JP2010126766A - PLATED BASE MATERIAL HAVING Sn PLATING LAYER AND METHOD OF MANUFACTURING THE SAME - Google Patents

PLATED BASE MATERIAL HAVING Sn PLATING LAYER AND METHOD OF MANUFACTURING THE SAME Download PDF

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JP2010126766A
JP2010126766A JP2008302804A JP2008302804A JP2010126766A JP 2010126766 A JP2010126766 A JP 2010126766A JP 2008302804 A JP2008302804 A JP 2008302804A JP 2008302804 A JP2008302804 A JP 2008302804A JP 2010126766 A JP2010126766 A JP 2010126766A
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plating
base material
plating layer
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Takashi Nomura
隆史 野村
Yasufumi Shibata
靖文 柴田
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Toyota Motor Corp
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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
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment
    • C25D5/505—After-treatment of electroplated surfaces by heat-treatment of electroplated tin coatings, e.g. by melting
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
    • H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
    • H01L23/495—Lead-frames or other flat leads
    • H01L23/49579—Lead-frames or other flat leads characterised by the materials of the lead frames or layers thereon
    • H01L23/49582—Metallic layers on lead frames
    • 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
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/24—Reinforcing the conductive pattern
    • H05K3/244—Finish plating of conductors, especially of copper conductors, e.g. for pads or lands
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
    • 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
    • H05K2203/11—Treatments characterised by their effect, e.g. heating, cooling, roughening
    • H05K2203/1105—Heating or thermal processing not related to soldering, firing, curing or laminating, e.g. for shaping the substrate or during finish plating

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  • Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing a plated base material in which the occurrence of whisker is suppressed by an easy means and which has a Pb-free Sn plating layer. <P>SOLUTION: In the manufacture of the plated base material 1 having the Pb-free Sn plating layer 3 on the surface of a base material 2 comprising Cu or Cu alloy at least in the surface, after the Pb-free Sn plating layer 3 is formed on the surface of the base material, the base material is heat treated at a temperature equal to or below the melting temperature of the plating layer 3 to form SnCu compound layer between the surface formed plating layer 3 and the surface of the base material 2. The growth of the whisker on the plating layer 3 in the manufactured base material 1 is remarkably suppressed. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

本発明は、ＰｂフリーのＳｎめっき層を有するめっき基材とその製造方法に関する。   The present invention relates to a plating substrate having a Pb-free Sn plating layer and a method for producing the same.

半導体装置のような電子部品において、外部端子の基材にはＣｕ、Ｃｕ合金、４２アロイ（鉄とＮｉが４２％の合金）などが用いられるが、素地のままでは端子表面が酸化してはんだ付け不良等による導通不良を引き起こす恐れがある。そのために、通常、めっき等により端子表面に保護膜（めっき層）を形成して酸化を防いでいる。   In an electronic component such as a semiconductor device, Cu, Cu alloy, 42 alloy (an alloy of 42% of iron and Ni), etc. are used for the base material of the external terminal. There is a risk of poor conduction due to improper attachment. For this purpose, a protective film (plating layer) is usually formed on the terminal surface by plating or the like to prevent oxidation.

めっき層の材料として純ＳｎまたはＳｎ合金を用いる場合、従来からＰｂを含む材料が用いられてきた。近年、環境負荷を軽減する観点からＰｂフリー化が求められるようになり、前記端子のめっき層材料にも、例えば、純ＳｎあるいはＳｎ−Ｃｕ，Ｓｎ−Ｂｉ，Ｓｎ−ＡｇのようなＳｎ合金のように、Ｐｂを含まない材料が使用されるようになっている。しかし、Ｐｂフリーの材料で電子部品の端子表面をめっき処理すると、めっき層から例えば径が３μｍ程度のＳｎ結晶である針状のウィスカが発生する。   In the case of using pure Sn or Sn alloy as the material of the plating layer, a material containing Pb has been conventionally used. In recent years, Pb-free material has been demanded from the viewpoint of reducing environmental load, and the plating layer material of the terminal is made of, for example, pure Sn or Sn alloy such as Sn—Cu, Sn—Bi, Sn—Ag. As described above, a material not containing Pb is used. However, when the surface of the terminal of the electronic component is plated with a Pb-free material, a needle-like whisker that is, for example, Sn crystal having a diameter of about 3 μm is generated from the plating layer.

近年、例えばＩＣチップをリードフレームに搭載した半導体装置のような電子部品は一層の小型化が求められており、結果として、その端子間の間隔は数百μｍ程度まで狭くなってきている。前記ウィスカは数百μｍの長さにまで成長することがあり、前記のように端子間の間隔が数百μｍ程度と狭い場合には、発生したウィスカにより端子間ショートが発生する恐れがあるので、ウィスカの発生を抑制するための対策が求められている。   In recent years, for example, electronic components such as a semiconductor device in which an IC chip is mounted on a lead frame have been required to be further reduced in size, and as a result, the distance between the terminals has been reduced to about several hundred μm. The whisker may grow to a length of several hundred μm. If the distance between the terminals is as narrow as several hundred μm as described above, a short circuit between the terminals may occur due to the generated whisker. Measures for suppressing the occurrence of whiskers are required.

針状ウィスカの発生および成長のメカニズムは完全には解明されていないが、めっき層中に蓄積された内部応力が一因であるとの考えから、めっき層の内部応力を除去することで針状ウィスカの発生を抑制しようとする提案がなされており、特許文献１には、Ｐｂを含まないＳｎ合金めっき層を、めっき後にその融点より高い温度で加熱してリフローさせて内部応力を開放することで、ウィスカの発生を抑制できることが記載されている。   The mechanism of the generation and growth of needle-like whiskers has not been fully elucidated, but it is considered that the internal stress accumulated in the plating layer is a cause, and therefore the needle-like whisker is removed by removing the internal stress in the plating layer. A proposal to suppress the generation of whiskers has been made, and in Patent Document 1, a Pb-free Sn alloy plating layer is heated at a temperature higher than its melting point after plating and reflowed to release internal stress. It is described that the generation of whiskers can be suppressed.

また、特許文献２には、少なくとも表面がＣｕまたはＣｕ合金からなる基体の表面に、Ｓｎめっき浴またはＳｎ合金めっき浴の中で電気めっきを行って含ＣｕＳｎ層である表面層を形成し、その後リフロー処理を行うことにより、表面層におけるウィスカの存在を解消するとともに、表面層と基体の表面間にＣｕ3Ｓｎ（ε相）層とＣｕ6Ｓｎ5（η’相）層とがこの順序で積層されて成る中間層を形成して、はんだ接合部における接合信頼性を高めることができる電気・電子部品用材料とその製造方法が記載されている。 Further, in Patent Document 2, at least the surface of a substrate made of Cu or a Cu alloy is subjected to electroplating in a Sn plating bath or a Sn alloy plating bath to form a surface layer which is a CuSn-containing layer. By performing the reflow treatment, the presence of whiskers in the surface layer is eliminated, and a Cu 3 Sn (ε phase) layer and a Cu 6 Sn 5 (η ′ phase) layer are arranged in this order between the surface layer and the surface of the substrate. A material for an electric / electronic component that can form a laminated intermediate layer to increase the bonding reliability in a solder joint and a method for manufacturing the same are described.

また、めっき層の結晶方位面およびその配向指数を制御することで、ウィスカの発生を抑制できることも提案されており、特許文献３には、Ｓｎめっき層の結晶粒界にＳｎ合金相を形成してウィスカの発生を抑制技術であって、Ｓｎ合金相が形成しやすくするために、めっき層における（２２０）面と（３２１）面の配向指数を高くすることが記載されている。   It has also been proposed that whisker generation can be suppressed by controlling the crystal orientation plane and the orientation index of the plating layer. Patent Document 3 forms an Sn alloy phase at the grain boundary of the Sn plating layer. It is a technique for suppressing the generation of whiskers, and it is described that the orientation index of the (220) plane and the (321) plane in the plating layer is increased in order to facilitate the formation of the Sn alloy phase.

特開平１０−１４４８３９号公報Japanese Patent Laid-Open No. 10-144839 特開平１１−３４３５９４号公報JP 11-343594 A 特開２００６−２４９４６０号公報JP 2006-249460 A

本発明者らは、Ｐｂフリーのめっき層でのウィスカの発生について多くの実験と研究を継続して行ってきているが、Ｐｂフリーのめっき層の内部応力を緩和してウィスカの発生を抑制する従来技術は、いずれも充分な成果を上げているとは言い難い。また、特許文献１あるいは２に記載のように、めっき後にめっき層をリフローさせると、めっきの厚みに偏りが生じる恐れがあり、ウィスカ発生防止手段としてはなお改善すべき点がある。特定の結晶配向面の配向指数を制御してウィスカの発生を制御する技術は、そのような特定の結晶配向面を見出すこと自体が困難であり、さらに特定した結晶配向面が優先するようにめっき面での結晶面の配向指数を制御することも容易でない。   The present inventors have continued many experiments and research on the generation of whiskers in the Pb-free plating layer, but the internal stress of the Pb-free plating layer is relieved to suppress the generation of whiskers. It is hard to say that all the prior arts have achieved satisfactory results. Further, as described in Patent Document 1 or 2, if the plating layer is reflowed after plating, there is a possibility that the thickness of the plating is biased, and there is still a point to be improved as a whisker generation preventing means. The technology that controls the occurrence of whiskers by controlling the orientation index of a specific crystal orientation plane is difficult to find such a specific crystal orientation plane, and plating is performed so that the specified crystal orientation plane takes precedence. It is not easy to control the orientation index of the crystal plane in the plane.

本発明は、上記の事情を考慮してなされたものであり、より容易な手段でもってウィスカの発生を抑制できるようにした、ＰｂフリーのＳｎめっき層を有するめっき基材の製造方法を開示することを課題とする。   The present invention has been made in view of the above circumstances, and discloses a method for producing a plating base material having a Pb-free Sn plating layer that can suppress the generation of whiskers with easier means. This is the issue.

上記の課題を解決するために、本発明者らは、ＰｂフリーのＳｎめっき層におけるウィスカの発生について、さらに多くの実験を行う過程において、母材がＣｕまたはＣｕ合金の場合、めっき層を形成した母材に対してめっき層の溶融温度以下の温度で熱処理を行うことによって、めっき層の厚みに偏りを生じさせることなく、ウィスカの発生を抑制できることを知見した。その理由は明確ではないが、熱処理により母材表面とめっき層との間にＣｕＳｎ化合物層が形成され、形成されたＣｕＳｎ化合物層よって、ウィスカの発生が抑制されたものと解される。   In order to solve the above problems, the present inventors formed a plating layer when the base material is Cu or Cu alloy in the process of conducting more experiments on the generation of whiskers in the Pb-free Sn plating layer. It was found that the occurrence of whiskers can be suppressed without causing a bias in the thickness of the plating layer by heat-treating the base material at a temperature not higher than the melting temperature of the plating layer. Although the reason is not clear, it is understood that a CuSn compound layer is formed between the base material surface and the plating layer by heat treatment, and the formation of whisker is suppressed by the formed CuSn compound layer.

本発明は上記の知見に基づくものであり、本発明は、少なくとも表面がＣｕまたはＣｕ合金からなる母材の前記表面にＰｂフリーのＳｎめっき層を有するめっき基材の製造方法であって、前記母材表面にＰｂフリーのＳｎめっき層を形成する工程と、形成しためっき層と母材表面との間にＳｎＣｕ化合物層を生成する温度以上でありめっき層の溶融温度以下の温度での熱処理を行う工程と、を少なくとも含むことを特徴とする。   The present invention is based on the above findings, and the present invention is a method for producing a plating substrate having a Pb-free Sn plating layer on the surface of a base material having at least a surface made of Cu or a Cu alloy, A step of forming a Pb-free Sn plating layer on the surface of the base material, and a heat treatment at a temperature not lower than the temperature at which the SnCu compound layer is formed between the formed plating layer and the surface of the base material and not higher than the melting temperature of the plating layer. And performing the process.

本発明による製造方法では、めっき層の溶融温度以下の温度で熱処理を行うために、形成しためっき層の膜厚が変動することはなく、良品のめっき基材が得られる。また、めっき層と母材表面との間にＳｎＣｕ化合物層が形成されることにより、めっき基材にウィスカが発生するのも抑制される。前記加熱処理は、めっき処理の直後、遅くともめっき処理の後の５時間以内に行うことが、きわめて望ましい。   In the manufacturing method according to the present invention, since the heat treatment is performed at a temperature equal to or lower than the melting temperature of the plating layer, the thickness of the formed plating layer does not vary, and a good plating substrate is obtained. In addition, the formation of the SnCu compound layer between the plating layer and the base material surface suppresses the occurrence of whiskers on the plating base material. It is highly desirable to perform the heat treatment immediately after the plating treatment and within 5 hours after the plating treatment at the latest.

本発明によるＳｎめっき層を有するめっき基材の製造方法において、前記熱処理をＳｎＣｕ化合物層の厚さが少なくとも０．２μｍ以上となるまで行うことは好ましい態様である。後の実施例に示すように、０．２μｍ以上のＳｎＣｕ化合物層を形成することで、めっき基材でのウィスカの発生をほぼ完全に抑制することができる。   In the manufacturing method of the plating base material which has Sn plating layer by this invention, it is a preferable aspect to perform the said heat processing until the thickness of a SnCu compound layer becomes at least 0.2 micrometer or more. As shown in the following examples, by forming a SnCu compound layer of 0.2 μm or more, the generation of whiskers on the plating base material can be suppressed almost completely.

本発明は、さらに、上記の製造方法で製造されるめっき基材であって、少なくとも表面がＣｕまたはＣｕ合金からなる母材の表面にＰｂフリーのＳｎめっき層を有しており、前記母材表面と前記ＰｂフリーのＳｎめっき層の間にはめっき層形成面の全域にわたり０．２μｍ以上のＳｎＣｕ化合物層を有していることを特徴とするめっき基材をも開示する。   The present invention further comprises a plating base material manufactured by the above manufacturing method, wherein at least the surface has a Pb-free Sn plating layer on the surface of a base material made of Cu or a Cu alloy, Also disclosed is a plating substrate characterized by having a SnCu compound layer of 0.2 μm or more between the surface and the Pb-free Sn plating layer over the entire plating layer forming surface.

上記のめっき基材では、めっき層形成面の全域にわたり０．２μｍ以上のＳｎＣｕ化合物層が形成されており、ウィスカの発生を大きく抑制することができる。   In said plating base material, the SnCu compound layer of 0.2 micrometer or more is formed over the whole plating layer formation surface, and generation | occurrence | production of a whisker can be suppressed significantly.

本発明によるめっき基材の一態様では、Ｓｎめっき層表面には、Ｓｎ結晶流の（１１０）面が１０％以上存在しており、前記ＳｎＣｕ化合物層の厚さが０．３μｍ以上であることを特徴とする。   In one aspect of the plating substrate according to the present invention, the Sn plating layer surface has 10% or more of the (110) face of the Sn crystal flow, and the thickness of the SnCu compound layer is 0.3 μm or more. It is characterized by.

本発明者らは、多数の鉛フリーめっき層表面に対してＥＢＳＰ法によるＸ線回析を行い、ウィスカが発生した結晶方位面についての解析を行ったところ、ウィスカは、めっき材料の結晶粒における原子密度の高い結晶方位面から成長する確率が、原子密度の低い結晶方位面から成長する確率よりも高いことを知見している（本出願と同じ出願人に係る特願２００７−１９５０９０号出願が参照される）。Ｓｎ結晶粒において、（１００）面は比較して原子密度の高い面であり、従って、めっき材料がＳｎ系めっき材料の場合に、結晶粒における（１００）面から成長する確率が最も高いと考えられる。また、結晶粒の（１００）面がめっき表面に存在するということは、すなわち、めっき表面にウィスカが成長する確率の高い（１１０）面が存在することも推定できる。   The present inventors performed X-ray diffraction by EBSP method on the surface of many lead-free plating layers, and analyzed the crystal orientation plane where whiskers were generated. It has been found that the probability of growing from a crystal orientation plane having a high atomic density is higher than the probability of growing from a crystal orientation plane having a low atomic density (see Japanese Patent Application No. 2007-195090 filed by the same applicant as the present application). Referenced). In the Sn crystal grains, the (100) plane is a plane having a higher atomic density, and therefore, when the plating material is an Sn-based plating material, the probability of growing from the (100) plane in the crystal grains is considered to be the highest. It is done. Further, the fact that the (100) plane of the crystal grains exists on the plating surface, that is, it can also be estimated that the (110) plane having a high probability of growing whiskers exists on the plating surface.

それを前提に本発明者らが行った実験では、前記のように、Ｓｎめっき層表面に、ウィスカが成長する確率の高い（１１０）面が１０％以上存在している場合であっても、前記ＳｎＣｕ化合物層を０．３μｍ以上とすることにより、ウィスカの発生をほぼ完全に抑制することができた。また、（１１０）面の占める割合がめっき層形成面に対して１０％未満の場合では、ＳｎＣｕ化合物層が０．２μｍ以上であれば、ウィスカの発生を抑制できることも確認した。   In the experiment conducted by the present inventors on the premise thereof, as described above, even when the (110) plane having a high probability of growing whiskers is present on the Sn plating layer surface by 10% or more, By making the SnCu compound layer 0.3 μm or more, the generation of whiskers could be suppressed almost completely. In addition, when the proportion of the (110) plane is less than 10% with respect to the plating layer forming surface, it was also confirmed that whisker generation can be suppressed if the SnCu compound layer is 0.2 μm or more.

なお、本発明において、Ｓｎめっき層を形成するＳｎは、純Ｓｎが好ましいが、Ｓｎ−Ｃｕ，Ｓｎ−Ｂｉ，Ｓｎ−Ａｇのような、鉛を含まないＳｎ合金であってもよい。また、本発明において、母材は、すべてがＣｕまたはＣｕ合金からなる母材であってもよく、炭素鋼，Ｆｅ−Ｎｉ系合金、Ｆｅ−Ｎｉ−Ｃｏ系合金，ステンレス鋼などのＦｅ系材料を芯材とし、その表面をＣｕまたはＣｕ合金で被覆した母材であってもよい。   In the present invention, Sn forming the Sn plating layer is preferably pure Sn, but may be Sn alloy containing no lead such as Sn—Cu, Sn—Bi, Sn—Ag. Further, in the present invention, the base material may be a base material composed entirely of Cu or Cu alloy, and Fe-based materials such as carbon steel, Fe—Ni based alloy, Fe—Ni—Co based alloy, stainless steel, etc. May be a base material whose surface is covered with Cu or a Cu alloy.

本発明によれば、母材の表面にＰｂフリーのＳｎめっき層を有するめっき基材を製造するに際して、めっき層の溶融温度以下の温度での熱処理を行う工程を行うだけで、めっき基材にウィスカが発生するのを確実に抑制することができる。また、めっき層の膜厚の変動を伴わない良品のめっき基材を得ることができる。   According to the present invention, when a plating base material having a Pb-free Sn plating layer on the surface of the base material is manufactured, only by performing a heat treatment at a temperature lower than the melting temperature of the plating layer, The occurrence of whiskers can be reliably suppressed. In addition, a good plating base material with no variation in the thickness of the plating layer can be obtained.

以下、本発明を実施の形態に基づき説明する。図１は本発明により製造しためっき基材の一例を示す。   Hereinafter, the present invention will be described based on embodiments. FIG. 1 shows an example of a plating substrate manufactured according to the present invention.

図示の例で、めっき基材１は、ＣｕまたはＣｕ合金からなる母材２と、その上に形成されたＰｂフリーのＳｎめっき層３を備え、母材２の表面とＳｎめっき層３との間には、Ｓｎめっき層３の溶融温度以下、例えば２３０℃以下の温度で熱処理を行うことによって形成されたＳｎＣｕ化合物層４を有している。Ｓｎめっき層２は、電解めっき等の手段によって、母材２の表面に形成される。厚さは、めっき基材１の使用場所や使用目的等によって適宜設定されるが、通常、５〜１０μｍ程度である。用いるめっき液は、Ｐｂを含まないことを条件に任意であり、従来知られたものを適宜用いることができる。   In the illustrated example, the plating substrate 1 includes a base material 2 made of Cu or Cu alloy, and a Pb-free Sn plating layer 3 formed thereon, and includes a surface of the base material 2 and the Sn plating layer 3. In between, it has the SnCu compound layer 4 formed by performing heat processing at the temperature below the melting temperature of the Sn plating layer 3, for example, 230 degrees C or less. The Sn plating layer 2 is formed on the surface of the base material 2 by means such as electrolytic plating. The thickness is appropriately set depending on the place of use and purpose of use of the plating substrate 1, but is usually about 5 to 10 μm. The plating solution to be used is arbitrary on the condition that it does not contain Pb, and a conventionally known one can be used as appropriate.

めっき層３を形成した後、好ましくはめっき層３側からその溶融温度以下の温度での加熱処理を施すことにより、母材２の表面とＳｎめっき層３との間に前記したＳｎＣｕ化合物層４が形成される。ＳｎＣｕ化合物層４の厚さは、熱処理の温度と時間によって変化するので、所望の厚さのＳｎＣｕ化合物層４が形成されるように、温度と時間を設定して、熱処理を行う。   After the plating layer 3 is formed, the above-described SnCu compound layer 4 is preferably formed between the surface of the base material 2 and the Sn plating layer 3 by performing a heat treatment at a temperature not higher than the melting temperature from the plating layer 3 side. Is formed. Since the thickness of the SnCu compound layer 4 varies depending on the temperature and time of the heat treatment, the heat treatment is performed by setting the temperature and time so that the SnCu compound layer 4 having a desired thickness is formed.

後の実施例に示すように、本発明によるめっき基材１では、ＳｎＣｕ化合物層４を有しないものと比較して、Ｓｎめっき層３にウィスカが成長するのが、大きく抑制される。   As shown in the following examples, in the plating base 1 according to the present invention, the growth of whiskers on the Sn plating layer 3 is greatly suppressed as compared with the case where the SnCu compound layer 4 is not provided.

［実施例１］
図１に示すように、Ｃｕ合金（具体的には、Ｃ１９４）である母材２の表面に、Ｓｎ−１．５Ｃｕのめっき液を用い電流密度１．５Ａ／ｄｍ２で電解めっきを施し、母材表面に厚さ９μｍのＰｂフリーＳｎめっき層３を形成した試験体を多数用意した。各試験体のめっき層表面でのＳｎ結晶粒の（１１０）面は１０％以上となっていた。 [Example 1]
As shown in FIG. 1, the surface of the base material 2 which is a Cu alloy (specifically, C194) is subjected to electrolytic plating at a current density of 1.5 A / dm 2 using a Sn-1.5Cu plating solution, A number of test bodies were prepared in which a Pb-free Sn plating layer 3 having a thickness of 9 μm was formed on the surface of the base material. The (110) plane of Sn crystal grains on the plating layer surface of each specimen was 10% or more.

Ｓｎめっき形成後の５時間以内に、各試験体に対して、熱処理温度と処理時間を変えて熱処理を行い、それぞれの試験体について、母材表面とＳｎめっき層の間に形成されたＳｎＣｕ化合物層４の厚さを測定した。その結果を表１に示した。なお、熱処理温度は、すべてＳｎめっき層３の溶融温度よりも低い温度とした。また、１つの試験体には熱処理を行わなかった。   Within 5 hours after the formation of Sn plating, each specimen was heat-treated at different heat treatment temperatures and treatment times, and for each specimen, SnCu compound formed between the base material surface and the Sn plating layer. The thickness of layer 4 was measured. The results are shown in Table 1. The heat treatment temperatures were all lower than the melting temperature of the Sn plating layer 3. One specimen was not heat-treated.

熱処理後の各試験体および熱処理を行わない試験体を、室温で５００時間放置した後、電子顕微鏡（ＳＥＭ）を用いて、Ｓｎめっき層でのウィスカの発生状態を観察し、発生した場合に、最大ウィスカ長さを測定した。その結果も表１に示した。   After each specimen after heat treatment and a specimen not subjected to heat treatment were allowed to stand at room temperature for 500 hours, using an electron microscope (SEM), the state of whisker generation in the Sn plating layer was observed. The maximum whisker length was measured. The results are also shown in Table 1.

Figure 2010126766
Figure 2010126766

［考察］
表１に示すように、熱処理無しの場合、および熱処理を行ってもＳｎＣｕ化合物層４が形成されなかったものは、長さの長いウィスカが成長している。熱処理を行ってＳｎＣｕ化合物層が形成された場合でも、厚さが０．２μｍ以下の場合には、ウィスカが成長しているが、化合物層が０．２μｍ厚の場合には、１５μｍの長さにウィスカの成長は抑制されている。さらに、厚さが０．３μｍ以上の場合には、ウィスカはまったく成長していない。 [Discussion]
As shown in Table 1, whisker having a long length grows when no heat treatment is performed and when the SnCu compound layer 4 is not formed even after the heat treatment. Even when the SnCu compound layer is formed by heat treatment, whiskers are grown when the thickness is 0.2 μm or less, but when the compound layer is 0.2 μm thick, the length is 15 μm. Whisker growth is suppressed. Further, when the thickness is 0.3 μm or more, the whisker has not grown at all.

この結果から、めっき層の溶融温度以下の温度での熱処理を行うことにより、ウィスカの発生を抑制できること、また、めっき層と母材表面との間に生成するＳｎＣｕ化合物層の膜厚が０．２μｍ以上であれば、実用に支障を生じない程度にウィスカの成長を抑制することができ、厚さ０．３μｍ以上にＳｎＣｕ化合物層の膜厚を成長させることにより、完全にウィスカの発生を阻止できることがわかる。   From this result, it is possible to suppress the generation of whiskers by performing a heat treatment at a temperature lower than the melting temperature of the plating layer, and the SnCu compound layer formed between the plating layer and the base material surface has a thickness of 0. If it is 2 μm or more, whisker growth can be suppressed to such an extent that it does not interfere with practical use. By growing the thickness of the SnCu compound layer to a thickness of 0.3 μm or more, whisker generation is completely prevented. I understand that I can do it.

［実施例２］
実施例１と同様にした多数の試験体を作った。但し、めっき時の電流密度０．５Ａ／ｄｍ２にして、各試験体のめっき層表面でのＳｎ結晶粒の（１１０）面が１０％未満となるようにした。 [Example 2]
A number of specimens similar to Example 1 were made. However, the current density at the time of plating was set to 0.5 A / dm 2 so that the (110) plane of the Sn crystal grains on the plating layer surface of each specimen was less than 10%.

Ｓｎめっき形成後の５時間以内に、各試験体に対して、熱処理温度と処理時間を変えて熱処理を行い、それぞれの試験体について、母材表面とＳｎめっき層の間に形成されたＳｎＣｕ化合物層４の厚さを測定した。その結果を表２に示した。なお、熱処理温度は、すべてＳｎめっき層３の溶融温度よりも低い温度とした。また、１つの試験体には熱処理を行わなかった。   Within 5 hours after the formation of Sn plating, each specimen was heat-treated at different heat treatment temperatures and treatment times, and for each specimen, SnCu compound formed between the base material surface and the Sn plating layer. The thickness of layer 4 was measured. The results are shown in Table 2. The heat treatment temperatures were all lower than the melting temperature of the Sn plating layer 3. One specimen was not heat-treated.

熱処理後の各試験体および熱処理を行わない試験体を、室温で５００時間放置した後、電子顕微鏡（ＳＥＭ）を用いて、Ｓｎめっき層でのウィスカの発生状態を観察し、発生した場合に、最大ウィスカ長さを測定した。その結果も表２に示した。   After each specimen after heat treatment and a specimen not subjected to heat treatment were allowed to stand at room temperature for 500 hours, using an electron microscope (SEM), the state of whisker generation in the Sn plating layer was observed. The maximum whisker length was measured. The results are also shown in Table 2.

Figure 2010126766
Figure 2010126766

［考察］
表２に示すように、熱処理無しの場合、および熱処理を行ってもＳｎＣｕ化合物層が形
成されなかったものは、長さの長いウィスカが成長している。しかし、ウィスカが成長しやすい（１１０）面の占める割合が１０％未満であることから、実施例１と比較して、ウィスカの長さは短くなっている。熱処理を行ってＳｎＣｕ化合物層が形成された場合でも、層厚さが０．１μｍ以下の場合には、２７．５μｍの長さにウィスカの成長は抑制されている。さらに、ウィスカが成長しやすい（１１０）面の占める割合が１０％未満であることから、ＳｎＣｕ化合物層が０．２μｍを越えると、ウィスカはまったく成長していない。 [Discussion]
As shown in Table 2, whisker having a long length grows when no heat treatment is performed and when the SnCu compound layer is not formed even after the heat treatment. However, since the proportion of the (110) plane in which the whisker easily grows is less than 10%, the length of the whisker is shorter than that of the first embodiment. Even when the SnCu compound layer is formed by heat treatment, whisker growth is suppressed to a length of 27.5 μm when the layer thickness is 0.1 μm or less. Furthermore, since the proportion of the (110) plane in which whiskers are easy to grow is less than 10%, the whisker does not grow at all when the SnCu compound layer exceeds 0.2 μm.

この結果から、ウィスカが成長しやすい（１１０）面の占める割合が１０％未満である場合には、めっき層と母材表面との間に生成するＳｎＣｕ化合物層の膜厚が０．１μｍ以上であれば、実用に支障を生じない程度にウィスカの成長を抑制することができ、厚さ０．２μｍ以上にＳｎＣｕ化合物層の膜厚を成長させることにより、完全にウィスカの発生を阻止できることがわかる。   From this result, when the proportion of the (110) plane in which whiskers are easy to grow is less than 10%, the film thickness of the SnCu compound layer formed between the plating layer and the base material surface is 0.1 μm or more. If so, it can be seen that whisker growth can be suppressed to such an extent that it does not hinder practical use, and the growth of whisker can be completely prevented by growing the thickness of the SnCu compound layer to a thickness of 0.2 μm or more. .

本発明によるめっき部材の模式図。The schematic diagram of the plating member by this invention.

符号の説明Explanation of symbols

１…めっき部材、
２…ＣｕまたはＣｕ合金からなる母材、
３…めっき層、
４…熱処理によりめっき層と母材表面との間に形成されたＳｎＣｕ化合物層、 1 ... plating member,
2 ... Base material made of Cu or Cu alloy,
3 ... plating layer,
4 ... SnCu compound layer formed between the plating layer and the base material surface by heat treatment,

Claims (4)

少なくとも表面がＣｕまたはＣｕ合金からなる母材の前記表面にＰｂフリーのＳｎめっき層を有するめっき基材の製造方法であって、前記母材表面にＰｂフリーのＳｎめっき層を形成する工程と、形成しためっき層と母材表面との間にＳｎＣｕ化合物層を生成する温度以上でありめっき層の溶融温度以下の温度での熱処理を行う工程と、を少なくとも含むことを特徴とするめっき基材の製造方法。   A method of manufacturing a plating base material having a Pb-free Sn plating layer on the surface of a base material comprising at least a surface of Cu or a Cu alloy, the step of forming a Pb-free Sn plating layer on the surface of the base material; A step of performing a heat treatment at a temperature not lower than the temperature at which the SnCu compound layer is formed between the formed plating layer and the base material surface and not higher than the melting temperature of the plating layer. Production method. 前記熱処理をＳｎＣｕ化合物層の厚さが少なくとも０．２μｍ以上となるまで行うことを特徴とする請求項１に記載のめっき基材の製造方法。   The method of manufacturing a plating substrate according to claim 1, wherein the heat treatment is performed until the thickness of the SnCu compound layer is at least 0.2 µm or more. 請求項１ないし２のいずれかの製造方法で製造されるめっき基材であって、少なくとも表面がＣｕまたはＣｕ合金からなる母材の前記表面にＰｂフリーのＳｎめっき層を有しており、前記母材表面と前記ＰｂフリーのＳｎめっき層の間にはめっき層形成面の全域にわたり０．２μｍ以上のＳｎＣｕ化合物層を有していることを特徴とするめっき基材。   A plating substrate produced by the production method according to claim 1, wherein at least the surface has a Pb-free Sn plating layer on the surface of the base material made of Cu or a Cu alloy, A plating base material having a SnCu compound layer of 0.2 μm or more across the entire surface of the plating layer forming surface between the surface of the base material and the Pb-free Sn plating layer. 請求項３に記載のめっき基材であって、Ｓｎめっき層表面には、Ｓｎ結晶流の（１１０）面が１０％以上存在しており、前記ＳｎＣｕ化合物層の厚さが０．３μｍ以上であることを特徴とするめっき基材。   It is a plating base material of Claim 3, Comprising: On the Sn plating layer surface, the (110) surface of Sn crystal flow exists 10% or more, and the thickness of the said SnCu compound layer is 0.3 micrometer or more. A plating substrate characterized by being.
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