JP2015229791A - Metal material for electronic part and connector terminal, connector and electronic part using the same - Google Patents
Metal material for electronic part and connector terminal, connector and electronic part using the same Download PDFInfo
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本発明は、電子部品用金属材料、それを用いたコネクタ端子、コネクタ及び電子部品に関する。 The present invention relates to a metal material for electronic parts, a connector terminal using the same, a connector, and an electronic part.
民生用及び車載用電子機器用接続部品であるコネクタには、黄銅やリン青銅の表面にＮｉやＣｕの下地めっきを施し、さらにその上にＳｎ又はＳｎ合金めっきを施した材料が使用されている。Ｓｎ又はＳｎ合金めっきは、一般的に低接触抵抗及び高はんだ濡れ性という特性が求められ、更に近年めっき材をプレス加工で成形したオス端子及びメス端子勘合時の挿入力の低減化も求められている。また、製造工程でめっき表面に、短絡等の問題を引き起こす針状結晶であるウィスカが発生することがあり、このウィスカを良好に抑制する必要もある。 A connector that is a connection part for consumer and in-vehicle electronic devices uses a material in which a surface of brass or phosphor bronze is plated with Ni or Cu and further plated with Sn or Sn alloy. . Sn or Sn alloy plating generally requires characteristics such as low contact resistance and high solder wettability, and in recent years, it is also required to reduce insertion force when mating a male terminal and a female terminal formed by plating a plated material. ing. In addition, whiskers that are needle-like crystals that cause problems such as short circuits may occur on the plating surface in the manufacturing process, and it is necessary to suppress these whiskers well.
これに対し、特許文献１には、接点基材と、前記接点基材の表面に形成されたＮｉもしくはＣｏまたは両者の合金から成る下地層と、前記下地層の表面に形成されたＡｇ−Ｓｎ合金層とを備え、前記Ａｇ−Ｓｎ合金層におけるＳｎの平均濃度は１０質量％未満であり、かつ前記Ａｇ−Ｓｎ合金層におけるＳｎの濃度は前記下地層との界面から前記Ａｇ−Ｓｎ合金層の表層部にかけて増大する濃度勾配で変化していることを特徴とする電気接点材料が開示されている。そしてこれによれば、耐摩耗性、耐食性、加工性が優れている電気接点材料とそれを極めて安価に製造することができると記載されている。 On the other hand, Patent Document 1 discloses a contact base material, a base layer made of Ni or Co or an alloy of both formed on the surface of the contact base material, and Ag-Sn formed on the surface of the base layer. And an average concentration of Sn in the Ag—Sn alloy layer is less than 10% by mass, and the Sn concentration in the Ag—Sn alloy layer is from the interface with the underlayer to the Ag—Sn alloy layer. An electrical contact material is disclosed that varies with a concentration gradient that increases over the surface layer of the substrate. According to this, it is described that an electrical contact material having excellent wear resistance, corrosion resistance, and workability can be produced at a very low cost.
また、特許文献２には、少なくとも表面がＣｕまたはＣｕ合金から成る基体の前記表面に、ＮｉまたはＮｉ合金層から成る中間層を介して、いずれもＡｇ3Ｓｎ（ε相）化合物を含有する厚み０．５〜２０μｍのＳｎ層またはＳｎ合金層から成る表面層が形成されていることを特徴とする電気・電子部品用材料が開示されている。そしてこれによれば、表面層はＳｎより低融点であり、はんだ付け性に優れ、またウィスカの発生もなく、はんだ付け後に形成された接合部の接合強度が高いと同時に、その接合強度の高温下における経時的な低下も起こりづらいのでリード材料として好適であり、また高温環境下で使用したときでも接触抵抗の上昇が抑制され、相手材との間で接続信頼性の低下を招くこともないのでコンタクト材料としても好適な電気・電子部品用材料とその製造方法、およびその材料を用いた電気・電子部品の提供を目的とすることが記載されている。 In Patent Document 2, at least the surface of the substrate made of Cu or a Cu alloy has a thickness containing an Ag 3 Sn (ε phase) compound via an intermediate layer made of Ni or a Ni alloy layer on the surface of the substrate. A material for electric / electronic parts is disclosed, in which a surface layer composed of a Sn layer or a Sn alloy layer of 0.5 to 20 μm is formed. And according to this, the surface layer has a lower melting point than Sn, excellent solderability, no whisker generation, high joint strength of the joint formed after soldering, and at the same time high joint strength This is suitable as a lead material because it does not easily degrade over time, and even when used in a high temperature environment, the increase in contact resistance is suppressed, and the connection reliability with the counterpart material is not reduced. Therefore, it is described that the object is to provide a material for an electric / electronic component suitable as a contact material, a method for manufacturing the same, and an electric / electronic component using the material.
また特許文献３には、導電性を有する基材と、前記基材に形成された被覆層とを備えた被覆材において、 前記被覆層は少なくとも表面側に、Ｓｎと、貴金属との金属間化合物を含むことを特徴とする被覆材が開示されている。そしてこれによれば、接触抵抗が低く、低摩擦係数を有して挿入力の低減に有効であって、かつ、耐酸化性に優れて長期に亘って安定した特性を有する被覆材、及びその製造方法の提供を目的とすることが記載されている。 Patent Document 3 discloses a covering material comprising a conductive base material and a coating layer formed on the base material, wherein the coating layer is an intermetallic compound of Sn and a noble metal at least on the surface side. The coating | covering material characterized by including is disclosed. According to this, a coating material having a low contact resistance, a low friction coefficient, effective in reducing the insertion force, excellent in oxidation resistance and stable over a long period of time, and its It describes that it aims to provide a manufacturing method.
しかしながら、特許文献１に記載の技術では、近年求められている挿入力の低減化やウィスカ発生の有無との関係が明らかになっていない。またＡｇ−Ｓｎ合金層におけるＳｎの平均濃度は１０質量％未満であり、Ａｇ−Ｓｎ合金層中のＡｇの割合がかなり多いため本発明者らの評価では、塩素ガス、亜硫酸ガス、硫化水素等のガスに対する耐ガス腐食性が十分ではなかった。
また、特許文献２に記載の技術では、Ａｇ3Ｓｎ（ε相）化合物を含有する厚み０．５〜２０μｍのＳｎ層またはＳｎ合金層から成る表面層であり、本発明者らの評価では、この表面層厚みでは十分に挿入力を下げることはできない領域が存在した。更にＳｎ層またはＳｎ合金層から成る表面層のＡｇ3Ｓｎ（ε相）の含有量が、Ａｇ換算にして０．５〜５質量％であるとも記載されており、Ｓｎ層またはＳｎ合金層から成る表面層におけるＳｎの割合が多く、Ｓｎ層またはＳｎ合金層から成る表面層の厚みも厚いために本発明者らの評価ではウィスカが発生し、耐微摺動磨耗性が十分ではなかった。耐熱性やはんだ濡れ性も十分ではなかった。
また、特許文献３に記載の技術では、被覆層がＳｎと、貴金属との金属間化合物を含んでいるが、Ｓｎと貴金属との金属間化合物（Ａｇ3Ｓｎ）の厚みが好ましくは１μｍ以上３μｍ以下となっている。本発明者らの評価では、この厚みでは、十分に挿入力を下げることができなかった。
このように、従来のＳｎ−Ａｇ合金／Ｎｉ下地めっき構造を有する電子部品用金属材料にはまだ十分に挿入力を下げることができず、またウィスカが発生するという問題が残されていた。また耐久性（耐熱性、はんだ濡れ性、耐微摺動磨耗性及び耐ガス腐食性）についても十分満足できる仕様とすることは困難であり、明らかになっていない。
本発明は上記の課題を解決するためになされたものであり、低ウィスカ性、低凝着磨耗性及び高耐久性を有する電子部品用金属材料、それを用いたコネクタ端子、コネクタ及び電子部品を提供することを課題とする。なお、凝着磨耗とは固体間の真実接触面積を構成する凝着部分が、摩擦運動によりせん断されることに基因して生ずる摩耗現象のことをいう。この凝着磨耗が大きくなると、オス端子とメス端子を勘合した時の挿入力が高くなる。
However, in the technique described in Patent Document 1, the relationship between the reduction in insertion force and the presence or absence of whisker generation, which have been required in recent years, has not been clarified. Moreover, since the average concentration of Sn in the Ag—Sn alloy layer is less than 10% by mass and the proportion of Ag in the Ag—Sn alloy layer is considerably large, the evaluation by the present inventors shows that chlorine gas, sulfurous acid gas, hydrogen sulfide, etc. The gas corrosion resistance to the gas was not sufficient.
Moreover, in the technique described in Patent Document 2, it is a surface layer composed of a Sn layer or Sn alloy layer having a thickness of 0.5 to 20 μm containing an Ag 3 Sn (ε phase) compound. There was a region where the insertion force could not be lowered sufficiently with this surface layer thickness. Furthermore, it is described that the content of Ag 3 Sn (ε phase) in the surface layer composed of the Sn layer or the Sn alloy layer is 0.5 to 5% by mass in terms of Ag, and from the Sn layer or the Sn alloy layer. In the evaluation by the present inventors, whisker was generated because the ratio of Sn in the surface layer formed was large and the thickness of the surface layer made of Sn layer or Sn alloy layer was also thick, and the resistance to fine sliding wear was not sufficient. Heat resistance and solder wettability were not sufficient.
In the technique described in Patent Document 3, the coating layer contains an intermetallic compound of Sn and a noble metal. The thickness of the intermetallic compound of Sn and the noble metal (Ag 3 Sn) is preferably 1 μm or more and 3 μm. It is as follows. According to the evaluation of the present inventors, the insertion force could not be lowered sufficiently with this thickness.
As described above, the metal material for electronic parts having the conventional Sn—Ag alloy / Ni base plating structure still has a problem that the insertion force cannot be sufficiently lowered and whiskers are generated. In addition, it is difficult to make the specification sufficiently satisfactory in terms of durability (heat resistance, solder wettability, fine sliding wear resistance, and gas corrosion resistance), and it has not been clarified.
The present invention has been made in order to solve the above-mentioned problems. A metal material for electronic parts having low whisker properties, low adhesion wear and high durability, and a connector terminal, a connector and an electronic component using the same. The issue is to provide. Adhesive wear refers to a wear phenomenon that occurs due to the fact that an adhesive portion constituting a real contact area between solids is sheared by frictional motion. When this adhesion wear increases, the insertion force when the male terminal and the female terminal are fitted together increases.
本発明者らは、鋭意検討の結果、基材上に下層と中層とを順に設け、下層と中層とに所定の金属を用い、且つ、下層の上部領域の酸素濃度を制御することで、低ウィスカ性、高はんだ濡れ性、低凝着磨耗性を有する電子部品用金属材料を作製することができることを見出した。 As a result of intensive studies, the inventors of the present invention have provided a lower layer and an intermediate layer in order on the base material, using a predetermined metal for the lower layer and the intermediate layer, and controlling the oxygen concentration in the upper region of the lower layer, thereby reducing It has been found that a metal material for electronic parts having whisker properties, high solder wettability, and low adhesion wear can be produced.
以上の知見を基礎として完成した本発明は一側面において、基材と、Ｎｉで構成された下層と、（i）Ａｇ及びＰｄからなる群であるＡ構成元素群から選択された１種又は２種、又は、（ii）前記Ａ構成元素群と、Ｓｎ及びＩｎからなる群であるＢ構成元素群から選択された１種又は２種との合金で構成された上層とをこの順に備え、ＸＰＳ分析を行ったときに最表面から深さ１ｎｍまでの領域に単体のＳｎ又はＩｎが残存せず、ＳＥＭによる３．５ｎｍ間隔の線分析を行ったときに前記下層側表面から上層側へ０．１μｍの厚み領域における酸素濃度が１０ｐｐｍ以下である電子部品用金属材料である。 In one aspect, the present invention completed based on the above knowledge is one or two selected from a base material, a lower layer composed of Ni, and (i) an A constituent element group which is a group consisting of Ag and Pd. A seed, or (ii) the A constituent element group and an upper layer composed of an alloy of one or two selected from the B constituent element group, which is a group consisting of Sn and In, in this order, and XPS When the analysis was performed, no single Sn or In remained in the region from the outermost surface to a depth of 1 nm. It is a metal material for electronic parts having an oxygen concentration of 10 ppm or less in a thickness region of 1 μm.
本発明の電子部品用金属材料は一実施形態において、ＳＥＭによる３．５ｎｍ間隔の線分析を行ったときに前記下層側表面から上層側へ０．１μｍの厚み領域における酸素濃度が５ｐｐｍ以下である。 In one embodiment, the metal material for electronic parts of the present invention has an oxygen concentration of 5 ppm or less in a thickness region of 0.1 μm from the lower layer side surface to the upper layer side when performing line analysis at intervals of 3.5 nm by SEM. .
本発明の電子部品用金属材料は別の一実施形態において、ＸＰＳ分析を行ったときに最表面から深さ１ｎｍまでの領域における、前記Ａ構成元素の含有量の最大値が１０ａｔ％以上である。 In another embodiment of the metal material for electronic parts according to the present invention, the maximum value of the content of the A constituent element in the region from the outermost surface to a depth of 1 nm when XPS analysis is performed is 10 at% or more. .
本発明の電子部品用金属材料は更に別の一実施形態において、前記下層と上層との間に、Ｎｉと、Ｓｎ及びＩｎからなる群であるＢ構成元素群から選択された１種又は２種とで合金が構成された中層をさらに備え、下層側表面から中層側へ０．１μｍの厚み領域における酸素濃度が１０ｐｐｍ以下である。 In still another embodiment, the metal material for electronic parts according to the present invention is one or two selected from a group B constituent element, which is a group consisting of Ni, Sn and In, between the lower layer and the upper layer. And an oxygen layer in the 0.1 μm thickness region from the lower surface to the middle layer is 10 ppm or less.
本発明の電子部品用金属材料は更に別の一実施形態において、前記下層の厚みが０．１〜０．８μｍである。 In still another embodiment of the metal material for electronic parts according to the present invention, the lower layer has a thickness of 0.1 to 0.8 μm.
本発明の電子部品用金属材料は更に別の一実施形態において、前記上層と中層との厚み比率を、上層／中層とした場合、１．８〜３．０である。 In another embodiment of the metal material for electronic parts of the present invention, the thickness ratio of the upper layer to the middle layer is 1.8 to 3.0 when the upper layer / middle layer is used.
本発明は別の一側面において、本発明の電子部品用金属材料を接点部分に用いたコネクタ端子である。 In another aspect, the present invention is a connector terminal using the metal material for electronic parts of the present invention as a contact portion.
本発明は更に別の一側面において、本発明のコネクタ端子を用いたコネクタである。 In still another aspect, the present invention is a connector using the connector terminal of the present invention.
本発明は更に別の一側面において、本発明の電子部品用金属材料を接点部分に用いたＦＦＣ端子である。 In still another aspect of the present invention, there is provided an FFC terminal using the metal material for electronic parts of the present invention as a contact portion.
本発明は更に別の一側面において、本発明の電子部品用金属材料を接点部分に用いたＦＰＣ端子である。 In still another aspect, the present invention is an FPC terminal using the metal material for electronic parts of the present invention as a contact portion.
本発明は更に別の一側面において、本発明のＦＦＣ端子を用いたＦＦＣである。 In still another aspect, the present invention is an FFC using the FFC terminal of the present invention.
本発明は更に別の一側面において、本発明のＦＰＣ端子を用いたＦＰＣである。 In still another aspect, the present invention is an FPC using the FPC terminal of the present invention.
本発明は更に別の一側面において、本発明の電子部品用金属材料を外部接続用電極に用いた電子部品である。 In still another aspect of the present invention, an electronic component using the metal material for an electronic component of the present invention as an external connection electrode.
本発明は更に別の一側面において、本発明の電子部品用金属材料を、ハウジングに取り付ける装着部の一方側にメス端子接続部が、他方側に基板接続部がそれぞれ設けられ、前記基板接続部を基板に形成されたスルーホールに圧入して前記基板に取り付ける圧入型端子に用いた電子部品である。 In yet another aspect of the present invention, the metal material for electronic components of the present invention is provided with a female terminal connection portion on one side of a mounting portion for mounting on the housing and a substrate connection portion on the other side, and the substrate connection portion. Is an electronic component used for a press-fit terminal that is press-fitted into a through-hole formed in the substrate and attached to the substrate.
本発明によれば、低ウィスカ性、高はんだ濡れ性、低凝着磨耗性を有する電子部品用金属材料、それを用いたコネクタ端子、コネクタ及び電子部品を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the metal material for electronic components which has low whisker property, high solder wettability, and low adhesive wear property, a connector terminal using the same, a connector, and an electronic component can be provided.
＜電子部品用金属材料の構成＞
本発明に係る電子部品用金属材料は、基材と、Ｎｉで構成された下層と、Ａｇ及びＰｄからなる群であるＡ構成元素群から選択された１種又は２種以上と、前記Ａ構成元素群と、Ｓｎ及びＩｎからなる群であるＢ構成元素群から選択された１種又は２種とで合金が構成された上層とをこの順に備える。
<Configuration of metal materials for electronic parts>
The metal material for electronic parts according to the present invention includes a base material, a lower layer composed of Ni, one or more selected from the group A constituent elements that are a group composed of Ag and Pd, and the A configuration An element group and an upper layer in which an alloy is composed of one or two elements selected from a group B element group, which is a group consisting of Sn and In, are provided in this order.
（基材）
基材としては、特に限定されないが、例えば、銅及び銅合金、Ｆｅ系材、ステンレス、チタン及びチタン合金、アルミニウム及びアルミニウム合金などの金属基材を用いることができる。また、金属基材に樹脂層を複合させたものであっても良い。金属基材に樹脂層を複合させたものとは、例としてＦＰＣまたはＦＦＣ基材上の電極部分などがある。
(Base material)
Although it does not specifically limit as a base material, For example, metal base materials, such as copper and a copper alloy, Fe type material, stainless steel, titanium and a titanium alloy, aluminum, and an aluminum alloy, can be used. Alternatively, a metal base and a resin layer may be combined. Examples of composites of metal layers and resin layers include electrode portions on FPC or FFC substrates.
（上層）
上層は、（i）Ａｇ及びＰｄからなる群であるＡ構成元素群から選択された１種又は２種類、又は、（ii）Ａ構成元素群と、Ｓｎ及びＩｎからなる群であるＢ構成元素群から選択された１種又は２種との合金で構成されている。Ｓｎ及びＩｎは、酸化性を有する金属ではあるが、金属の中では比較的柔らかいという特徴がある。よって、Ｓｎ及びＩｎ表面に酸化膜が形成されていても、例えば電子部品用金属材料を接点材料としてオス端子とメス端子を勘合する時に、容易に酸化膜が削られ、接点が金属同士となるため、低接触抵抗が得られる。
また、Ｓｎ及びＩｎは塩素ガス、亜硫酸ガス、硫化水素ガス等のガスに対する耐ガス腐食性に優れ、例えば、上層に耐ガス腐食性に劣るＡｇ、下層に耐ガス腐食性に劣るＮｉ、基材に耐ガス腐食性に劣る銅及び銅合金を用いた場合には、電子部品用金属材料の耐ガス腐食性を向上させる働きがある。なおＳｎ及びＩｎでは、厚生労働省の健康障害防止に関する技術指針に基づき、Ｉｎは規制が厳しいため、Ｓｎが好ましい。
(Upper layer)
The upper layer is (i) one or two types selected from an A constituent element group that is a group consisting of Ag and Pd, or (ii) a B constituent element that is a group consisting of an A constituent element group and Sn and In. It is comprised by the alloy with 1 type or 2 types selected from the group. Sn and In are oxidizable metals, but are relatively soft among metals. Therefore, even if an oxide film is formed on the Sn and In surfaces, for example, when a male terminal and a female terminal are mated using a metal material for electronic parts as a contact material, the oxide film is easily scraped, and the contact becomes metal-to-metal. Therefore, low contact resistance is obtained.
Sn and In are excellent in gas corrosion resistance against gases such as chlorine gas, sulfurous acid gas and hydrogen sulfide gas, for example, Ag inferior in gas corrosion resistance in the upper layer, Ni inferior in gas corrosion resistance in the lower layer, base material In the case of using copper and a copper alloy inferior in gas corrosion resistance, there is a function of improving the gas corrosion resistance of the metal material for electronic parts. For Sn and In, Sn is preferable because In is strictly regulated based on the technical guidelines for preventing health problems of the Ministry of Health, Labor and Welfare.
Ａｇ及びＰｄは、金属の中では比較的耐熱性を有するという特徴がある。よって基材、下層の組成が上層側に拡散するのを抑制して耐熱性を向上させる。また、これら金属は、上層のＳｎやＩｎと化合物を形成してＳｎやＩｎの酸化膜形成を抑制し、はんだ濡れ性を向上させる。なお、Ａｇ及びＰｄでは、導電率の観点でＡｇがより望ましい。Ａｇは導電率が高い。例えば高周波の信号用途にＡｇを用いた場合、表皮効果により、インピーダンス抵抗が低くなる。 Ag and Pd are characterized by relatively high heat resistance among metals. Therefore, it suppresses that the composition of a base material and a lower layer diffuses to the upper layer side, and improves heat resistance. Further, these metals form a compound with Sn or In in the upper layer to suppress the formation of an oxide film of Sn or In and improve solder wettability. For Ag and Pd, Ag is more desirable from the viewpoint of conductivity. Ag has high conductivity. For example, when Ag is used for high frequency signal applications, the impedance resistance is lowered due to the skin effect.
本発明の電子部品用金属材料において、最表面から深さ１ｎｍまでの領域に単体のＳｎ又はＩｎが残存しない。このように、「最表面から深さ１ｎｍまでの領域」という最表層において、単体のＳｎ又はＩｎが存在しないことで、凝着摩耗が抑制されて耐摩耗性が良好となり、さらにウィスカ性も良好となる。 In the metal material for electronic parts of the present invention, no single Sn or In remains in the region from the outermost surface to a depth of 1 nm. In this way, in the outermost layer “region from the outermost surface to a depth of 1 nm”, the absence of single Sn or In suppresses adhesive wear and improves wear resistance, and whisker properties are also good. It becomes.
本発明の電子部品用金属材料において、最表面から深さ１ｎｍまでの領域における、Ａ構成元素の含有量の最大値が１０ａｔ％以上であるのが好ましい。このように、最表層において、Ａ構成元素の含有量の最大値が１０ａｔ％以上であると、最表層のＳｎ又はＩｎの含有量がより抑えられ、凝着摩耗が抑制されて耐摩耗性がより良好となり、さらにウィスカ性もより良好となる。 In the metal material for electronic parts of the present invention, it is preferable that the maximum value of the content of the A constituent element in the region from the outermost surface to a depth of 1 nm is 10 at% or more. Thus, in the outermost layer, when the maximum value of the content of the A constituent element is 10 at% or more, the content of Sn or In in the outermost layer is further suppressed, adhesive wear is suppressed, and wear resistance is reduced. It becomes better and whisker property becomes better.
上層の厚みは０．０５μｍ以上１．００μｍ未満であるのが好ましい。上層の厚みが０．０５μｍ未満であると、基材や下層の組成が上層側に拡散しやすくなって耐熱性やはんだ濡れ性が悪くなることがある。また微摺動によって上層が磨耗し、接触抵抗の高い下層が露出しやすくなるため耐微摺動磨耗性が悪く、微摺動によって接触抵抗が上昇しやすくなることがある。更に耐ガス腐食性が悪い下層が露出しやすくなるため耐ガス腐食性も悪く、ガス腐食試験を行うと外観が変色してしまうことがある。一方、上層の厚みが１．００μｍ以上であると、硬い基材または下層による薄膜潤滑効果が低下して凝着磨耗が大きくなることがある。また機械的耐久性が低下して、めっき削れが発生しやすくなることがある。 The thickness of the upper layer is preferably 0.05 μm or more and less than 1.00 μm. When the thickness of the upper layer is less than 0.05 μm, the composition of the base material or the lower layer tends to diffuse to the upper layer side, and heat resistance and solder wettability may be deteriorated. Further, the upper layer is worn by fine sliding, and the lower layer having a high contact resistance is easily exposed, so the resistance to fine sliding wear is poor, and the contact resistance is likely to increase due to fine sliding. Furthermore, since the lower layer with poor gas corrosion resistance is easily exposed, the gas corrosion resistance is also poor, and when the gas corrosion test is performed, the appearance may be discolored. On the other hand, if the thickness of the upper layer is 1.00 μm or more, the thin film lubrication effect by the hard base material or the lower layer may be lowered and adhesion wear may be increased. In addition, mechanical durability may be reduced, and plating scraping may occur easily.
上層は、Ｂ構成元素群の金属を１０〜５０ａｔ％含有することが好ましい。Ｂ構成元素群の金属が１０ａｔ％未満であると、例えばＡ構成元素群の金属がＡｇの場合、耐ガス腐食性が悪く、ガス腐食試験を行うと外観が変色する場合がある。一方、Ｂ構成元素群の金属が５０ａｔ％を超えると、上層におけるＢ構成元素群の金属の割合が大きくなって凝着磨耗が大きくなり、またウィスカも発生しやすくなる。更に耐微摺動磨耗性が悪い場合もある。 The upper layer preferably contains 10 to 50 at% of the metal of the B constituent element group. When the metal of the B constituent element group is less than 10 at%, for example, when the metal of the A constituent element group is Ag, the gas corrosion resistance is poor, and when the gas corrosion test is performed, the appearance may be discolored. On the other hand, if the metal of the B constituent element group exceeds 50 at%, the proportion of the metal of the B constituent element group in the upper layer is increased and adhesion wear is increased, and whiskers are easily generated. Furthermore, there are cases where the resistance to fine sliding wear is poor.
上層に、Ｓｎを１１．８〜２２．９ａｔ％含むＳｎＡｇ合金であるζ（ゼータ）相が存在することが好ましい。当該ζ（ゼータ）相が存在することで耐ガス腐食性が向上し、ガス腐食試験を行っても外観が変色しにくくなる。
上層に、ζ（ゼータ）相と、Ａｇ3Ｓｎであるε（イプシロン）相とが存在することが好ましい。ε（イプシロン）相の存在によって、上層にζ（ゼータ）相のみが存在する場合と比較して皮膜が硬くなり凝着磨耗が低下する。また上層のＳｎ割合が多くなることで耐ガス腐食性が向上する。
上層に、Ａｇ3Ｓｎであるε（イプシロン）相のみが存在することが好ましい。上層にε（イプシロン）相が単独に存在することによって、上層にζ（ゼータ）相とＡｇ3Ｓｎであるε（イプシロン）相とが存在する場合と比較して皮膜が更に硬くなり凝着磨耗が低下する。また上層のＳｎ割合がより多くなることで耐ガス腐食性も向上する。
上層に、Ａｇ3Ｓｎであるε（イプシロン）相と、Ｓｎ単相であるβＳｎとが存在することが好ましい。Ａｇ3Ｓｎであるε（イプシロン）相と、Ｓｎ単相であるβＳｎとが存在することによって、上層にε（イプシロン）相のみが存在する場合と比較して更に上層のＳｎ割合がより多くなることで耐ガス腐食性が向上する。
上層に、Ｓｎを１１．８〜２２．９ａｔ％含むＳｎＡｇ合金であるζ（ゼータ）相と、Ａｇ3Ｓｎであるε（イプシロン）相と、Ｓｎ単相であるβＳｎとが存在することが好ましい。ζ（ゼータ）相と、Ａｇ3Ｓｎであるε（イプシロン）相と、Ｓｎ単相であるβＳｎとが存在することによって、耐ガス腐食性が向上し、ガス腐食試験を行っても外観が変色しにくく、凝着磨耗が低下する。この組成は拡散で生じるものであり、平衡状態の構造ではない。
It is preferable that a ζ (zeta) phase which is a SnAg alloy containing 11.8 to 22.9 at% of Sn exists in the upper layer. The presence of the ζ (zeta) phase improves the gas corrosion resistance, and the appearance hardly changes even when a gas corrosion test is performed.
It is preferable that a ζ (zeta) phase and an ε (epsilon) phase that is Ag 3 Sn exist in the upper layer. Due to the presence of the ε (epsilon) phase, the film becomes harder and adhesion wear is reduced compared to the case where only the ζ (zeta) phase is present in the upper layer. Further, the gas corrosion resistance is improved by increasing the Sn ratio of the upper layer.
It is preferable that only an ε (epsilon) phase that is Ag 3 Sn exists in the upper layer. The presence of the ε (epsilon) phase alone in the upper layer makes the coating harder and adhesive wear than in the case where the ζ (zeta) phase and Ag 3 Sn ε (epsilon) phase are present in the upper layer. Decreases. Further, the gas corrosion resistance is improved by increasing the Sn ratio in the upper layer.
It is preferable that an ε (epsilon) phase that is Ag 3 Sn and βSn that is a single Sn phase exist in the upper layer. The presence of the ε (epsilon) phase that is Ag 3 Sn and βSn that is the Sn single phase further increases the Sn ratio of the upper layer compared to the case where only the ε (epsilon) phase exists in the upper layer. This improves gas corrosion resistance.
It is preferable that a ζ (zeta) phase that is a SnAg alloy containing 11.8 to 22.9 at% of Sn, an ε (epsilon) phase that is Ag 3 Sn, and βSn that is a Sn single phase are present in the upper layer. . The presence of the ζ (zeta) phase, the ε (epsilon) phase that is Ag 3 Sn, and βSn that is the Sn single phase improves the gas corrosion resistance, and the appearance changes even when a gas corrosion test is performed. It is difficult to wear and adhesion wear decreases. This composition occurs by diffusion and is not an equilibrium structure.
（下層）
基材と中層との間には、Ｎｉで構成された下層を形成することで、硬い下層形成により薄膜潤滑効果が向上して凝着磨耗が低下し、下層は基材の構成金属が中層、上層に拡散するのを防止して耐熱性やはんだ濡れ性などを向上させる。
(Underlayer)
Between the base material and the middle layer, by forming a lower layer composed of Ni, the thin film lubrication effect is improved by the formation of the hard lower layer and the adhesion wear is reduced. Prevents diffusion to the upper layer to improve heat resistance and solder wettability.
下層の厚みは０．０５〜５．０μｍであるのが好ましく、０．１〜０．８μｍがより好ましく、０．３〜０．５μｍであるのが更に好ましい。下層の厚みが０．０５μｍ未満であると、硬い下層による薄膜潤滑効果が低下して凝着磨耗が大きくなる場合がある。また、基材の構成金属が上層に拡散しやすくなり、耐熱性やはんだ濡れ性が劣化する場合がある。下層の厚みが５．０μｍを超えると、耐摩耗性が劣化するおそれがある。 The thickness of the lower layer is preferably 0.05 to 5.0 μm, more preferably 0.1 to 0.8 μm, and still more preferably 0.3 to 0.5 μm. If the thickness of the lower layer is less than 0.05 μm, the thin film lubricating effect of the hard lower layer may be reduced, and adhesion wear may be increased. In addition, the constituent metal of the base material tends to diffuse into the upper layer, and heat resistance and solder wettability may deteriorate. When the thickness of the lower layer exceeds 5.0 μm, the wear resistance may be deteriorated.
下層側表面から上層側へ０．１μｍの厚み領域における酸素濃度は、１０ｐｐｍ以下に制御されている。このような構成によれば、はんだ濡れ性を向上させるという効果が得られる。下層側表面から上層側へ０．１μｍの厚み領域における酸素濃度は、５ｐｐｍ以下であるのが好ましく、１ｐｐｍ以下であるのがより好ましい。 The oxygen concentration in the thickness region of 0.1 μm from the lower surface to the upper layer is controlled to 10 ppm or less. According to such a structure, the effect of improving solder wettability is acquired. The oxygen concentration in the thickness region of 0.1 μm from the lower layer side surface to the upper layer side is preferably 5 ppm or less, and more preferably 1 ppm or less.
（中層）
下層と上層との間に、Ｎｉと、Ｓｎ及びＩｎからなる群であるＢ構成元素群から選択された１種又は２種とで合金が構成された中層がさらに設けられていてもよい。Ｓｎ及びＩｎは塩素ガス、亜硫酸ガス、硫化水素ガス等のガスに対する耐ガス腐食性に優れ、電子部品用金属材料の耐ガス腐食性を向上させる働きがある。Ｎｉは、ＳｎやＩｎと比較して皮膜が硬いために凝着磨耗が生じにくく、基材の構成金属が上層に拡散するのを防止し、耐熱性試験やはんだ濡れ性劣化を抑制するなどの耐久性を向上させる。
(Middle layer)
Between the lower layer and the upper layer, an intermediate layer in which an alloy is composed of Ni and one or two selected from the B constituent element group that is a group consisting of Sn and In may be further provided. Sn and In are excellent in gas corrosion resistance against gases such as chlorine gas, sulfurous acid gas, and hydrogen sulfide gas, and have a function of improving the gas corrosion resistance of metal materials for electronic parts. Ni has a harder film than Sn and In, so that it is difficult for adhesive wear to occur, prevents the constituent metals of the base material from diffusing into the upper layer, and suppresses heat resistance tests and solder wettability degradation. Improve durability.
中層の厚みは、０．０１μｍ以上０．４０μｍ未満であるのが好ましい。中層の厚みが０．０１μｍ以上であると皮膜が硬くなり凝着磨耗が減少する。一方中層の厚みが０．４０μｍ以上であると曲げ加工性が低下し、また機械的耐久性が低下して、めっき削れが発生する場合がある。
Ｓｎ及びＩｎの中では、厚生労働省の健康障害防止に関する技術指針に基づき、Ｉｎは規制が厳しいため、Ｓｎが好ましい。
The thickness of the middle layer is preferably 0.01 μm or more and less than 0.40 μm. When the thickness of the middle layer is 0.01 μm or more, the coating becomes hard and adhesion wear decreases. On the other hand, if the thickness of the middle layer is 0.40 μm or more, the bending workability is lowered, the mechanical durability is lowered, and plating scraping may occur.
Among Sn and In, Sn is preferable because In is strictly regulated based on the technical guideline for preventing health problems of the Ministry of Health, Labor and Welfare.
中層においてＢ構成元素群の金属が３５ａｔ％以上であることが好ましい。Ｓｎが３５ａｔ％以上になることで皮膜が硬くなり凝着磨耗が減少する場合がある。
中層に、Ｎｉ3Ｓｎ4と、Ｎｉ3Ｓｎ2とが存在することが好ましい。これらが存在することによって耐熱性やはんだ濡れ性を向上させる場合がある。
中層に、Ｎｉ3Ｓｎ4と、Ｓｎ単相であるβＳｎとが存在することが好ましい。これらが存在することによって耐熱性やはんだ濡れ性は、Ｎｉ3Ｓｎ4とＮｉ3Ｓｎ2が存在する場合と比較して耐熱性やはんだ濡れ性が向上する場合がある。
In the middle layer, the B group element group metal is preferably 35 at% or more. If the Sn content is 35 at% or more, the film becomes hard and adhesion wear may be reduced.
Ni 3 Sn 4 and Ni 3 Sn 2 are preferably present in the middle layer. The presence of these may improve heat resistance and solder wettability.
It is preferable that Ni 3 Sn 4 and βSn which is a Sn single phase exist in the middle layer. The presence of these may improve the heat resistance and solder wettability as compared with the case where Ni 3 Sn 4 and Ni 3 Sn 2 exist.
上層と中層との厚み比率を、上層／中層とした場合、１．８〜３．０であることが好ましい。上層／中層が３．０を超えると、凝着磨耗が大きくなる。一方、上層／中層が１．８を下回ると、接触抵抗が高く、はんだも濡れ難く、耐ガス腐食性が劣るＮｉが表面に露出しやすくなるため、耐熱性、はんだ濡れ性、耐微摺動磨耗性及び耐ガス腐食性が悪くなる場合がある。上層／中層は、より好ましくは２．０〜２．８であり、更により好ましくは２．４〜２．７である。 When the thickness ratio of the upper layer to the middle layer is defined as upper layer / middle layer, it is preferably 1.8 to 3.0. When the upper layer / middle layer exceeds 3.0, adhesion wear increases. On the other hand, when the upper layer / middle layer is less than 1.8, the contact resistance is high, the solder is difficult to wet, and Ni having poor gas corrosion resistance is easily exposed on the surface. Abrasion and gas corrosion resistance may deteriorate. The upper layer / middle layer is more preferably 2.0 to 2.8, and even more preferably 2.4 to 2.7.
本発明の電子部品用金属材料は、中層を備える場合、下層側表面から中層側へ０．１μｍの厚み領域における酸素濃度が１０ｐｐｍ以下に制御されているのが好ましい。このような構成によれば、はんだ濡れ性をより向上させるという効果が得られる。下層側表面から中層側へ０．１μｍの厚み領域における酸素濃度は５ｐｐｍ以下であるのがより好ましく、１ｐｐｍ以下であるのが更により好ましい。 When the metal material for electronic components of the present invention includes an intermediate layer, it is preferable that the oxygen concentration in the 0.1 μm thickness region is controlled to 10 ppm or less from the lower layer surface to the intermediate layer side. According to such a structure, the effect of improving solder wettability more is acquired. The oxygen concentration in the thickness region of 0.1 μm from the lower layer side surface to the middle layer side is more preferably 5 ppm or less, and even more preferably 1 ppm or less.
（拡散処理）
上層、中層及び下層が、基材上にＮｉを成膜し、その後、Ａ構成元素群から選択された１種又は２種を成膜し、その後、前記Ａ構成元素群と、Ｂ構成元素群から選択された１種又は２種を成膜し、Ｎｉ、Ａ構成元素群及びＢ構成元素群の各元素が拡散することでそれぞれ形成されていても良い。例えばＢ構成元素群の金属がＳｎ、Ａ構成元素群の金属がＡｇの場合、ＳｎへのＡｇの拡散は速く、自然拡散によってＳｎ−Ａｇ合金層を形成する。合金層を形成しＳｎを残存させないことにより凝着力を一層小さくし、また低ウィスカ性及び耐久性も更に向上させることができる。
(Diffusion processing)
The upper layer, the middle layer, and the lower layer are formed by forming Ni on the base material, and then forming one or two selected from the A constituent element group, and then forming the A constituent element group and the B constituent element group. 1 type or 2 types selected from the above may be formed, and each element of Ni, A constituent element group, and B constituent element group may be diffused. For example, when the metal of the B constituent element group is Sn and the metal of the A constituent element group is Ag, the diffusion of Ag into Sn is fast, and a Sn—Ag alloy layer is formed by natural diffusion. By forming an alloy layer and leaving no Sn remaining, the adhesion force can be further reduced, and the low whisker property and durability can be further improved.
（熱処理）
上層を形成させた後に更に凝着磨耗抑制し、また低ウィスカ性及び耐久性を更に向上させる目的で熱処理を施しても良い。熱処理によって上層のＡ構成元素群の金属とＢ構成元素群の金属、中層のＮｉとＢ構成元素群の金属とが合金層をより形成しやすくなり、Ｓｎの凝着力を一層小さくし、また低ウィスカ性及び耐久性も更に向上させることができる。
なお、この熱処理については、処理条件（温度×時間）は適宜選択できる。また、特にこの熱処理はしなくてもよい。なお熱処理を施す場合にはＢ構成元素群の金属の融点以上の温度で行った方が上層のＡ構成元素群の金属とＢ構成元素群の金属、中層のＮｉとＢ構成元素群の金属とが合金層をより形成しやすくなる。合金層は熱処理を行わなくとも、常温で反応が進み、合金化するが、熱処理により合金化を促進させた方が、凝着摩耗の抑制には好ましい。
(Heat treatment)
After the upper layer is formed, heat treatment may be performed for the purpose of further suppressing adhesion wear and further improving the low whisker property and durability. The heat treatment makes it easier to form an alloy layer with the upper layer metal of the A constituent element group and the metal of the B constituent element group, the middle layer Ni and the metal of the B constituent element group, further reducing the adhesion force of Sn, and low Whisker properties and durability can be further improved.
In addition, about this heat processing, process conditions (temperature x time) can be selected suitably. Further, this heat treatment is not particularly required. When heat treatment is performed at a temperature equal to or higher than the melting point of the B constituent element group metal, the upper A constituent element group metal, the B constituent element group metal, the middle layer Ni, and the B constituent element group metal However, it becomes easier to form an alloy layer. Even if the alloy layer is not subjected to heat treatment, the reaction proceeds at room temperature and is alloyed. However, it is preferable to promote the alloying by heat treatment in order to suppress adhesion wear.
（後処理）
上層上に、または上層上に熱処理を施した後に、更に凝着磨耗を低下させ、また低ウィスカ性及び耐久性も向上させる目的で後処理を施しても良い。後処理によって潤滑性が向上し、更に凝着磨耗が低下しまた上層の酸化が抑制されて、耐熱性やはんだ濡れ性等の耐久性を向上させることができる。具体的な後処理としてはインヒビターを用いた、リン酸塩処理、潤滑処理、シランカップリング処理等がある。
(Post-processing)
After heat treatment is performed on the upper layer or on the upper layer, post-treatment may be performed for the purpose of further reducing adhesion wear and improving low whisker property and durability. Post-treatment improves lubricity, further reduces adhesion wear, suppresses oxidation of the upper layer, and improves durability such as heat resistance and solder wettability. Specific post-treatment includes phosphate treatment, lubrication treatment, silane coupling treatment, etc. using an inhibitor.
＜電子部品用金属材料の用途＞
本発明の電子部品用金属材料の用途は特に限定しないが、例えば電子部品用金属材料を接点部分に用いたコネクタ端子、電子部品用金属材料を接点部分に用いたＦＦＣ端子またはＦＰＣ端子、電子部品用金属材料を外部接続用電極に用いた電子部品などが挙げられる。なお、端子については、圧着端子、はんだ付け端子、プレスフィット端子等、配線側との接合方法によらない。外部接続用電極には、タブに表面処理を施した接続部品や半導体のアンダーバンプメタル用に表面処理を施した材料などがある。
また、このように形成されたコネクタ端子を用いてコネクタを作製しても良く、ＦＦＣ端子またはＦＰＣ端子を用いてＦＦＣまたはＦＰＣを作製しても良い。
また本発明の電子部品用金属材料は、ハウジングに取り付ける装着部の一方側にメス端子接続部が、他方側に基板接続部がそれぞれ設けられ、該基板接続部を基板に形成されたスルーホールに圧入して該基板に取り付ける圧入型端子に用いても良い。
コネクタはオス端子とメス端子の両方が本発明の電子部品用金属材料であっても良いし、オス端子またはメス端子の片方だけであっても良い。なおオス端子とメス端子の両方を本発明の電子部品用金属材料にすることで、更に低挿抜性が向上する。
<Applications of metal materials for electronic parts>
The use of the metal material for electronic parts of the present invention is not particularly limited. For example, a connector terminal using the metal material for electronic parts as a contact part, an FFC terminal or FPC terminal using the metal material for electronic parts as a contact part, and an electronic part Electronic parts using metal materials for external connection as electrodes for external connection. In addition, about a terminal, it does not depend on the joining method with a wiring side, such as a crimp terminal, a solder terminal, and a press fit terminal. Examples of the external connection electrode include a connection component in which a surface treatment is performed on a tab and a material in which a surface treatment is applied to a semiconductor under bump metal.
Moreover, a connector may be produced using the connector terminal formed in this way, and an FFC or FPC may be produced using an FFC terminal or an FPC terminal.
In the metal material for electronic parts of the present invention, the female terminal connection portion is provided on one side of the mounting portion to be attached to the housing, and the substrate connection portion is provided on the other side. The substrate connection portion is formed in a through hole formed on the substrate. You may use for the press-fit type terminal which press-fits and attaches to this board | substrate.
In the connector, both the male terminal and the female terminal may be the metal material for electronic parts of the present invention, or only one of the male terminal and the female terminal. In addition, low insertion property is further improved by making both the male terminal and the female terminal into the metal material for electronic parts of the present invention.
＜電子部品用金属材料の製造方法＞
本発明の電子部品用金属材料の製造方法としては、湿式（電気）を用いて行う。また、下層を成膜させた後にＡｇ及びＰｄの低イオンのストライクめっきを高電流密度にてめっきを施すことによって、下層の上部領域における酸素濃度を制御することができ、はんだ濡れ性を向上させることができる。ストライクめっき濃度は１ｇ／Ｌ〜５ｇ／Ｌが好ましく、２ｇ／Ｌ〜３ｇ／Ｌがより好ましく、電流密度（Ｄｋ）は３Ａ／ｄｍ2〜８Ａ／ｄｍ2が好ましく、５Ａ／ｄｍ2〜６Ａ／ｄｍ2がより好ましい。ストライクめっきの厚みは、０．０２〜０．１μｍであるのが好ましい。
<Method for producing metal material for electronic parts>
The method for producing the metal material for electronic parts of the present invention is performed using wet (electric). In addition, by depositing Ag and Pd low-ion strike plating at a high current density after forming the lower layer, the oxygen concentration in the upper region of the lower layer can be controlled, and solder wettability is improved. be able to. The strike plating concentration is preferably 1 g / L to 5 g / L, more preferably 2 g / L to 3 g / L, and the current density (Dk) is preferably 3 A / dm 2 to 8 A / dm 2 , preferably 5 A / dm 2 to 6 A / L. dm 2 is more preferred. The thickness of the strike plating is preferably 0.02 to 0.1 μm.
以下、本発明の実施例と比較例を共に示すが、これらは本発明をより良く理解するために提供するものであり、本発明が限定されることを意図するものではない。
実施例及び比較例として、表１に示す条件で、素材（１）〜（３）に対し、それぞれ、電解脱脂、酸洗、第１めっき、ストライクＡｇめっき、第２めっき、第３めっき、及び、熱処理の順で表面処理を行った。また、熱処理前の前記第１めっき、第２めっき、第３めっきによって基材側から順に作製された、被覆層（１）、被覆層（２）、被覆層（３）の組成及び厚みを表２に示す。当該厚みは、蛍光Ｘ線膜厚計（Ｓｅｉｋｏ Ｉｎｓｔｒｕｍｅｎｔｓ製 ＳＥＡ５１００、コリメータ０．１ｍｍΦ）で任意の１０点測定した値の平均である。
Hereinafter, although the Example and comparative example of this invention are shown together, these are provided in order to understand this invention better, and this invention is not intended to be limited.
As examples and comparative examples, the materials (1) to (3) were subjected to electrolytic degreasing, pickling, first plating, strike Ag plating, second plating, third plating, and the conditions shown in Table 1, respectively. Surface treatment was performed in the order of heat treatment. In addition, the composition and thickness of the coating layer (1), the coating layer (2), and the coating layer (3) prepared in order from the substrate side by the first plating, the second plating, and the third plating before the heat treatment are shown. It is shown in 2. The said thickness is the average of the value measured by arbitrary 10 points | pieces with the fluorescent-X-ray-film thickness meter (Seiko Instruments SEA5100, collimator 0.1mm (PHI)).
（素材）
（１）板材：厚み０．３０ｍｍ、幅３０ｍｍ、成分Ｃｕ−３０Ｚｎ
（２）オス端子：厚み０．６４ｍｍ、幅２．３ｍｍ、成分Ｃｕ−３０Ｚｎ
（３）圧入型端子：常盤商行、プレスフィット端子ＰＣＢコネクタ、Ｒ８００
(Material)
(1) Plate material: thickness 0.30 mm, width 30 mm, component Cu-30Zn
(2) Male terminal: thickness 0.64 mm, width 2.3 mm, component Cu-30Zn
(3) Press-fit type terminals: Tokiwa Shoko, press-fit terminal PCB connector, R800
（第１めっき条件）
（１）半光沢Ｎｉめっき条件
表面処理方法：電気めっき
めっき液：スルファミン酸Ｎｉめっき液＋サッカリン
めっき温度：５５℃
電流密度：０．５〜４Ａ／ｄｍ2
(First plating condition)
(1) Semi-bright Ni plating conditions Surface treatment method: electroplating plating solution: sulfamic acid Ni plating solution + saccharin plating temperature: 55 ° C
Current density: 0.5-4 A / dm 2
（ストライクＡｇめっき条件）
表２に記載の条件にて、それぞれストライクめっきを行った。
(Strike Ag plating conditions)
Strike plating was performed under the conditions shown in Table 2, respectively.
（第２めっき条件）
（１）Ａｇめっき条件
表面処理方法：電気めっき
めっき液：シアン化Ａｇめっき液
めっき温度：４０℃
電流密度：０．２〜４Ａ／ｄｍ2
（２）Ｐｄめっき条件
表面処理方法：電気めっき
めっき液：メタンスルホン酸Ｐｄめっき液
めっき温度：４０℃
電流密度：０．５〜４Ａ／ｄｍ2
(Second plating condition)
(1) Ag plating conditions Surface treatment method: electroplating Plating solution: cyanide Ag plating solution Plating temperature: 40 ° C
Current density: 0.2-4 A / dm 2
(2) Pd plating conditions Surface treatment method: electroplating Plating solution: methanesulfonic acid Pd plating solution Plating temperature: 40 ° C
Current density: 0.5-4 A / dm 2
（第３めっき条件）
（１）Ｓｎめっき条件
表面処理方法：電気めっき
めっき液：メタンスルホン酸Ｓｎめっき液
めっき温度：４０℃
電流密度：０．５〜４Ａ／ｄｍ2
（２）Iｎめっき条件
表面処理方法：電気めっき
めっき液：メタンスルホン酸Iｎめっき液
めっき温度：４０℃
電流密度：０．５〜４Ａ／ｄｍ2
(Third plating condition)
(1) Sn plating conditions Surface treatment method: electroplating plating solution: methanesulfonic acid Sn plating solution Plating temperature: 40 ° C
Current density: 0.5-4 A / dm 2
(2) In plating conditions Surface treatment method: Electroplating Plating solution: Methanesulfonic acid In plating solution Plating temperature: 40 ° C
Current density: 0.5-4 A / dm 2
（熱処理）
ホットプレートにサンプルを置き、ホットプレートの表面が所定の温度になったことを確認して所定時間加熱した。
(Heat treatment)
A sample was placed on a hot plate, and after confirming that the surface of the hot plate had reached a predetermined temperature, it was heated for a predetermined time.
（表層、上層及び中層の組成及び厚み測定）
得られた試料の表層、上層、中層の厚み及び組成については、ＳＴＥＭ（日本電子株式会社製ＪＥＭ−２１００Ｆ）の線分析で評価し、熱処理により基材に被覆した元素が反応して合金化し、上層、中層を形成していることが確認された。上層、中層の厚さの比に関しては上記線分析を任意の１０点について行った平均値を求めた。
(Surface layer, upper layer and middle layer composition and thickness measurement)
About the thickness and composition of the surface layer, the upper layer, and the middle layer of the obtained sample, they are evaluated by the line analysis of STEM (JEM-2100F manufactured by JEOL Ltd.), and the elements coated on the base material by heat treatment react and alloy, It was confirmed that an upper layer and a middle layer were formed. Regarding the ratio of the thicknesses of the upper layer and the middle layer, an average value obtained by performing the above line analysis on arbitrary 10 points was obtained.
（下層の厚み測定）
下層の厚みは、蛍光Ｘ線膜厚計（Ｓｅｉｋｏ Ｉｎｓｔｒｕｍｅｎｔｓ製 ＳＥＡ５１００、コリメータ０．１ｍｍΦ）で測定し、任意の１０点について評価を行って平均化した。
上記試験条件及び試験結果を表１〜３に示す。
(Under layer thickness measurement)
The thickness of the lower layer was measured with a fluorescent X-ray film thickness meter (SEA 5100, manufactured by Seiko Instruments, collimator 0.1 mmΦ), and an arbitrary 10 points were evaluated and averaged.
The said test conditions and a test result are shown to Tables 1-3.
（評価）
各試料について以下の評価を行った。
・最表面から深さ１ｎｍまでの領域における単体のＳｎ及びＩｎ、及び、Ａ構成元素の原子濃度の最大値
各試料の最表面から深さ１ｎｍまでの領域における単体のＳｎ及びＩｎ、及び、Ａ構成元素の原子濃度を分析するために、アルバック・ファイ株式会社製ＸＰＳ分析装置（型式：PHI5000 Versa Probe II）を用いて、以下の条件にてＸＰＳによる測定を行った。これにより、最表面から深さ１ｎｍまでの領域におけるＡ構成元素の原子濃度を測定し、単体のＳｎ及びＩｎが残存しているか否か、その中のピークの濃度、すなわち、Ａ構成元素の原子濃度の最大値を求めた。
（測定条件）
到達真空度：２．２×１０-7Ｐａ
励起源：単色化 ＡｌＫ
出力： ２５Ｗ
検出面積： １００μｍφ
入射角： ９０度
取り出し角： ４５度
中和銃：なし
（スパッタ条件）
イオン種：Ａｒ+
加速電圧：２ｋＶ
掃引領域：３ｍｍ×３ｍｍ
レート：０．４ｎｍ／ｍｉｎ(ＳｉＯ2換算）
(Evaluation)
The following evaluation was performed for each sample.
Single element Sn and In in the region from the outermost surface to a depth of 1 nm, and the maximum value of the atomic concentration of the A constituent element Single element Sn and In and A in the region from the outermost surface of each sample to a depth of 1 nm In order to analyze the atomic concentration of the constituent elements, measurement by XPS was performed under the following conditions using an XPS analyzer (model: PHI5000 Versa Probe II) manufactured by ULVAC-PHI. Thereby, the atomic concentration of the A constituent element in the region from the outermost surface to a depth of 1 nm is measured, whether or not single Sn and In remain, the concentration of the peak therein, that is, the atom of the A constituent element The maximum concentration was determined.
(Measurement condition)
Ultimate vacuum: 2.2 × 10 −7 Pa
Excitation source: Monochromatic AlK
Output: 25W
Detection area: 100μmφ
Incident angle: 90 degrees Extraction angle: 45 degrees Neutralizing gun: None (Sputtering conditions)
Ion species: Ar +
Acceleration voltage: 2 kV
Sweep area: 3mm x 3mm
Rate: 0.4 nm / min (SiO 2 conversion)
・下層の上側領域の酸素濃度
ＳＴＥＭ（走査型電子顕微鏡）分析による線分析で、下層側表面から上層側、或いは、中層側へ０．１μｍの厚み領域に対し、酸素濃度の測定を行った。ＳＴＥＭ装置は、日本電子株式会社製ＪＥＭ−２１００Ｆを用いた。本装置の加速電圧は２００ｋＶである。測定は、３．５ｎｍ間隔で５回の線分析を行い、最大値を表に示した。また、本装置のコンデンサレンズ絞りは２０μｍで行った。
-Oxygen concentration in upper region of lower layer In line analysis by STEM (scanning electron microscope) analysis, an oxygen concentration was measured from a lower layer surface to an upper layer side or an intermediate layer side with respect to a thickness region of 0.1 μm. JEM-2100F manufactured by JEOL Ltd. was used as the STEM apparatus. The acceleration voltage of this device is 200 kV. For the measurement, line analysis was performed 5 times at intervals of 3.5 nm, and the maximum values were shown in the table. Further, the condenser lens diaphragm of this apparatus was 20 μm.
・はんだ濡れ性
はんだ濡れ性はめっき後のサンプルを評価した。サンプルとして、めっき直後（初期）のサンプル、及び、温度８５℃、湿度８５％の環境下で４８時間経過後のサンプルをそれぞれ評価した。ソルダーチェッカ（レスカ社製ＳＡＴ−５２００）を使用し、フラックスとして市販のＵＬＦ−３００Ｒ（タムラ製作所）を用い、メニスコグラフ法にてはんだ濡れ時間を測定した。はんだはＳｎ−３Ａｇ−０．５Ｃｕ（２５０℃）を用いた。サンプル数は５個とし、各サンプルの最小値から最大値の範囲を採用した。目標とする特性は、ゼロクロスタイム１秒（ｓ）以下である。
-Solder wettability The solder wettability evaluated the sample after plating. As samples, samples immediately after plating (initial stage) and samples after 48 hours in an environment of temperature 85 ° C. and humidity 85% were evaluated. Solder checker (SAT-5200 manufactured by Reska Co., Ltd.) was used, and a commercially available ULF-300R (Tamura Seisakusho) was used as a flux, and the solder wetting time was measured by the meniscograph method. The solder used was Sn-3Ag-0.5Cu (250 ° C.). The number of samples was 5, and the range from the minimum value to the maximum value of each sample was adopted. The target characteristic is a zero cross time of 1 second (s) or less.
・耐微摺動磨耗性
耐微摺動磨耗性は、山崎精機研究所製精密摺動試験装置ＣＲＳ−Ｇ２０５０型を使用し、摺動距離０．５ｍｍ、摺動速度１ｍｍ／ｓ、接触荷重１Ｎ、摺動回数５００往復条件で摺動回数と接触抵抗との関係を評価した。サンプル数は２個とし、各サンプルの値を記した。また、サンプルを摺動させながら接触抵抗を測定し、接触抵抗が５０ｍΩとなった時の摺動回数を記録した。
・ Small sliding wear resistance Fine sliding wear resistance is measured using a precision sliding test device CRS-G2050 manufactured by Yamazaki Seiki Laboratories, with a sliding distance of 0.5 mm, a sliding speed of 1 mm / s, and a contact load of 1 N. The relationship between the number of sliding times and the contact resistance was evaluated under the condition that the number of sliding times was 500. The number of samples was 2, and the value of each sample was noted. Further, the contact resistance was measured while sliding the sample, and the number of times of sliding when the contact resistance reached 50 mΩ was recorded.
・ウィスカ
ウィスカは、ＪＥＩＴＡ ＲＣ−５２４１の荷重試験（球圧子法）にて評価した。すなわち、各サンプルに対して荷重試験を行い、荷重試験を終えたサンプルをＳＥＭ（ＪＥＯＬ社製、型式ＪＳＭ−５４１０）にて１００〜１００００倍の倍率で観察して、ウィスカの発生状況を観察した。荷重試験条件を以下に示す。
球圧子の直径：Φ１ｍｍ±０．１ｍｍ
試験荷重：２Ｎ±０．２Ｎ
試験時間：１２０時間
サンプル数：１０個
評価結果を表４に示す。
-Whisker Whisker was evaluated by a load test (ball indenter method) of JEITA RC-5241. That is, a load test was performed on each sample, and the sample after the load test was observed at a magnification of 100 to 10,000 times with a SEM (manufactured by JEOL, model JSM-5410) to observe the occurrence of whiskers. . The load test conditions are shown below.
Diameter of ball indenter: Φ1mm ± 0.1mm
Test load: 2N ± 0.2N
Test time: 120 hours Number of samples: 10 Table 4 shows the evaluation results.
実施例１〜１０は、高はんだ濡れ性、低ウィスカ性、低凝着磨耗性のいずれも優れた電子部品金属材料であった。
比較例１〜９は、高はんだ濡れ性、低ウィスカ性、低凝着磨耗性の少なくともいずれかが不良であった。
比較例１、２は、熱処理不足で最表層にＳｎ及びＩｎが残存しており、凝着摩耗が大きくなり耐摩耗性を低下させてしまった。また、最表層にＳｎ及びＩｎが残存することでウィスカ性も悪化した。比較例７はＳｎの膜厚が厚く、熱処理で十分な拡散が出来ず、最表層にＳｎが残存してしまい、同じように耐摩耗性、ウィスカ性が悪化した。Ｓｎの残存量が０．０５μｍと多く、はんだ濡れ性も悪化した。
図１、２に、それぞれ実施例５及び比較例４に係る電子部品用金属材料のＳＴＥＭ（透過型電子顕微鏡）の断面観察写真を示す。
図３に、実施例４（ロット番号１）の下層の上側領域の酸素濃度の線分析結果及び分析方法の概要を示す。図４に、実施例４（ロット番号１）の下層の上側領域の酸素濃度の線分析結果を示す。図５に、実施例４（ロット番号２）の下層の上側領域の酸素濃度の線分析結果を示す。図６に、比較例４の下層の上側領域の酸素濃度の線分析結果を示す。
Examples 1 to 10 were electronic component metal materials excellent in all of high solder wettability, low whisker properties, and low adhesion wear properties.
In Comparative Examples 1 to 9, at least one of high solder wettability, low whisker property, and low adhesion wear was poor.
In Comparative Examples 1 and 2, Sn and In remained in the outermost layer due to insufficient heat treatment, adhesion wear increased, and the wear resistance was reduced. Moreover, whisker property deteriorated because Sn and In remained in the outermost layer. In Comparative Example 7, the Sn film was thick and could not be sufficiently diffused by the heat treatment, and Sn remained in the outermost layer, and the wear resistance and whisker properties were similarly deteriorated. The remaining amount of Sn was as large as 0.05 μm, and the solder wettability was also deteriorated.
1 and 2 show cross-sectional observation photographs of STEM (transmission electron microscope) of metal materials for electronic components according to Example 5 and Comparative Example 4, respectively.
FIG. 3 shows an outline of the results of the line analysis of the oxygen concentration in the upper region of the lower layer of Example 4 (lot number 1) and the analysis method. In FIG. 4, the line analysis result of the oxygen concentration of the upper side area | region of the lower layer of Example 4 (lot number 1) is shown. In FIG. 5, the line analysis result of the oxygen concentration of the upper side area | region of the lower layer of Example 4 (lot number 2) is shown. In FIG. 6, the line analysis result of the oxygen concentration of the upper side area | region of the lower layer of the comparative example 4 is shown.
Claims (14)
（i）Ａｇ及びＰｄからなる群であるＡ構成元素群から選択された１種又は２種、又は、
（ii）前記Ａ構成元素群と、Ｓｎ及びＩｎからなる群であるＢ構成元素群から選択された１種又は２種との合金
で構成された上層と、
をこの順に備え、
ＸＰＳ分析を行ったときに最表面から深さ１ｎｍまでの領域に単体のＳｎ又はＩｎが残存せず、
ＳＥＭによる３．５ｎｍ間隔の線分析を行ったときに前記下層側表面から前記上層側へ０．１μｍの厚み領域における酸素濃度が１０ｐｐｍ以下である電子部品用金属材料。 A base material, a lower layer composed of Ni,
(I) 1 type or 2 types selected from A group element group which is the group which consists of Ag and Pd, or
(Ii) an upper layer composed of an alloy of the A constituent element group and one or two selected from the B constituent element group which is a group consisting of Sn and In;
In this order,
When XPS analysis was performed, no single Sn or In remained in the region from the outermost surface to a depth of 1 nm,
A metal material for electronic parts having an oxygen concentration of 10 ppm or less in a thickness region of 0.1 μm from the lower surface to the upper layer when performing line analysis at an interval of 3.5 nm by SEM.
前記下層側表面から前記中層側へ０．１μｍの厚み領域における酸素濃度が１０ｐｐｍ以下である請求項１〜３のいずれか一項に記載の電子部品用金属材料。 Between the lower layer and the upper layer, further comprising an intermediate layer in which an alloy is composed of Ni and one or two selected from the B constituent element group which is a group consisting of Sn and In,
The metal material for an electronic component according to any one of claims 1 to 3, wherein an oxygen concentration in a thickness region of 0.1 µm from the lower surface to the middle layer is 10 ppm or less.
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| JP2020196910A (en) * | 2019-05-31 | 2020-12-10 | 古河電気工業株式会社 | Material for electric contact and its manufacturing method, connector terminal, connector and electronic component |
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