JP2016056389A - Plating pretreatment method of Al-Cu conjugate - Google Patents

Plating pretreatment method of Al-Cu conjugate Download PDF

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JP2016056389A
JP2016056389A JP2014180930A JP2014180930A JP2016056389A JP 2016056389 A JP2016056389 A JP 2016056389A JP 2014180930 A JP2014180930 A JP 2014180930A JP 2014180930 A JP2014180930 A JP 2014180930A JP 2016056389 A JP2016056389 A JP 2016056389A
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copper
aluminum
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JP6386310B2 (en
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宏人 成枝
Hiroto Narueda
宏人 成枝
智胤 青山
Tomotane Aoyama
智胤 青山
歴 米澤
Reki Yonezawa
歴 米澤
遠藤 秀樹
Hideki Endo
秀樹 遠藤
堀 久司
Hisashi Hori
久司 堀
貴訓 小久保
Takakuni Kokubo
貴訓 小久保
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Dowaメタルテック株式会社
Dowa Metaltech Kk
日本軽金属株式会社
Nippon Light Metal Co Ltd
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Abstract

PROBLEM TO BE SOLVED: To provide a plating pretreatment method of an Al-Cu conjugate capable of forming a plating film having high adhesion and excellent solderability on each surface of an aluminum member and a copper member of the Al-Cu conjugate.SOLUTION: The surface of an Al-Cu conjugate formed by bonding an aluminum member comprising aluminum or an aluminum alloy with a copper member comprising copper or a copper alloy is subjected to a defatting treatment, and an etching treatment with an etchant containing hydrofluoric acid, and then to an acid treatment with a sulfuric acid-based chemical such as a sulfuric acid solution containing sodium persulfate, and thereafter to a zincate treatment with alkaline zinc substitution liquid.SELECTED DRAWING: None

Description

本発明は、アルミニウム部材に銅部材が接合したAl−Cu接合体のめっき前処理方法に関し、特に、Al−Cu接合体のアルミニウム部材と銅部材の表面にめっきを施す際の前処理方法に関する。   The present invention relates to a pretreatment method for plating an Al—Cu joined body in which a copper member is joined to an aluminum member, and more particularly, to a pretreatment method for plating the surface of an aluminum member and a copper member of an Al—Cu joined body.

従来、電子機器などの発熱部からの放熱装置として、熱伝導性に優れた銅からなる放熱板(ベース板)に、熱伝導性が多少劣るが軽量なアルミニウムからなるフィンを接合したフィン付放熱板(放熱装置)が知られており、このようなフィン付放熱板のベース板にろう付けや半田付けによりフィンを接合する際のベース板とフィンの接合性を改善するために、ベース板のフィンとの接合面側がフィンと同じ系統のアルミニウムまたはアルミニウム合金からなるように、銅部材とアルミニウムまたはアルミニウム合金からなる部材を合わせた部材をベース板として使用することが知られている(例えば、特許文献1参照)。   Conventionally, as a heat radiating device from heat generating parts such as electronic equipment, heat dissipation with fins, which is made of copper with excellent thermal conductivity (base plate) joined with fins made of lightweight aluminum with slightly lower thermal conductivity In order to improve the bondability between the base plate and the fin when the fin is joined to the base plate of such a finned heat sink by brazing or soldering, It is known to use a member obtained by combining a copper member and a member made of aluminum or an aluminum alloy as a base plate so that a joint surface side with the fin is made of aluminum or an aluminum alloy of the same system as the fin (for example, a patent Reference 1).

また、セラミックス基板の一方の面にアルミニウム合金箔からなるアルミニウム回路が形成され、他方の面にアルミニウム合金箔を介して銅ヒートシンクが接合された銅ヒートシンク一体型アルミニウム回路基板のアルミニウム回路の表面に無電解Ni−Pめっきを施す際の前処理として、銅ヒートシンク一体型アルミニウム回路基板の表面をアルカリ脱脂した後、フッ硝酸溶液に浸漬し、その後、塩化パラジウムと塩化第一スズと塩酸からなるキャタリスト液に浸漬した後、硫酸に浸漬することが知られている(例えば、特許文献2参照)。   Also, an aluminum circuit made of aluminum alloy foil is formed on one surface of the ceramic substrate, and a copper heat sink is joined to the other surface via the aluminum alloy foil. As a pretreatment for electrolytic Ni-P plating, the surface of the copper heat sink integrated aluminum circuit board is degreased with alkali, then immersed in a hydrofluoric acid solution, and then a catalyst composed of palladium chloride, stannous chloride and hydrochloric acid. It is known to immerse in sulfuric acid after being immersed in a liquid (see, for example, Patent Document 2).

特開平11−204968号公報(段落番号0002−0006)JP-A-11-204968 (paragraph numbers 0002-0006) 特開平2002−9212号公報(段落番号0035−0038)Japanese Patent Laid-Open No. 2002-9212 (paragraph numbers 0035-0038)

しかし、特許文献1の合わせ部材のようなアルミニウム部材に銅部材が接合したAl−Cu接合体の腐食を防止するために、Al−Cu接合体の全面をめっきした場合には、このめっきした銅部材上に(セラミックス基板の少なくとも一方の面に銅板が接合した)銅−セラミックス接合基板の銅板などを半田付けする際のめっきの前処理方法として、特許文献2の前処理方法を適用すると、Al−Cu接合体の銅部材の表面のめっきの表面粗さが大きくなって表面積が増大することにより、銅部材上に銅−セラミックス接合基板の銅板などを半田付けした際に、界面張力の増大により半田ボイドや半田はじきが生じ、半田付け性が低下するという問題がある。   However, in order to prevent corrosion of the Al—Cu joined body in which the copper member is joined to the aluminum member such as the matching member of Patent Document 1, when the entire surface of the Al—Cu joined body is plated, this plated copper As a pretreatment method for plating when soldering a copper plate of a copper-ceramic bonding substrate (with a copper plate bonded to at least one surface of the ceramic substrate) on a member, when the pretreatment method of Patent Document 2 is applied, Al -The surface roughness of the plating on the surface of the copper member of the Cu joined body is increased and the surface area is increased, so that when the copper plate of the copper-ceramic bonding substrate is soldered on the copper member, the interfacial tension is increased. There is a problem that solder voids and solder repelling occur and solderability is lowered.

したがって、本発明は、このような従来の問題点に鑑み、Al−Cu接合体のアルミニウム部材と銅部材の表面に密着性が高く且つ半田付け性が良好なめっき皮膜を形成することができる、Al−Cu接合体のめっき前処理方法を提供することを目的とする。   Therefore, in view of such a conventional problem, the present invention can form a plating film having high adhesion and good solderability on the surfaces of the aluminum member and the copper member of the Al-Cu joined body. It aims at providing the plating pre-processing method of an Al-Cu joined object.

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、アルミニウム部材と銅部材が接合したAl−Cu接合体の表面を硫酸系薬液で酸処理した後にアルカリ性の亜鉛置換液でジンケート処理することにより、アルミニウム部材と銅部材の表面に密着性が高く半田付け性が良好なめっき皮膜を形成することができることを見出し、本発明を完成するに至った。   As a result of diligent research to solve the above-mentioned problems, the inventors of the present invention have carried out a zincate treatment with an alkaline zinc substitution solution after acid-treating the surface of an Al-Cu joined body in which an aluminum member and a copper member are joined with a sulfuric acid chemical solution. As a result, it has been found that a plating film having high adhesion and good solderability can be formed on the surfaces of the aluminum member and the copper member, and the present invention has been completed.

すなわち、本発明によるAl−Cu接合体のめっき前処理方法は、アルミニウム部材と銅部材が接合したAl−Cu接合体の表面を硫酸系薬液で酸処理した後にアルカリ性の亜鉛置換液でジンケート処理することを特徴とする。   That is, in the pre-plating method for an Al—Cu joined body according to the present invention, the surface of the Al—Cu joined body in which the aluminum member and the copper member are joined is acid-treated with a sulfuric acid chemical solution and then zincated with an alkaline zinc substitution solution. It is characterized by that.

このAl−Cu接合体のめっき前処理方法において、硫酸系薬液が過硫酸ナトリウムを含む硫酸溶液であるのが好ましく、酸処理とジンケート処理を再度繰り返すのが好ましい。また、酸処理前にAl−Cu接合体の表面をエッチング処理するのが好ましく、エッチング処理前にAl−Cu接合体の表面を脱脂処理するのが好ましい。エッチング処理は、フッ酸を含有するエッチング液で行うのが好ましい。また、アルミニウム部材がアルミニウムまたはアルミニウム合金からなるのが好ましく、銅部材が銅または銅合金からなるのが好ましい。   In this Al—Cu joined plating pretreatment method, the sulfuric acid chemical solution is preferably a sulfuric acid solution containing sodium persulfate, and it is preferable to repeat the acid treatment and the zincate treatment again. Further, the surface of the Al—Cu joined body is preferably etched before the acid treatment, and the surface of the Al—Cu joined body is preferably degreased before the etching treatment. The etching treatment is preferably performed with an etching solution containing hydrofluoric acid. The aluminum member is preferably made of aluminum or an aluminum alloy, and the copper member is preferably made of copper or a copper alloy.

また、本発明によるAl−Cu接合体は、アルミニウム部材と銅部材が接合したAl−Cu接合体において、アルミニウム部材と銅部材の表面にめっき皮膜が形成され、銅部材上のめっき皮膜の表面粗さRaが0.3μm以下であり、JIS H8504に準じたクロスカットテープピーリング試験においてめっき皮膜の剥離がないことを特徴とする。   Further, the Al—Cu joined body according to the present invention is an Al—Cu joined body in which an aluminum member and a copper member are joined, and a plating film is formed on the surfaces of the aluminum member and the copper member, and the surface of the plated film on the copper member is roughened. Ra is 0.3 μm or less, and there is no peeling of the plating film in a cross-cut tape peeling test according to JIS H8504.

このAl−Cu接合体において、めっき皮膜がニッケルまたはニッケル合金からなるのが好ましい。また、アルミニウム部材がアルミニウムまたはアルミニウム合金からなるのが好ましく、銅部材が銅または銅合金からなるのが好ましい。   In this Al—Cu joined body, the plating film is preferably made of nickel or a nickel alloy. The aluminum member is preferably made of aluminum or an aluminum alloy, and the copper member is preferably made of copper or a copper alloy.

本発明によれば、Al−Cu接合体のアルミニウム部材と銅部材の表面に密着性が高く且つ半田付け性が良好なめっき皮膜を形成することができる、Al−Cu接合体のめっき前処理方法を提供することができる。   ADVANTAGE OF THE INVENTION According to this invention, the plating pre-processing method of an Al-Cu joined body which can form the plating film with high adhesiveness and favorable solderability on the surface of the aluminum member and copper member of an Al-Cu joined body Can be provided.

本発明によるAl−Cu接合体のめっき前処理方法の実施の形態では、アルミニウム部材と銅部材が接合したAl−Cu接合体の表面を硫酸系薬液で酸処理した後にアルカリ性の亜鉛置換液でジンケート処理する。   In the embodiment of the plating pretreatment method for an Al—Cu joined body according to the present invention, the surface of the Al—Cu joined body where the aluminum member and the copper member are joined is acid-treated with a sulfuric acid chemical solution and then zincated with an alkaline zinc substitution solution. To process.

このAl−Cu接合体のめっき前処理方法において、酸処理は、過硫酸ナトリウムを含む硫酸溶液などの硫酸系薬液で行う。硝酸で酸処理すると、Cuとの反応が激しく、銅部材の表面粗さが大きくなり、銅部材上のめっき皮膜の表面に銅−セラミックス接合基板の銅板や半導体チップなどを半田付けした際に半田ボイドや半田はじきが発生して半田付け性が低下する。一方、硫酸系薬液で酸処理すると、酸処理とジンケート処理を行った後の銅部材の表面粗さが大きくなるのを抑制し、銅部材上のめっき皮膜の表面に銅−セラミックス接合基板の銅板や半導体チップなどを半田付けした際に半田ボイドや半田はじきの発生を防止して半田付け性が良好になる。この酸処理では、過硫酸ナトリウムを含む硫酸溶液として、50〜150g/Lの過硫酸ナトリウムと10〜30g/Lの硫酸を含む水溶液を使用するのが好ましい。   In this Al—Cu bonded body pretreatment method, the acid treatment is performed with a sulfuric acid chemical solution such as a sulfuric acid solution containing sodium persulfate. When acid treatment is performed with nitric acid, the reaction with Cu is intense, the surface roughness of the copper member increases, and soldering is performed when a copper plate of a copper-ceramic bonding substrate or a semiconductor chip is soldered to the surface of the plating film on the copper member. Voids and solder repelling occur and solderability decreases. On the other hand, when acid treatment is performed with a sulfuric acid-based chemical solution, the surface roughness of the copper member after acid treatment and zincate treatment is suppressed, and the copper plate of the copper-ceramic bonding substrate is formed on the surface of the plating film on the copper member. When soldering a semiconductor chip or the like, solder voids and solder repelling are prevented and solderability is improved. In this acid treatment, it is preferable to use an aqueous solution containing 50 to 150 g / L sodium persulfate and 10 to 30 g / L sulfuric acid as the sulfuric acid solution containing sodium persulfate.

また、ジンケート処理は、アルカリ性の亜鉛置換液で行う。酸性の亜鉛置換液でジンケート処理すると、アルミニウム部材と銅部材の表面のいずれにも、めっき皮膜の密着性が悪くなり、半田付け性も低下する。   The zincate treatment is performed with an alkaline zinc replacement solution. When the zincate treatment is performed with the acidic zinc replacement solution, the adhesion of the plating film is deteriorated on both the surfaces of the aluminum member and the copper member, and the solderability is also lowered.

また、1回目の亜鉛置換で表面の亜鉛置換膜が粗くて不均一になる場合には、酸処理とジンケート処理を再度繰り返すのが好ましい。すなわち、1回目のジンケート処理の後に再びジンケート処理を行うダブルジンケート処理(2回亜鉛置換)を行うのが好ましい。   In addition, when the zinc substitution film on the surface becomes rough and non-uniform by the first zinc substitution, it is preferable to repeat the acid treatment and the zincate treatment again. That is, it is preferable to perform double zincate treatment (twice zinc substitution) after the first zincate treatment.

また、酸処理前にAl−Cu接合体の表面をエッチング処理するのが好ましく、エッチング処理前にAl−Cu接合体の表面を脱脂処理するのが好ましい。エッチング処理は、フッ酸を含有するエッチング液で行うのが好ましい。   Further, the surface of the Al—Cu joined body is preferably etched before the acid treatment, and the surface of the Al—Cu joined body is preferably degreased before the etching treatment. The etching treatment is preferably performed with an etching solution containing hydrofluoric acid.

さらに、アルミニウム部材が、アルミニウムまたはアルミニウム合金からなるのが好ましく、銅部材が、銅または銅合金からなるのが好ましい。   Furthermore, the aluminum member is preferably made of aluminum or an aluminum alloy, and the copper member is preferably made of copper or a copper alloy.

なお、このAl−Cu接合体のめっき前処理方法によって前処理した後、無電解ニッケル−リンにより銅部材上にニッケルめっき皮膜を形成するのが好ましい。   In addition, it is preferable to form a nickel plating film on a copper member with electroless nickel-phosphorus after pre-processing by the plating pre-processing method of this Al-Cu joined body.

また、本発明によるAl−Cu接合体の実施の形態は、アルミニウム部材と銅部材が接合したAl−Cu接合体において、アルミニウム部材と銅部材の表面にめっき皮膜が形成され、銅部材上の表面粗さRaが0.3μm以下、好ましくは0.2μm以下であり、JIS H8504に準じたクロスカットテープピーリング試験においてめっき皮膜の剥離がない。   The embodiment of the Al—Cu joined body according to the present invention is an Al—Cu joined body in which an aluminum member and a copper member are joined, and a plating film is formed on the surfaces of the aluminum member and the copper member, and the surface on the copper member. The roughness Ra is 0.3 μm or less, preferably 0.2 μm or less, and there is no peeling of the plating film in the cross-cut tape peeling test according to JIS H8504.

このAl−Cu接合体において、めっき皮膜がニッケルまたはニッケル合金からなるのが好ましい。また、アルミニウム部材がアルミニウムまたはアルミニウム合金からなるのが好ましく、銅部材が銅または銅合金からなるのが好ましい。   In this Al—Cu joined body, the plating film is preferably made of nickel or a nickel alloy. The aluminum member is preferably made of aluminum or an aluminum alloy, and the copper member is preferably made of copper or a copper alloy.

以下、本発明によるAl−Cu接合体のめっき前処理方法の実施例について詳細に説明する。   Hereinafter, the Example of the plating pre-processing method of the Al-Cu joined body by this invention is described in detail.

[実施例1]
まず、アルミニウム部材として94mm×26mm×3mmの大きさのアルミニウム板(日本軽金属株式会社製のA1050)、銅部材として108mm×67mm×4mmの大きさの銅合金板(DOWAメタルテック株式会社製のDSC−3N、表面粗さRa=0.18μm)を用意するとともに、Al(75質量%)−Si(5質量%)−Cu(20質量%)粉末からなるろう材とフラックス(CF−15(CsF系とノコロックの混合物)とを5:1の比率で含むろう材ペーストを用意した。
[Example 1]
First, an aluminum plate having a size of 94 mm × 26 mm × 3 mm (A1050 made by Nippon Light Metal Co., Ltd.) as an aluminum member, and a copper alloy plate having a size of 108 mm × 67 mm × 4 mm (DSC made by DOWA Metaltech Co., Ltd.) as a copper member. -3N, surface roughness Ra = 0.18 μm) and a brazing material and flux (CF-15 (CsF) made of Al (75 mass%)-Si (5 mass%)-Cu (20 mass%) powder A braze paste containing a 5: 1 ratio of the system and the nocolok mixture was prepared.

次に、銅合金板上に20mg/cmの量で塗布したろう材ペースト上にアルミニウム板を載せて窒素(100%)雰囲気の炉内に入れ、ろう付温度540℃で2分間保持した後、約150℃まで冷却し、炉内から取り出して、ろう接によりアルミニウム板と銅合金板を接合したAl−Cu接合体(Al−Cu複合部材)を得た。 Next, after placing an aluminum plate on a brazing filler paste applied in an amount of 20 mg / cm 2 on a copper alloy plate and placing it in a furnace in a nitrogen (100%) atmosphere, the brazing temperature was maintained at 540 ° C. for 2 minutes. Then, it was cooled to about 150 ° C., taken out from the furnace, and an Al—Cu joined body (Al—Cu composite member) in which an aluminum plate and a copper alloy plate were joined by brazing was obtained.

次に、苛性ソーダを含む脱脂液(100mL/Lのギルライト650(上村工業株式会社製)を含む水溶液)を50℃に保持し、この脱脂液にAl−Cu接合体を10分間浸漬することにより、Al−Cu接合体の表面の脱脂処理を行った後、Al−Cu接合体を水洗して脱脂液を洗い流した。   Next, a degreasing liquid containing caustic soda (an aqueous solution containing 100 mL / L of Gillite 650 (manufactured by Uemura Kogyo Co., Ltd.)) is maintained at 50 ° C., and the Al—Cu joined body is immersed in this degreasing liquid for 10 minutes, After degreasing the surface of the Al—Cu joined body, the Al—Cu joined body was washed with water to wash away the degreasing liquid.

次に、フッ酸を含有するエッチング液(100mL/LのAD−101F(上村工業株式会社製)を含む水溶液)を65℃に保持し、このエッチング液にAl−Cu接合体を4分間浸漬してエッチング処理を行った後、Al−Cu接合体を水洗してエッチング液を洗い流した。   Next, an etching solution containing hydrofluoric acid (an aqueous solution containing 100 mL / L AD-101F (manufactured by Uemura Kogyo Co., Ltd.)) is maintained at 65 ° C., and the Al—Cu joined body is immersed in this etching solution for 4 minutes. After performing the etching process, the Al—Cu joined body was washed with water to wash away the etching solution.

次に、100g/Lの過硫酸ナトリウムと18g/Lの硫酸を含む水溶液を25℃に保持し、この過硫酸ナトリウム水溶液にAl−Cu接合体を30秒間浸漬して、1回目の酸処理を行った。   Next, an aqueous solution containing 100 g / L sodium persulfate and 18 g / L sulfuric acid is maintained at 25 ° C., and the Al—Cu joined body is immersed in this aqueous sodium persulfate solution for 30 seconds to perform the first acid treatment. went.

次に、アルカリ性の亜鉛置換液(250mL/LのMCT−17(上村工業株式会社製)を含む水溶液)を20℃に保持し、この亜鉛置換液にAl−Cu接合体を20秒間浸漬して、1回目のジンケート処理を行った後、Al−Cu接合体を水洗した。   Next, an alkaline zinc replacement liquid (an aqueous solution containing 250 mL / L of MCT-17 (manufactured by Uemura Kogyo Co., Ltd.)) is maintained at 20 ° C., and the Al—Cu joined body is immersed in this zinc replacement liquid for 20 seconds. After the first zincate treatment, the Al—Cu joined body was washed with water.

次に、1回目の酸処理と同じ(25℃に保持した)過硫酸ナトリウム水溶液にAl−Cu接合体を1分間浸漬して、2回目の酸処理を行った。   Next, the second acid treatment was performed by immersing the Al—Cu joined body in the same sodium persulfate aqueous solution (held at 25 ° C.) as the first acid treatment for 1 minute.

次に、1回目のジンケート処理と同じ(20℃に保持した)亜鉛置換液にAl−Cu接合体を40秒間浸漬して、2回目のジンケート処理を行った後、Al−Cu接合体を水洗した。   Next, after the second zincate treatment was performed by immersing the Al—Cu joined body in the same zinc replacement solution as the first zincate treatment (maintained at 20 ° C.) for 40 seconds, the Al—Cu joined body was washed with water. did.

次に、無電解ニッケル−リンめっき液(150mL/LのニムデンKLP−1−MM(上村工業株式会社製)と60mL/LのニムデンKLP−1−MA(上村工業株式会社製)含む水溶液)を90℃に保持し、この無電解ニッケルめっき液に前処理後のAl−Cu接合体を20分間浸漬して、Al−Cu接合体の表面にニッケル−リン合金めっき皮膜を形成した。   Next, an electroless nickel-phosphorous plating solution (150 mL / L Nimden KLP-1-MM (manufactured by Uemura Kogyo Co., Ltd.) and 60 mL / L Nimden KLP-1-MA (manufactured by Uemura Kogyo Co., Ltd.)) While maintaining at 90 ° C., the pretreated Al—Cu joined body was immersed in this electroless nickel plating solution for 20 minutes to form a nickel-phosphorus alloy plating film on the surface of the Al—Cu joined body.

このようにしてニッケル−リン合金めっきを施したAl−Cu接合体の銅板上のめっき皮膜の表面粗さ(ISO 4287−1997)で規定される算術平均粗さ)Raを求めたところ、0.16μmであった。この表面粗さは、表面粗さ測定機(株式会社小坂研究所製のサーフコーダSE4000)を用いて、測定長さ2.5mm、送り速さ0.1mm/s、カットオフ値0.8mmで測定した。   Thus, when surface roughness (arithmetic mean roughness prescribed | regulated by ISO 4287-1997) Ra of the plating film on the copper plate of the Al-Cu joined body which gave nickel-phosphorus alloy plating was calculated | required, 0. It was 16 μm. This surface roughness was measured using a surface roughness measuring machine (Surfcoder SE4000 manufactured by Kosaka Laboratory Ltd.) with a measurement length of 2.5 mm, a feed rate of 0.1 mm / s, and a cutoff value of 0.8 mm. It was measured.

また、Al−Cu接合体の表面に形成しためっき皮膜の密着性について、JIS H8504に準じてクロスカットテープピーリング試験を行って、めっき皮膜の剥離の有無を目視によって評価したところ、Al−Cu接合体のアルミニウム部材と銅部材の表面のいずれも、めっき皮膜の剥離はなく、めっき皮膜の密着性が良好であった。   Moreover, about the adhesiveness of the plating film formed on the surface of the Al-Cu joined body, a cross-cut tape peeling test was conducted according to JIS H8504, and the presence or absence of peeling of the plating film was visually evaluated. Neither the aluminum member of the body nor the surface of the copper member had any peeling of the plating film, and the adhesion of the plating film was good.

また、Al−Cu接合体の銅板上のニッケル−リン合金めっき皮膜上に(厚さ0.6mmのアルミナからなるセラミックス基板の両面に厚さ0.3mmのタフピッチ銅板が直接接合した)銅−セラミックス接合基板の一方の銅板を半田付けしたところ、半田ボイドや半田はじきの発生はなかった。   Also, a copper-ceramic (a tough pitch copper plate having a thickness of 0.3 mm is directly bonded to both surfaces of a ceramic substrate made of alumina having a thickness of 0.6 mm) on a nickel-phosphorus alloy plating film on a copper plate of an Al-Cu joined body When one copper plate of the bonding substrate was soldered, no solder voids or solder repelling occurred.

[実施例2]
2回目の酸処理と2回目のジンケート処理を行わなかった以外は、実施例1と同様の方法によりニッケル−リン合金めっきを施したAl−Cu接合体について、実施例1と同様の方法により、Al−Cu接合体の銅板上の表面粗さRaを求めるとともに、めっき皮膜の密着性を評価し、半田ボイドと半田はじきの有無を確認した。その結果、銅板上のめっき皮膜の表面粗さRaは0.18μmであり、Al−Cu接合体のアルミニウム部材と銅部材の表面のいずれも、めっき皮膜の剥離はなく、めっき皮膜の密着性が良好であり、半田ボイドや半田はじきの発生もなかった。
[Example 2]
Except for not performing the second acid treatment and the second zincate treatment, for the Al-Cu bonded body subjected to nickel-phosphorus alloy plating by the same method as in Example 1, by the same method as in Example 1, While calculating | requiring the surface roughness Ra on the copper plate of an Al-Cu joined body, the adhesiveness of the plating film was evaluated and the presence or absence of a solder void and solder repelling was confirmed. As a result, the surface roughness Ra of the plating film on the copper plate is 0.18 μm, and there is no peeling of the plating film on the surface of the aluminum member and the copper member of the Al—Cu joined body, and the adhesion of the plating film is good. It was good and there was no generation of solder voids or solder repellency.

[比較例1]
実施例1と同様の方法によりAl−Cu接合体を得た後、銅部材について一般的に行われている前処理(電解脱脂および活性化処理)と無電解ニッケルめっきを行った。すなわち、70℃に保持したアルカリ性の脱脂液にAl−Cu接合体とSUS板を入れ、Al−Cu接合体を陽極、SUS板を陰極として、電圧5Vで30秒間電解脱脂し、水洗した後、フッ化物を含む硫酸溶液に室温で30秒間浸漬する活性化処理を行い、その後、実施例1と同様の方法により、Al−Cu接合体の表面にニッケル−リン合金めっき皮膜を形成した。
[Comparative Example 1]
After obtaining an Al—Cu joined body by the same method as in Example 1, pretreatment (electrolytic degreasing and activation treatment) and electroless nickel plating generally performed on copper members were performed. That is, after putting an Al-Cu joined body and a SUS plate in an alkaline degreasing liquid kept at 70 ° C, using the Al-Cu joined body as an anode and a SUS plate as a cathode, electrolytically degreased at a voltage of 5 V for 30 seconds, and washed with water. An activation treatment was performed by immersing in a sulfuric acid solution containing a fluoride at room temperature for 30 seconds, and then a nickel-phosphorus alloy plating film was formed on the surface of the Al—Cu joined body by the same method as in Example 1.

このようにしてニッケル−リン合金めっきを施したAl−Cu接合体について、実施例1と同様の方法により、Al−Cu接合体の銅板上のめっき皮膜の表面粗さRaを求めるとともに、めっき皮膜の密着性を評価し、半田ボイドと半田はじきの有無を確認した。その結果、銅板上のめっき皮膜の表面粗さRaは0.16μmであり、半田ボイドや半田はじきの発生もなかったが、Al−Cu接合体のアルミニウム部材と銅部材の表面のいずれも、めっき皮膜の剥離があり、めっき皮膜の密着性が良好でなかった。   For the Al-Cu joined body thus plated with nickel-phosphorus alloy, the surface roughness Ra of the plated film on the copper plate of the Al-Cu joined body was obtained by the same method as in Example 1, and the plated film The adhesion of the solder was evaluated, and the presence or absence of solder voids and solder repelling was confirmed. As a result, the surface roughness Ra of the plating film on the copper plate was 0.16 μm and no solder voids or solder repelling occurred, but both the aluminum member of the Al—Cu joined body and the surface of the copper member were plated. There was peeling of the film, and the adhesion of the plating film was not good.

[比較例2]
実施例1と同様の方法により、Al−Cu接合体の表面の脱脂処理とエッチング処理を行った後、Al−Cu接合体を、硝酸溶液(500mL/Lの硝酸を含む水溶液)に室温で30秒間浸漬して、1回目の酸処理を行った。
[Comparative Example 2]
After performing the degreasing process and the etching process on the surface of the Al—Cu joined body in the same manner as in Example 1, the Al—Cu joined body was placed in a nitric acid solution (an aqueous solution containing 500 mL / L nitric acid) at room temperature. The first acid treatment was performed by dipping for 2 seconds.

次に、1回目の酸処理後のAl−Cu接合体を、実施例1と同様の方法により、亜鉛置換液に浸漬して、1回目のジンケート処理を行った後、Al−Cu接合体を水洗した。   Next, the Al—Cu joined body after the first acid treatment was immersed in a zinc-substituting solution by the same method as in Example 1, and the first zincate treatment was performed. Washed with water.

次に、1回目のジンケート処理後のAl−Cu接合体を1回目の酸処理と同じ硝酸溶液に室温で30秒間浸漬して、2回目の酸処理を行った。   Next, the Al—Cu joined body after the first zincate treatment was immersed in the same nitric acid solution as the first acid treatment for 30 seconds at room temperature to perform the second acid treatment.

次に、2回目の酸処理後のAl−Cu接合体を、実施例1と同様の方法により、亜鉛置換液に浸漬して、2回目のジンケート処理を行った後、Al−Cu接合体を水洗した。   Next, the Al—Cu joined body after the second acid treatment was immersed in a zinc replacement solution by the same method as in Example 1, and after the second zincate treatment was performed, the Al—Cu joined body was Washed with water.

次に、実施例1と同様の方法により、Al−Cu接合体の表面にニッケル−リン合金めっき皮膜を形成した。   Next, a nickel-phosphorus alloy plating film was formed on the surface of the Al—Cu joined body by the same method as in Example 1.

このようにしてニッケル−リン合金めっきを施したAl−Cu接合体について、実施例1と同様の方法により、Al−Cu接合体の銅板上のめっき皮膜の表面粗さRaを求めるとともに、めっき皮膜の密着性を評価し、半田ボイドと半田はじきの有無を確認した。その結果、Al−Cu接合体のアルミニウム部材と銅部材の表面のいずれも、めっき皮膜の剥離はなく、めっき皮膜の密着性は良好であったが、銅板上のめっき皮膜の表面粗さRaが0.32μmと大きく、半田ボイドや半田はじきの発生があった。   For the Al-Cu joined body thus plated with nickel-phosphorus alloy, the surface roughness Ra of the plated film on the copper plate of the Al-Cu joined body was obtained by the same method as in Example 1, and the plated film The adhesion of the solder was evaluated, and the presence or absence of solder voids and solder repelling was confirmed. As a result, neither the aluminum member of the Al—Cu joined body nor the surface of the copper member had any peeling of the plating film, and the adhesion of the plating film was good, but the surface roughness Ra of the plating film on the copper plate was As large as 0.32 μm, solder voids and solder repelling occurred.

[比較例3]
実施例1と同様の方法により、Al−Cu接合体の表面の脱脂処理とエッチング処理を行った後、酸性の亜鉛置換液(500mL/LのAZ−501(上村工業株式会社製)を含む水溶液)にAl−Cu接合体を室温で2分間浸漬して、ジンケート処理を行い、その後、Al−Cu接合体を水洗した後、実施例1と同様の方法により、Al−Cu接合体の表面にニッケル−リン合金めっき皮膜を形成した。
[Comparative Example 3]
After performing the degreasing process and the etching process on the surface of the Al—Cu joined body by the same method as in Example 1, an aqueous solution containing an acidic zinc replacement liquid (500 mL / L AZ-501 (manufactured by Uemura Kogyo Co., Ltd.)). The Al—Cu joined body is soaked at room temperature for 2 minutes to perform zincate treatment, and then the Al—Cu joined body is washed with water, and then the surface of the Al—Cu joined body is formed by the same method as in Example 1. A nickel-phosphorus alloy plating film was formed.

このようにしてニッケル−リン合金めっきを施したAl−Cu接合体について、実施例1と同様の方法により、Al−Cu接合体の銅板上のめっき皮膜の表面粗さRaを求めるとともに、めっき皮膜の密着性を評価し、半田ボイドの有無を確認した。その結果、銅板上のめっき皮膜の表面粗さRaは0.15μmと小さかったが、Al−Cu接合体のアルミニウム部材と銅部材の表面のいずれも、めっき皮膜の剥離があり、めっき皮膜の密着性が良好でなく、半田ボイドと半田はじきの発生の有無を評価することができなかった。   For the Al-Cu joined body thus plated with nickel-phosphorus alloy, the surface roughness Ra of the plated film on the copper plate of the Al-Cu joined body was obtained by the same method as in Example 1, and the plated film The adhesion was evaluated and the presence or absence of solder voids was confirmed. As a result, the surface roughness Ra of the plating film on the copper plate was as small as 0.15 μm, but both the aluminum member of the Al—Cu joined body and the surface of the copper member had peeling of the plating film, and the adhesion of the plating film It was not possible to evaluate the presence or absence of solder voids and solder repellency.

Claims (12)

  1. アルミニウム部材と銅部材が接合したAl−Cu接合体の表面を硫酸系薬液で酸処理した後にアルカリ性の亜鉛置換液でジンケート処理することを特徴とする、Al−Cu接合体のめっき前処理方法。 A plating pretreatment method for an Al-Cu joined body, wherein the surface of an Al-Cu joined body in which an aluminum member and a copper member are joined is subjected to an acid treatment with a sulfuric acid chemical solution and then a zincate treatment with an alkaline zinc substitution solution.
  2. 前記硫酸系薬液が過硫酸ナトリウムを含む硫酸溶液であることを特徴とする、請求項1に記載のAl−Cu接合体のめっき前処理方法。 The plating pretreatment method for an Al-Cu joined body according to claim 1, wherein the sulfuric acid chemical solution is a sulfuric acid solution containing sodium persulfate.
  3. 前記酸処理と前記ジンケート処理を再度繰り返すことを特徴とする、請求項1または2に記載のAl−Cu接合体のめっき前処理方法。 The pretreatment method for plating an Al—Cu joined body according to claim 1, wherein the acid treatment and the zincate treatment are repeated again.
  4. 前記酸処理前に前記Al−Cu接合体の表面をエッチング処理することを特徴とする、請求項1乃至3のいずれかに記載のAl−Cu接合体のめっき前処理方法。 The pre-plating method for an Al-Cu joined body according to any one of claims 1 to 3, wherein the surface of the Al-Cu joined body is etched before the acid treatment.
  5. 前記エッチング処理前に前記Al−Cu接合体の表面を脱脂処理することを特徴とする、請求項4に記載のAl−Cu接合体のめっき前処理方法。 5. The pre-plating method for an Al—Cu joined body according to claim 4, wherein the surface of the Al—Cu joined body is degreased before the etching treatment.
  6. 前記エッチング処理を、フッ酸を含有するエッチング液で行うことを特徴とする、請求項4または5に記載のAl−Cu接合体のめっき前処理方法。 The pre-plating treatment method for an Al—Cu joined body according to claim 4, wherein the etching treatment is performed with an etching solution containing hydrofluoric acid.
  7. 前記アルミニウム部材がアルミニウムまたはアルミニウム合金からなることを特徴とする、請求項1乃至6のいずれかに記載のAl−Cu接合体のめっき前処理方法。 The pretreatment method for plating an Al—Cu joined body according to claim 1, wherein the aluminum member is made of aluminum or an aluminum alloy.
  8. 前記銅部材が銅または銅合金からなることを特徴とする、請求項1乃至7のいずれかに記載のAl−Cu接合体のめっき前処理方法。 The said copper member consists of copper or a copper alloy, The plating pre-processing method of the Al-Cu joined body in any one of the Claims 1 thru | or 7 characterized by the above-mentioned.
  9. アルミニウム部材と銅部材が接合したAl−Cu接合体において、アルミニウム部材と銅部材の表面にめっき皮膜が形成され、銅部材上のめっき皮膜の表面粗さRaが0.3μm以下であり、JIS H8504に準じたクロスカットテープピーリング試験においてめっき皮膜の剥離がないことを特徴とする、Al−Cu接合体。 In an Al—Cu joined body in which an aluminum member and a copper member are joined, a plating film is formed on the surfaces of the aluminum member and the copper member, and the surface roughness Ra of the plating film on the copper member is 0.3 μm or less, JIS H8504 In the cross-cut tape peeling test according to the above, there is no peeling of the plating film, an Al-Cu joined body.
  10. 前記めっき皮膜がニッケルまたはニッケル合金からなることを特徴とする、請求項9に記載のAl−Cu接合体。 The Al—Cu joined body according to claim 9, wherein the plating film is made of nickel or a nickel alloy.
  11. 前記アルミニウム部材がアルミニウムまたはアルミニウム合金からなることを特徴とする、請求項9または10に記載のAl−Cu接合体。 The Al-Cu joined body according to claim 9 or 10, wherein said aluminum member consists of aluminum or an aluminum alloy.
  12. 前記銅部材が銅または銅合金からなることを特徴とする、請求項9乃至11のいずれかに記載のAl−Cu接合体。 The Al—Cu joined body according to claim 9, wherein the copper member is made of copper or a copper alloy.
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