用する際に異物を最小化するために用いられる。前記不溶性陽極を用いた電気銅めっき方式は、銅（Ｃｕ）を供給する方法によって、ＣｕＯをめっき液に補充する方式と、めっき液内にＦｅ３＋イオンを溶解させて銅イオンを本槽に供給する方式と、に大別される。 In electrolytic copper plating, the insoluble anode is used for minimizing foreign matters when copper is used by melting. The electrolytic copper plating method using the insoluble anode is a method of replenishing CuO with a plating solution by supplying copper (Cu), and supplying copper ions to the main tank by dissolving Fe 3+ ions in the plating solution. It is divided roughly into the method to do.

図１はＣｕＯ補充方式による不溶性陽極を用いた電気銅めっき装置であり、本槽１０でめっき反応により消耗されるＣｕを、別の溶解槽１４に粉末状のＣｕＯ１５を投入して空気撹拌などで溶解させた後本槽１０に再循環して補充する方式である。この際、前記本槽１０には陰極１１及び陽極１２が含まれており、めっき液１３の主成分としては硫酸銅／硫酸／塩素の無機物が用いられる。   FIG. 1 shows an electrolytic copper plating apparatus using an insoluble anode by a CuO replenishment method, in which Cu consumed by the plating reaction in the main tank 10 is charged and powdered CuO 15 is charged into another dissolution tank 14 and air stirring is performed. In this method, after being dissolved, the tank 10 is recirculated and replenished. At this time, the main tank 10 includes a cathode 11 and an anode 12, and an inorganic substance of copper sulfate / sulfuric acid / chlorine is used as a main component of the plating solution 13.

図２はＦｅ３＋方式による不溶性陽極を用いた電気銅めっき装置であり、本槽２０でめっき反応により消耗される銅を、別の溶解槽２４のめっき液に純粋な銅ボール２５を投入して循環させると、Ｆｅ３＋２６の自発的な還元反応によって銅ボール２５が溶けて銅イオンが供給される方式である。この際、前記本槽２０には陰極２１及び陽極２２が含まれており、めっき液２３の主成分としては硫酸銅／硫酸／塩素の無機物が用いられる。 FIG. 2 shows an electrolytic copper plating apparatus using an insoluble anode by the Fe 3+ method, in which copper consumed by the plating reaction in the main tank 20 is poured into a pure copper ball 25 into a plating solution in another dissolution tank 24. When circulating, the copper ball 25 is melted by the spontaneous reduction reaction of Fe 3+ 26 and copper ions are supplied. At this time, the main tank 20 includes a cathode 21 and an anode 22, and an inorganic substance of copper sulfate / sulfuric acid / chlorine is used as a main component of the plating solution 23.

上記の二つの方式は垂直及び水平めっき設備方式に広く用いられているが、ＣｕＯの場合、無機及び有機不純物の流入によって補充（Ｆｉｌｌ）性能の低下が誘発される場合が多く、Ｆｅ３＋の場合、特定企業の独占により、改善／改造に対する制約が大きい状況であるため、これに代替可能な装置の開発が求められている状況である。 The above two methods are widely used in vertical and horizontal plating equipment methods, but in the case of CuO, inflow of inorganic and organic impurities often induces a drop in refill performance, and in the case of Fe 3+ Since the restrictions on improvement / modification are large due to the monopoly of a specific company, the development of a device that can replace this is demanded.

特表２００８−５１３９８５号公報Special table 2008-513985 gazette

本発明は、従来の不溶性陽極を用いた電気銅めっき方式の問題を誘発することなく、これに代替可能な新しい電気銅めっき装置を提供することをその目的とする。   It is an object of the present invention to provide a new electrolytic copper plating apparatus that can replace the conventional copper electroplating system using an insoluble anode without inducing the problems.

本発明の一実施形態による電気銅めっき装置は、陰極、不溶性陽極、銅ボール、及びめっき液が単一の槽（ｂａｔｈ）に含まれる電気銅めっき装置であって、前記めっき液はマンガン酸化物を含むことを特徴とする。   An electrolytic copper plating apparatus according to an embodiment of the present invention is an electrolytic copper plating apparatus including a cathode, an insoluble anode, a copper ball, and a plating solution in a single bath, wherein the plating solution is a manganese oxide. It is characterized by including.

前記マンガン酸化物は、ＫＭｎＯ４及びＮａＭｎＯ４から選択されるものであることができる。 The manganese oxide may be selected from KMnO 4 and NaMnO 4 .

前記マンガン酸化物は、０．１〜１０ｇ／Ｌの濃度で含まれることが好ましい。   The manganese oxide is preferably contained at a concentration of 0.1 to 10 g / L.

前記めっき液は、５０〜３５０ｇ／Ｌの硫酸銅、１０〜１５０ｇ／Ｌの硫酸、及び１０〜２００ｍｇ／Ｌの塩素を含む。   The plating solution contains 50 to 350 g / L copper sulfate, 10 to 150 g / L sulfuric acid, and 10 to 200 mg / L chlorine.

前記不溶性陽極は、チタン（Ｔｉ）に白金（Ｐｔ）またはＩｒＯ２がコーティングされた材質を用いることが好ましい。 The insoluble anode, it is preferable to use a titanium (Ti) to platinum (Pt) or IrO 2 was coated material.

また、本発明の他の一実施形態による電気銅めっき装置は、陰極、不溶性陽極、及びめっき液を含む本槽と、銅ボール及び前記不溶性陽極の銅供給源としてマンガン酸化物を含む溶解槽と、を含む。   In addition, an electrolytic copper plating apparatus according to another embodiment of the present invention includes a main tank containing a cathode, an insoluble anode, and a plating solution, and a dissolution tank containing manganese oxide as a copper supply source for copper balls and the insoluble anode. ,including.

前記溶解槽から本槽のめっき液への銅の供給は、前記溶解槽のマンガン酸化物と銅ボールの反応により銅が銅イオンに溶解されてなされることができる。   The supply of copper from the dissolution tank to the plating solution in the main tank can be performed by dissolving copper in copper ions by the reaction of manganese oxide and copper balls in the dissolution tank.

前記マンガン酸化物は、ＫＭｎＯ４及びＮａＭｎＯ４から選択されるものであることが好ましい。 The manganese oxide is preferably selected from KMnO 4 and NaMnO 4 .

前記マンガン酸化物は、０．１〜１０ｇ／Ｌの濃度で含まれることが好ましい。   The manganese oxide is preferably contained at a concentration of 0.1 to 10 g / L.

前記電気銅めっき装置のめっき液は、５０〜３５０ｇ／Ｌの硫酸銅、１０〜１５０ｇ／Ｌの硫酸 、及び１０〜２００ｍｇ／Ｌの塩素を含む。   The plating solution of the electrolytic copper plating apparatus contains 50 to 350 g / L copper sulfate, 10 to 150 g / L sulfuric acid, and 10 to 200 mg / L chlorine.

本発明によると、電気銅めっき装置における銅供給源として、従来のＦｅ３＋の代わりにより高い酸化還元電位を有するマンガン酸化物を用いることにより、低濃度で適用する場合にも、優れた表面めっき抑制効果が得られる。また、スルーホール（Ｔｈｒｏｕｇｈ Ｈｏｌｅ）またはブラインドビアホール（Ｂｌｉｎｄ ｖｉａ ｈｏｌｅ）のような構造物において、ホールの内部より表面のめっき速度を抑制して、均一電着性を改善することができる。 According to the present invention, by using manganese oxide having a higher redox potential instead of conventional Fe 3+ as a copper supply source in an electrolytic copper plating apparatus, excellent surface plating suppression even when applied at a low concentration An effect is obtained. In addition, in a structure such as a through hole or a blind via hole, it is possible to improve the throwing power by suppressing the plating rate of the surface from the inside of the hole.

従来のＣｕＯ補充方式による不溶性陽極を用いた電気銅めっき装置を示す図面である。1 is a drawing showing a conventional copper electroplating apparatus using an insoluble anode by a CuO replenishment method. 従来のＦｅ３＋方式による不溶性陽極を用いた電気銅めっき装置を示す図面である。It is drawing which shows the electrolytic copper plating apparatus using the insoluble anode by the conventional Fe3 + system. 本発明の一実施形態による不溶性陽極を用いた電気銅めっき装置を示す図面である。It is drawing which shows the electrolytic copper plating apparatus using the insoluble anode by one Embodiment of this invention. 本発明の他の実施形態による不溶性陽極を用いた電気銅めっき装置を示す図面である。4 is a view showing an electrolytic copper plating apparatus using an insoluble anode according to another embodiment of the present invention.

以下、本発明について詳細に説明する。   Hereinafter, the present invention will be described in detail.

本明細書で用いられる用語は、特定実施形態を説明するためのものであり、本発明を限定しようとするものではない。本明細書で用いられたように、単数型は文句で特別に言及しない限り複数型も含む。明細書で用いられる「含む（ｃｏｍｐｒｉｓｅ）」及び／または「含んでいる（ｃｏｍｐｒｉｓｉｎｇ）」は言及された形状、数字、段階、動作、部材、要素及び／またはこれらの組合せの存在を得するものであり、一つ以上の他の形状、数字、段階、動作、部材、要素及び／またはこれらの組合せの存在または追加を排除しない。   The terminology used herein is for the purpose of describing particular embodiments and is not intended to be limiting of the invention. As used herein, the singular form also includes the plural form unless the context clearly indicates otherwise. As used herein, “comprise” and / or “comprising” is to obtain the presence of the mentioned shape, number, step, action, member, element and / or combination thereof. Does not exclude the presence or addition of one or more other shapes, numbers, steps, actions, members, elements and / or combinations thereof.

本発明は不溶性陽極を用いた電気銅めっき装置に関するものであって、本発明の一実施形態による電気銅めっき装置は、図３に示したとおりである。   The present invention relates to an electrolytic copper plating apparatus using an insoluble anode, and the electrolytic copper plating apparatus according to an embodiment of the present invention is as shown in FIG.

これを参照すると、本発明の一実施形態による電気銅めっき装置は、陰極１１１、不溶性陽極１１２、銅ボール１１５、及びめっき液１１３が単一の槽１１０に含まれる電気銅めっき装置であり、前記めっき液１１３にはマンガン酸化物１１６が含まれる。   Referring to this, an electrolytic copper plating apparatus according to an embodiment of the present invention is an electrolytic copper plating apparatus in which a cathode 111, an insoluble anode 112, a copper ball 115, and a plating solution 113 are included in a single tank 110, The plating solution 113 contains a manganese oxide 116.

前記図３による電気銅めっき装置は、一つの槽１１０内に、電気銅めっきを行うための全ての構成要素が含まれている構造を有する。   The electrolytic copper plating apparatus according to FIG. 3 has a structure in which all components for performing electrolytic copper plating are included in one tank 110.

前記電気銅めっき装置における陰極１１１は、電気銅めっきがなされる被めっき体であり、例えば、パネル形態のプリント回路基板であることができる。   The cathode 111 in the electrolytic copper plating apparatus is an object to be plated with electrolytic copper plating, and can be, for example, a printed circuit board in the form of a panel.

また、前記不溶性陽極１１２としては、チタン（Ｔｉ）に白金（Ｐｔ）またはＩｒＯ２がコーティングされた材質を用いることができる。前記不溶性陽極１１２は、電気銅めっきにおいて、銅を用いてめっきする際に異物を最小化するために用いられる。 The insoluble anode 112 may be made of a material in which titanium (Ti) is coated with platinum (Pt) or IrO 2 . The insoluble anode 112 is used for minimizing foreign matters when plating with copper in electrolytic copper plating.

また、前記電気銅めっきに用いられる銅めっき液は、５０〜３５０ｇ／Ｌの硫酸銅、１０〜１５０ｇ／Ｌの硫酸、１０〜２００ｍｇ／Ｌの塩素イオンを含む。特に、本発明では、不溶性陽極のＣｕ供給のための成分として強い酸化力を有するマンガン酸化物を含む。   Moreover, the copper plating solution used for the said electrolytic copper plating contains 50-350 g / L copper sulfate, 10-150 g / L sulfuric acid, and 10-200 mg / L chlorine ion. In particular, in the present invention, manganese oxide having strong oxidizing power is included as a component for supplying Cu of the insoluble anode.

前記マンガン酸化物は、ＫＭｎＯ４及びＮａＭｎＯ４から選択されるものであることができる。前記マンガン酸化物は、銅ボールを溶解させて、銅イオンを生成させる役割をする。また、この反応後に生成された副産物であるＫＭｎＯ２は、ＫＭｎＯ４にさらに酸化されて再生される。前記マンガン酸化物は、被めっき体である陰極の表面に作用して、めっきを抑制する効果を有する。 The manganese oxide may be selected from KMnO 4 and NaMnO 4 . The manganese oxide serves to dissolve copper balls and generate copper ions. Further, KMnO 2 which is a by-product generated after this reaction is further oxidized to KMnO 4 and regenerated. The said manganese oxide acts on the surface of the cathode which is a to-be-plated body, and has the effect which suppresses plating.

前記マンガン酸化物は０．１〜１０ｇ／Ｌの濃度で含まれることが好ましい。前記マンガン酸化物の濃度が０．１ｇ／Ｌ未満である場合には、表面めっき抑制効果が微小であるため均一電着性が得られず、また、１０ｇ／Ｌを超過する場合には、表面めっき抑制効果が過多であるため表面めっきの厚さが不足したり未めっきが発生して好ましくない。   The manganese oxide is preferably contained at a concentration of 0.1 to 10 g / L. When the concentration of the manganese oxide is less than 0.1 g / L, uniform electrodeposition cannot be obtained because the surface plating suppression effect is minute, and when the concentration exceeds 10 g / L, the surface Since the plating suppression effect is excessive, the thickness of the surface plating is insufficient or unplating occurs, which is not preferable.

また、前記めっき液に含まれる硫酸銅は、五水和物の形態で含まれることができ、その濃度が低すぎる場合には陰極電流の効率が低下するため、５０〜３５０ｇ／Ｌで含まれることが安定しためっき効率を得るために好ましい。   Further, the copper sulfate contained in the plating solution can be contained in the form of pentahydrate, and when the concentration is too low, the efficiency of the cathode current is reduced, so it is contained at 50 to 350 g / L. Is preferable in order to obtain stable plating efficiency.

また、前記めっき液の硫酸は１０〜１５０ｇ／Ｌの濃度で含まれることが、伝導度を増加させて通電を円滑にするという点で好ましい。   Moreover, it is preferable that the sulfuric acid of the said plating solution is contained by the density | concentration of 10-150 g / L from the point of increasing conductivity and smoothing electricity supply.

また、前記めっき液の塩素イオンは、ＨＣｌまたはＫＣｌの形態で含まれることができ、添加剤と相まって平滑作用が明確に現れるためには、その濃度が１０〜２００ｍｇ／Ｌであることが好ましい。   In addition, the chlorine ions of the plating solution may be included in the form of HCl or KCl, and the concentration is preferably 10 to 200 mg / L in order for the smoothing action to appear clearly in combination with the additive.

また、本発明の他の一実施形態による電気銅めっき装置は、図４に示したとおりであり、これを参照すると、陰極１２１、不溶性陽極１２２、及びめっき液１２３を含む本槽１２０と、銅ボール１２５及びマンガン酸化物１２６を含む溶解槽１２４と、を含む。   Further, an electrolytic copper plating apparatus according to another embodiment of the present invention is as shown in FIG. 4, and referring to this, a main tank 120 including a cathode 121, an insoluble anode 122, and a plating solution 123, and a copper A melting bath 124 containing balls 125 and manganese oxide 126.

前記実施形態による電気銅めっき装置は、陰極１２１、不溶性陽極１２２、及びめっき液１２３は本槽１２０に含まれ、銅供給のために銅ボール１２５及びマンガン酸化物１２６は溶解槽１２４に別に含まれる構造を有する。   In the electrolytic copper plating apparatus according to the embodiment, the cathode 121, the insoluble anode 122, and the plating solution 123 are included in the main tank 120, and the copper ball 125 and the manganese oxide 126 are separately included in the dissolution tank 124 for supplying copper. It has a structure.

従って、前記溶解槽１２４に銅ボール１２５を投入すると、この銅ボール１２５がマンガン酸化物１２６によって銅イオンに溶解され、本槽１２０のめっき液１２３に供給される。また、前記反応後に生成された副産物であるＫＭｎＯ２は、本槽１２０の陽極１２２でＫＭｎＯ４にさらに酸化されて再生される。従って、前記マンガン酸化物は、被めっき体である陰極１２１の表面に作用して、めっきを抑制する効果を有する。 Therefore, when the copper ball 125 is introduced into the dissolution tank 124, the copper ball 125 is dissolved in copper ions by the manganese oxide 126 and supplied to the plating solution 123 in the main tank 120. Further, KMnO 2 which is a by-product generated after the reaction is further oxidized and regenerated to KMnO 4 at the anode 122 of the main tank 120. Therefore, the manganese oxide acts on the surface of the cathode 121, which is an object to be plated, and has an effect of suppressing plating.

前記電気銅めっき装置における陰極１２１は、電気銅めっきがなされる被めっき体であり、例えば、パネル形態のプリント回路基板であることができる。   The cathode 121 in the electrolytic copper plating apparatus is an object to be plated, and can be, for example, a printed circuit board in the form of a panel.

また、前記不溶性陽極１２２としては、チタン（Ｔｉ）に白金（Ｐｔ）またはＩｒＯ２がコーティングされた材質を用いることができる。前記不溶性陽極１２２は、電気銅めっきにおいて、銅を用いてめっきする際に異物を最小化するために用いられる。 As the insoluble anode 122, a material in which titanium (Ti) is coated with platinum (Pt) or IrO 2 can be used. The insoluble anode 122 is used for minimizing foreign matters when plating using copper in electrolytic copper plating.

また、前記電気銅めっきに用いられる銅めっき液は、５０〜３５０ｇ／Ｌの硫酸銅、１０〜１５０ｇ／Ｌの硫酸、１０〜２００ｍｇ／Ｌの塩素イオンを含む。時に、本発明では、不溶性陽極のＣｕ供給のための成分として強い酸化力を有するマンガン酸化物を含む。   Moreover, the copper plating solution used for the said electrolytic copper plating contains 50-350 g / L copper sulfate, 10-150 g / L sulfuric acid, and 10-200 mg / L chlorine ion. Sometimes, the present invention includes manganese oxide having strong oxidizing power as a component for supplying Cu of the insoluble anode.

前記マンガン酸化物は、ＫＭｎＯ４及びＮａＭｎＯ４から選択されるものであることができ、その濃度は０．１〜１０ｇ／Ｌで含まれることが好ましい。前記マンガン酸化物の濃度が０．１ｇ／Ｌ未満である場合には、表面めっき抑制効果が微小であるため均一電着性が得られず、また、１０ｇ／Ｌを超過する場合には、表面めっき抑制効果が過多であるため表面めっきの厚さが不足したり未めっきが発生して好ましくない。 The manganese oxide may be selected from KMnO 4 and NaMnO 4 , and the concentration is preferably 0.1 to 10 g / L. When the concentration of the manganese oxide is less than 0.1 g / L, uniform electrodeposition cannot be obtained because the surface plating suppression effect is minute, and when the concentration exceeds 10 g / L, the surface Since the plating suppression effect is excessive, the thickness of the surface plating is insufficient or unplating occurs, which is not preferable.

この場合、前記不溶性陽極１１２、１２２での反応は、下記反応式１のとおりである。   In this case, the reaction at the insoluble anodes 112 and 122 is represented by the following reaction formula 1.

（反応式１）
Ｍｎ２＋＋４Ｈ２Ｏ→ＭｎＯ４ −＋８Ｈ＋＋５ｅ−
Ｍｎ２＋＋２Ｈ２Ｏ→ＭｎＯ２＋４Ｈ＋＋２ｅ− (Reaction Formula 1)
Mn 2+ + 4H 2 O → MnO 4 − + 8H + + 5e −
Mn 2+ + 2H 2 O → MnO 2 + 4H + + 2e −

また、前記陰極１１１、１２１での反応は、下記反応式２のとおりである。   The reaction at the cathodes 111 and 121 is represented by the following reaction formula 2.

（反応式２）
ＭｎＯ４ −＋８Ｈ＋＋５ｅ−→Ｍｎ２＋＋４Ｈ２Ｏ Ｅｏ＝＋１．５１Ｖ
Ｃｕ２＋＋２ｅ−→Ｃｕ Ｅｏ＝＋０．３４Ｖ (Reaction Formula 2)
MnO 4 − + 8H + + 5e − → Mn 2+ + 4H 2 O Eo = + 1.51V
Cu 2+ + 2e − → Cu Eo = + 0.34V

また、銅イオンを発生させる反応は、下記反応式３のとおりである。下記の反応は、本槽と溶解槽が別に構成された実施形態の場合、溶解槽で起こる。   The reaction for generating copper ions is as shown in the following reaction formula 3. The following reaction occurs in the dissolution tank in the case where the main tank and the dissolution tank are configured separately.

（反応式３）
２ＭｎＯ４ −＋１６Ｈ＋＋５Ｃｕ→２Ｍｎ２＋＋５Ｃｕ２＋＋８Ｈ２Ｏ (Reaction Formula 3)
2MnO 4 − + 16H + + 5Cu → 2Mn 2+ + 5Cu 2+ + 8H 2 O

本発明によると、銅供給源として用いられるマンガン酸化物の酸化還元電位は＋１．５１Ｖであり、Ｆｅ３＋／Ｆｅ２＋の酸化還元電位である＋０．７７Ｖに比べ高いため、低濃度で適用する場合にも優れた表面めっき抑制効果が得られる。 According to the present invention, the redox potential of the manganese oxide used as the copper supply source is +1.51 V, which is higher than the redox potential of Fe 3+ / Fe 2+ , which is +0.77 V. In addition, an excellent surface plating suppression effect can be obtained.

また、スルーホール（Ｔｈｒｏｕｇｈ Ｈｏｌｅ）またはブラインドビアホール（Ｂｌｉｎｄ ｖｉａ ｈｏｌｅ）のような構造物において、ホールの内部より表面のめっき速度を抑制して、均一電着性を改善することができる。   In addition, in a structure such as a through hole or a blind via hole, it is possible to improve the throwing power by suppressing the plating rate of the surface from the inside of the hole.

１０、２０、１１０、１２０ 本槽
１１、２１、１１１、１２１ 陰極
１２、２２、１１２、１２２ 陽極
１３、２３、１１３、１２３ めっき液
１４、２４、１２４ 溶解槽
２５、１２５ 銅ボール
２６ Ｆｅ３＋
１２６ マンガン酸化物 10, 20, 110, 120 Main tank 11, 21, 111, 121 Cathode 12, 22, 112, 122 Anode 13, 23, 113, 123 Plating solution 14, 24, 124 Dissolution tank 25, 125 Copper ball 26 Fe 3+
126 Manganese oxide

Claims (10)

陰極、不溶性陽極、銅ボール、及びめっき液が単一の槽（ｂａｔｈ）に含まれる電気銅めっき装置であって、
前記めっき液はマンガン酸化物を含むことを特徴とする電気銅めっき装置。 An electrolytic copper plating apparatus in which a cathode, an insoluble anode, a copper ball, and a plating solution are contained in a single bath,
The electrolytic copper plating apparatus, wherein the plating solution contains manganese oxide. 前記マンガン酸化物は、ＫＭｎＯ４及びＮａＭｎＯ４から選択されるものであることを特徴とする請求項１に記載の電気銅めっき装置。 2. The electrolytic copper plating apparatus according to claim 1, wherein the manganese oxide is selected from KMnO 4 and NaMnO 4 . 前記マンガン酸化物は、０．１〜１０ｇ／Ｌの濃度で含まれることを特徴とする請求項１に記載の電気銅めっき装置。   2. The electrolytic copper plating apparatus according to claim 1, wherein the manganese oxide is contained at a concentration of 0.1 to 10 g / L. 前記めっき液は、５０〜３５０ｇ／Ｌの硫酸銅、１０〜１５０ｇ／Ｌの硫酸、及び１０〜２００ｍｇ／Ｌの塩素を含むことを特徴とする請求項１に記載の電気銅めっき装置。   2. The electrolytic copper plating apparatus according to claim 1, wherein the plating solution contains 50 to 350 g / L of copper sulfate, 10 to 150 g / L of sulfuric acid, and 10 to 200 mg / L of chlorine. 前記不溶性陽極は、チタン（Ｔｉ）に白金（Ｐｔ）またはＩｒＯ２がコーティングされた材質を用いることを特徴とする請求項１に記載の電気銅めっき装置。 2. The electrolytic copper plating apparatus according to claim 1, wherein the insoluble anode is made of titanium (Ti) coated with platinum (Pt) or IrO 2 . 陰極、不溶性陽極、及びめっき液を含む本槽と、
銅ボール及びマンガン酸化物を含む溶解槽と、を含むことを特徴とする電気銅めっき装置。 A main tank containing a cathode, an insoluble anode, and a plating solution;
An electrolytic copper plating apparatus comprising: a dissolution tank containing copper balls and manganese oxide. 前記溶解槽から本槽のめっき液への銅の供給は、前記溶解槽のマンガン酸化物と銅ボールの反応により銅が銅イオンに溶解されてなされることを特徴とする請求項６に記載の電気銅めっき装置。   The supply of copper from the dissolution tank to the plating solution in the main tank is made by dissolving copper in copper ions by a reaction between manganese oxide and copper balls in the dissolution tank. Electro copper plating equipment. 前記マンガン酸化物は、ＫＭｎＯ４及びＮａＭｎＯ４から選択されるものであることを特徴とする請求項６に記載の電気銅めっき装置。 The electrolytic copper plating apparatus according to claim 6, wherein the manganese oxide is selected from KMnO 4 and NaMnO 4 . 前記マンガン酸化物は、０．１〜１０ｇ／Ｌの濃度で含まれることを特徴とする請求項６に記載の電気銅めっき装置。   The electrolytic copper plating apparatus according to claim 6, wherein the manganese oxide is contained at a concentration of 0.1 to 10 g / L. 前記電気銅めっき装置のめっき液は、５０〜３５０ｇ／Ｌの硫酸銅、１０〜１５０ｇ／Ｌの硫酸 、及び１０〜２００ｍｇ／Ｌの塩素を含むことを特徴とする請求項６に記載の電気銅めっき装置。   7. The electrolytic copper according to claim 6, wherein a plating solution of the electrolytic copper plating apparatus includes 50 to 350 g / L of copper sulfate, 10 to 150 g / L of sulfuric acid, and 10 to 200 mg / L of chlorine. Plating equipment.
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