JP6831161B2 - Conductive materials for electronic components such as connectors and their manufacturing methods - Google Patents
Conductive materials for electronic components such as connectors and their manufacturing methods Download PDFInfo
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- 239000004020 conductor Substances 0.000 title claims description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000010410 layer Substances 0.000 claims description 101
- 238000007747 plating Methods 0.000 claims description 58
- 229910000765 intermetallic Inorganic materials 0.000 claims description 38
- 239000000463 material Substances 0.000 claims description 29
- 229910017482 Cu 6 Sn 5 Inorganic materials 0.000 claims description 20
- 229910020888 Sn-Cu Inorganic materials 0.000 claims description 20
- 229910019204 Sn—Cu Inorganic materials 0.000 claims description 20
- 229910052802 copper Inorganic materials 0.000 claims description 19
- 239000002344 surface layer Substances 0.000 claims description 19
- 229910045601 alloy Inorganic materials 0.000 claims description 11
- 239000000956 alloy Substances 0.000 claims description 11
- 229910052718 tin Inorganic materials 0.000 claims description 11
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 229910018100 Ni-Sn Inorganic materials 0.000 claims description 3
- 229910018532 Ni—Sn Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 239000010953 base metal Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 239000010949 copper Substances 0.000 description 35
- 238000012360 testing method Methods 0.000 description 32
- 229910000679 solder Inorganic materials 0.000 description 20
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 17
- 238000010438 heat treatment Methods 0.000 description 17
- 229910017755 Cu-Sn Inorganic materials 0.000 description 15
- 229910017927 Cu—Sn Inorganic materials 0.000 description 15
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- LFOIDLOIBZFWDO-UHFFFAOYSA-N 2-methoxy-6-[6-methoxy-4-[(3-phenylmethoxyphenyl)methoxy]-1-benzofuran-2-yl]imidazo[2,1-b][1,3,4]thiadiazole Chemical compound N1=C2SC(OC)=NN2C=C1C(OC1=CC(OC)=C2)=CC1=C2OCC(C=1)=CC=CC=1OCC1=CC=CC=C1 LFOIDLOIBZFWDO-UHFFFAOYSA-N 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
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Description
この発明は、使用時に篏合を伴うコネクタ等の電子部品用導電材料及びその製造方法に関する。 The present invention relates to a conductive material for electronic parts such as a connector that is combined when used, and a method for manufacturing the same.
自動車等の電気配線の接続に使用されるＳｎめっきを施したコネクタ等の電子部品用導電材料において、一般的に要求されることは次のとおりである。
・摩擦係数が低い（コネクタ挿入力の低減）
・良好なはんだ濡れ性を有する
・接触抵抗が安定している（接続信頼性が高い。例えば、１６０℃‐１２０ｈ 加熱後も安定）
・微摺動摩耗性に優れる
・ウイスカが発生し難い
The following are generally required for conductive materials for electronic components such as Sn-plated connectors used for connecting electrical wiring of automobiles and the like.
・ Low coefficient of friction (reduction of connector insertion force)
-Has good solder wettability-Stable contact resistance (high connection reliability. For example, stable even after heating at 160 ° C-120h)
・ Excellent fine sliding wear resistance ・ Whiskers are less likely to occur
具体的に説明すると、自動車や民生機器の接続に使用されるコネクタでは、コストや電気的特性の観点からＳｎめっきが多用されている。その中で、接続信頼性を確保し向上させるためには、Ｓｎめっきの厚さの増加や電気接点部の接圧の増加が有効であるが、こうした場合に、他方では、篏合時の挿入力の増加を招くことで作業性が低下することや、Ｓｎめっきの変形や掘り起しによる電気的接続の劣化が生じることなどが問題となっている。いずれも、主として最表面のＳｎ被覆層の問題として提起されている（特許文献１，２）。
Specifically, Sn plating is often used in connectors used for connecting automobiles and consumer devices from the viewpoint of cost and electrical characteristics. Among them, in order to secure and improve the connection reliability, it is effective to increase the thickness of Sn plating and the contact pressure of the electrical contact part, but in such a case, on the other hand, insertion at the time of integration. There are problems such as a decrease in workability due to an increase in force and a deterioration of electrical connection due to deformation of Sn plating and digging. Both have been raised mainly as problems of the outermost Sn coating layer (
加えて、Ｓｎめっき材料をコネクタとして用いるにあたり、「はんだ濡れ性が良好であること」、「接触抵抗が安定していること」は必須となる特性である。特に接触抵抗に関しては、微摺動摩耗（一般的なＳｎめっきにおいて、自動車等の振動によって引き起こされる摩耗）にて生じる酸化摩耗粉による接触抵抗上昇も解決すべき課題となる。 In addition, when using the Sn plating material as a connector, "good solder wettability" and "stable contact resistance" are indispensable characteristics. In particular, regarding contact resistance, an increase in contact resistance due to oxidative wear powder caused by fine sliding wear (wear caused by vibration of an automobile or the like in general Sn plating) is also an issue to be solved.
特許文献１は、Ｃｕ合金板条からなる母材Ａの表面に、Ｃｕ‐Ｓｎ合金被覆層ＹとＳｎ被覆層Ｘがこの順に形成された導電材料を提示するものであるが（図４）、次の通り問題があった。
（１）表面に露出したＣｕ‐Ｓｎ合金被覆層Ｙが酸化し、はんだ濡れ性が低下し、接触抵抗が上昇する。ちなみに、Ｓｎの酸化ならば濡れ性および接触抵抗に大きな影響を与えない。
（２）Ｃｕめっき（またはＣｕ材）とＳｎめっきの加熱によりＣｕ‐Ｓｎ金属間化合物を形成してＣｕ−Ｓｎ合金被覆層とするため、合金層及び表層のＳｎ被覆層の制御が非常に難しい。Ｓｎ被覆層が厚くなった場合、摩擦係数が上昇し、Ｓｎ被覆層が薄くなった場合、はんだが濡れず接触抵抗が上昇するためである。
(1) The Cu—Sn alloy coating layer Y exposed on the surface is oxidized, the solder wettability is lowered, and the contact resistance is increased. By the way, the oxidation of Sn does not have a great influence on the wettability and contact resistance.
(2) Since a Cu-Sn intermetallic compound is formed by heating Cu plating (or Cu material) and Sn plating to form a Cu-Sn alloy coating layer, it is very difficult to control the Sn coating layer of the alloy layer and the surface layer. .. This is because when the Sn coating layer becomes thick, the friction coefficient increases, and when the Sn coating layer becomes thin, the solder does not get wet and the contact resistance increases.
特許文献２は、銅または銅合金からなる基材１０上に、Ｃｕ‐Ｓｎ合金１２ａとＳｎ１２ｂが混在したＳｎ‐Ｃｕめっき層１２を形成するもので、最表面のＳｎ層１４は電気めっきにより形成されるが（図５）、次のような問題があった。
（１）Ｓｎが溶融凝固処理されておらず結晶粒界が多数存在することに加え、Ｓｎ‐Ｃｕめっき層が加熱処理されていないため、Ｓｎ‐Ｃｕめっき層内の合金状態が安定していない。そのため、経時変化および加熱によって、Ｓｎめっきの結晶粒界に沿って金属間化合物が成長し、それが最表面に達し、酸化する。結果として、はんだ濡れ性が低下し、接触抵抗が上昇する。 (1) Sn is not melt-solidified and has many grain boundaries, and the Sn—Cu plating layer is not heat-treated, so that the alloy state in the Sn—Cu plating layer is not stable. .. Therefore, due to aging and heating, the intermetallic compound grows along the grain boundaries of Sn plating, reaches the outermost surface, and oxidizes. As a result, the solder wettability decreases and the contact resistance increases.
この発明は、上記のような実情に鑑みて、ＣｕまたはＣｕ合金基材を母材としてその最表面にＳｎ表層を設けた電子部品用導電材料において、Ｓｎ表層が加熱や層環境の変化にもかかわらず安定して機能する電子部品用導電材料及びその製造方法を提供することを課題とした。 In view of the above circumstances, the present invention is a conductive material for electronic components in which a Cu or Cu alloy base material is used as a base material and a Sn surface layer is provided on the outermost surface thereof, and the Sn surface layer is subject to heating and changes in the layer environment. An object of the present invention is to provide a conductive material for electronic parts that functions stably regardless of the above and a method for producing the same.
上記の課題を解決するために、この発明は、鋭意研究を重ねた結果知見を得たことによるもので、ＣｕまたはＣｕ合金基材を母材として最表面にＳｎ表層を設けた電子部品用導電材料において、該表層がＳｎめっき層を一旦溶融し凝固してなるＳｎ単独の凝固層として形成され、その下地の下層は、ＳｎとＣｕの総量に対するＣｕの含有量が１０．０〜５４．５ａｔ％であり、ＳｎとＣｕ６Ｓｎ５金属間化合物が混在した層に形成してあって、さらに、母材と該混在層との間に拡散防止のＮｉ層を設けたことを特徴としている。 In order to solve the above problems, the present invention has been obtained as a result of intensive research, and is conductive for electronic parts having a Cu or Cu alloy base material as a base material and a Sn surface layer on the outermost surface. In the material, the surface layer is formed as a solidified layer of Sn alone formed by temporarily melting and solidifying the Sn plating layer, and the lower layer of the base layer has a Cu content of 10.0 to 54.5 at relative to the total amount of Sn and Cu. %, Which is formed in a layer in which Sn and a Cu 6 Sn 5 intermetallic compound are mixed, and further, a diffusion-preventing Ni layer is provided between the base material and the mixed layer.
また、この発明は、ＣｕまたはＣｕ合金基材を母材として最表面にＳｎ表層を設けた電子部品用導電材料の製造方法において、母材の上方部に層厚が０．３〜５．０μｍかつＳｎとＣｕの総量に対するＣｕの含有量が１０．０〜５４．５ａｔ％であるＳｎ‐Ｃｕめっきを施し、その上に層厚０．２〜０．８μｍのＳｎめっきを施した後、溶融し冷却により凝固させることによって、前記Ｓｎ‐Ｃｕめっき層をＣｕ６Ｓｎ５金属間化合物とＳｎが混在した層とするとともに、Ｓｎ溶融凝固層を前記Ｓｎ表層として形成することを特徴とする電子部品用導電材料の製造方法を提供するものである。 Further, the present invention relates to a method for producing a conductive material for electronic parts in which a Cu or Cu alloy base material is used as a base material and a Sn surface layer is provided on the outermost surface, and the layer thickness is 0.3 to 5.0 μm above the base material. Then, Sn-Cu plating in which the Cu content is 10.0 to 54.5 at% with respect to the total amount of Sn and Cu is applied, and Sn plating having a layer thickness of 0.2 to 0.8 μm is applied thereto, and then melted. An electronic component characterized in that the Sn-Cu plating layer is formed as a layer in which a Cu 6 Sn 5 intermetallic compound and Sn are mixed, and the Sn melt-solidified layer is formed as the Sn surface layer by solidifying by cooling. It provides a method for producing a conductive material for copper.
電子部品用導電材料及びその製造方法を上記のように構成したため、これによると、最表層がＳｎ溶融凝固単独層であって、酸化されてもＳｎ酸化物のみとなる。Ｓｎ酸化物はＣｕやＣｕ‐Ｓｎ系酸化物と比較して、電気比抵抗が小さい、高温環境下でも厚く成長し難い、等の特性を持ち、接触抵抗およびはんだ濡れ性に影響を与えにくく、それらの良好な状態が保たれる。また、最表層の下地層は、Ｃｕ６Ｓｎ５金属間化合物とＳｎとのみで構成され、リフロー処理後であり、２００℃以下の使用環境を想定した場合、状態が変化しない。更に、Ｃｕ６Ｓｎ５金属間化合物の硬度がＳｎと比較して高いため、最表層のＳｎ溶融凝固単独層の下地として支持が確実であり、これで最表層を薄くすることが許容される結果、篏合時の摩擦係数を低下できる。 Since the conductive material for electronic parts and the method for producing the same are configured as described above, according to this, the outermost layer is a Sn melt-solidified single layer, and even if it is oxidized, only Sn oxide is formed. Compared with Cu and Cu-Sn oxides, Sn oxides have characteristics such as low electrical resistivity, thick growth even in a high temperature environment, and are less likely to affect contact resistance and solder wettability. Their good condition is maintained. Further, the underlying layer of the outermost layer is composed of only Cu 6 Sn 5 intermetallic compound and Sn, and after the reflow treatment, the state does not change when the usage environment of 200 ° C. or lower is assumed. Further, since the hardness of the Cu 6 Sn 5 intermetallic compound is higher than that of Sn, it is surely supported as a base for the Sn melt-solidification single layer of the outermost layer, and it is permissible to make the outermost layer thinner. , The coefficient of friction at the time of merging can be reduced.
特に、請求項３に関しては、溶融加熱が、「Ｓｎめっきを溶融凝固層とすること」のほかに、「Ｓｎ‐Ｃｕめっき層中の合金の状態を安定させること」も目的としている。これについては、Ｓｎ‐Ｃｕめっき層を溶融加熱処理しない場合、Ｓｎ‐Ｃｕめっき層中には「Ｃｕ」，「Ｓｎ」，「Ｃｕ３Ｓｎ金属間化合物」，「Ｃｕ６Ｓｎ５金属間化合物」の４種類が存在することになるが、溶融加熱処理を行った場合、急速な金属の拡散反応が生じ、「Ｓｎ」と「Ｃｕ６Ｓｎ５金属間化合物」の２種類のみの安定した構成が得られる。 In particular, with respect to claim 3, the purpose of melt heating is not only to "make Sn plating a melt solidified layer" but also to "stabilize the state of the alloy in the Sn—Cu plating layer". Regarding this, when the Sn-Cu plating layer is not melt-heated, "Cu", "Sn", "Cu 3 Sn intermetallic compound", and "Cu 6 Sn 5 intermetallic compound" are contained in the Sn-Cu plating layer. However, when the melt heat treatment is performed, a rapid metal diffusion reaction occurs, and only two types of "Sn" and "Cu 6 Sn 5 intermetallic compound" have a stable configuration. can get.
以上説明したように、この発明によれば、ＣｕまたはＣｕ合金基材を母材としてその最表面にＳｎ表層を設けた電子部品用導電材料について、最表面が酸化の影響を受けることが少なく、良好なはんだ濡れ性および接触抵抗を確保でき、また、Ｓｎ最表層が下地の硬いＣｕ６Ｓｎ５金属間化合物によって支持され、これで安定化するためＳｎ最表層を薄くして摩擦係数の低下を図ることができ、また、溶融凝固により最終表面が平滑化するので、これでも摩擦係数の低減が図られるなど、Ｓｎ表層の安定した構成を得る簡単な方法によっても、数々の優れた特性を発揮することができる。 As described above, according to the present invention, the outermost surface of a conductive material for electronic parts, which is made of a Cu or Cu alloy base material as a base material and has a Sn surface layer on the outermost surface, is less affected by oxidation. Good solder wettability and contact resistance can be ensured, and the Sn outermost layer is supported by a hard underlying Cu 6 Sn 5 intermetallic compound, which stabilizes the Sn outermost layer by thinning it to reduce the friction coefficient. In addition, since the final surface is smoothed by melt solidification, the friction coefficient can still be reduced, and many excellent characteristics are exhibited even by a simple method of obtaining a stable structure of the Sn surface layer. can do.
この発明においては、ＣｕまたはＣｕ合金基材を母材１としてその最表面にＳｎ表層を設けた電子部品用導電材料において、該表層のＳｎめっき層を一旦溶融してなるＳｎ単独の凝固層５（層厚０．２〜０．８μｍ）として形成し、その下層については、Ｓｎ（４‐１）とＣｕ６Ｓｎ５金属間化合物（４‐２）が混在した層（Ｃｕ含有率として１０．０〜５４．５ａｔ％ 層厚０．３〜５．０μｍ）を形成したものであって、さらに、母材１と混在層との間には、Ｎｉ層２（層厚０．２〜３．０μｍ）とその上層としてのＣｕ‐Ｎｉ‐Ｓｎ合金層３が設けられる。
In the present invention, in a conductive material for electronic parts in which a Cu or Cu alloy base material is used as a
実施例の図面は、電子部品用導電材料とその製造方法の発明とが共に具備する構成となっており，図３につき合わせて説明する。いずれにしても、母材１の上に幾つかのめっきが順次施されて製造される。なお、この層形成の前提となるめっき工程は次の通りである。
（１）アルカリ電解脱脂
↓（水洗い）
（２）酸活性
↓（水洗い）
（３）Ｎｉめっき
↓（水洗い）
（４）Ｓｎ‐Ｃｕめっき
↓（水洗い）
（５）Ｓｎめっき
↓（水洗い）
（６）乾燥
↓
（７）リフロー（溶融凝固）
※（１）（２）は前処理
The drawings of the examples have a configuration in which the conductive material for electronic parts and the invention of the manufacturing method thereof are both provided, and will be described together with reference to FIG. In any case, it is manufactured by sequentially applying several platings on the
(1) Alkaline electrolytic degreasing ↓ (washing with water)
(2) Acid activity ↓ (washing with water)
(3) Ni plating ↓ (washing with water)
(4) Sn-Cu plating ↓ (washing with water)
(5) Sn plating ↓ (washing with water)
(6) Drying ↓
(7) Reflow (molten solidification)
* (1) and (2) are pretreatment
次に、図３に基づいて各層を説明する。
「Ｓｎ溶融凝固層５」（最表層）について
（１）Ｓｎの単独めっきからなる。金属間化合物は存在しない。最表層がＳｎ単独層であれば酸化物はＳｎ酸化物のみとなる。Ｓｎ酸化物は、接触抵抗およびはんだ濡れ性に影響を与えにくく、接触抵抗およびはんだ濡れ性の良好な状態が保たれる。
ちなみに、最表層にＣｕまたはＮｉ（の酸化物）が存在した場合、はんだ濡れ性が低下し、接触抵抗が上昇する。
（２）Ｓｎ溶融凝固層５は、Ｓｎをめっき溶融させることで形成される。
（３）溶融凝固により最終表面が平滑化する結果、摩擦係数の低減が図られる。
（４）しかし、Ｓｎめっきの厚さが０．２μｍ未満の場合、経時変化および加熱によって最表層にＣｕ‐Ｓｎ金属間化合物が一定の割合で露出する。その結果Ｃｕ‐Ｓｎ金属間化合物の酸化によってはんだ濡れ性が悪くなる。
（５）Ｓｎめっきの厚さが０．８μｍを超える場合、Ｓｎ層が厚く摩擦係数が高くなる。
Next, each layer will be described with reference to FIG.
About "Sn
By the way, when Cu or Ni (oxide) is present on the outermost surface layer, the solder wettability decreases and the contact resistance increases.
(2) The Sn
(3) As a result of smoothing the final surface by melt solidification, the friction coefficient can be reduced.
(4) However, when the Sn plating thickness is less than 0.2 μm, the Cu-Sn intermetallic compound is exposed to the outermost layer at a constant ratio due to aging and heating. As a result, the solder wettability deteriorates due to the oxidation of the Cu-Sn intermetallic compound.
(5) When the thickness of Sn plating exceeds 0.8 μm, the Sn layer becomes thick and the friction coefficient becomes high.
「Ｓｎ（４‐１）と、Ｃｕ６Ｓｎ５金属間化合物（４‐２）が混在した層」について
（１）混在層は、Ｃｕ含有量がＣｕ６Ｓｎ５金属間化合物の割合である５４．５ａｔ％より少ない場合、ＳｎとＣｕ６Ｓｎ５金属間化合物のみが共存する状態となる。Ｃｕ含有量がＣｕ６Ｓｎ５金属間化合物の割合である５４．５ａｔ％を超える場合、Ｃｕ３Ｓｎ金属間化合物または単独Ｃｕが存在することとなる。経時変化および加熱環境を考えた場合、Ｓｎ単独層である最表層のＳｎ溶融凝固層５と混在層中のＣｕ３Ｓｎ金属間化合物または単独Ｃｕが反応し、最表層にＣｕ‐Ｓｎ金属間化合物が生成され、はんだ濡れ性が低下し、接触抵抗が上昇する。つまり、ＣｕがＣｕ６Ｓｎ５金属間化合物の割合よりも多い環境では、Ｓｎ単独層は存在しえない。最表層にＳｎ単独層を残存させることを前提に考えた場合、Ｃｕ６Ｓｎ５金属間化合物の割合に対し、Ｓｎ過多な環境が必要である。
Regarding "a layer in which Sn (4-1) and a Cu 6 Sn 5 intermetallic compound (4-2) are mixed" (1) The mixed layer has a Cu content of the ratio of the Cu 6 Sn 5 intermetallic compound 54. If it is less than .5 at%, only Sn and Cu 6 Sn 5 intermetallic compound coexist. When the Cu content exceeds 54.5 at%, which is the ratio of the Cu 6 Sn 5 intermetallic compound, the Cu 3 Sn 5 intermetallic compound or the single Cu is present. Considering the change over time and the heating environment, the Sn melt-solidified
（２）Ｃｕ含有量が１０．０％未満の場合、生成されるＣｕ６Ｓｎ５金属間化合物の量が十分ではなく、下層のＮｉと混在層内のＳｎによって生じた金属間化合物が最表層まで達し、はんだ濡れ性が低下し、接触抵抗が上昇する。Ｓｎ‐Ｃｕめっきにて処理を行った場合、混在層はＣｕ‐Ｓｎ金属間化合物だけでなく、Ｓｎ単独となる箇所も存在するためである。Ｃｕ‐Ｓｎ金属間化合物は、Ｎｉの最表層への拡散防止層という役割も担っている。 (2) When the Cu content is less than 10.0%, the amount of Cu 6 Sn 5 intermetallic compound produced is not sufficient, and the intermetallic compound generated by Ni in the lower layer and Sn in the mixed layer is the outermost layer. The solder wettability is reduced and the contact resistance is increased. This is because when the treatment is performed by Sn-Cu plating, the mixed layer includes not only the Cu-Sn intermetallic compound but also Sn alone. The Cu-Sn intermetallic compound also plays a role of a diffusion prevention layer for the outermost layer of Ni.
（３）混在層は、「Ｃｕめっき→Ｓｎめっき→リフロー」により形成するのではなく、「Ｓｎ‐Ｃｕめっき→リフロー」にて形成する。前者の場合、ＣｕとＳｎの界面からＣｕ‐Ｓｎ金属間化合物が生成されるため、表層に目的とする量のＳｎめっきを残存させることは非常に難しい。それはＳｎとＣｕの量および加熱条件を細かく制御する必要があるためである。更に、リフロー処理によって表層に残存するＳｎ層を正確に制御したとしても、リフロー後にＣｕ層が残存している場合、経時変化および加熱によってＣｕ‐Ｓｎ金属間化合物が成長し、Ｓｎ層が消失する。電気めっきでめっき処理を行う上で、製品全域においてそのバランスを制御することは不可能に近い。 (3) The mixed layer is not formed by "Cu plating-> Sn plating-> reflow", but is formed by "Sn-Cu plating-> reflow". In the former case, since a Cu-Sn intermetallic compound is generated from the interface between Cu and Sn, it is very difficult to leave the desired amount of Sn plating on the surface layer. This is because it is necessary to finely control the amounts of Sn and Cu and the heating conditions. Further, even if the Sn layer remaining on the surface layer is accurately controlled by the reflow treatment, if the Cu layer remains after the reflow, the Cu-Sn intermetallic compound grows due to aging and heating, and the Sn layer disappears. .. It is almost impossible to control the balance of the entire product when performing the plating process by electroplating.
Ｓｎ‐Ｃｕめっきとした場合、ＳｎとＣｕの比率やＳｎ‐Ｃｕめっきの厚さにバラつきが生じた際にも、ＳｎとＣｕを分散させた層としてめっきを行うため、Ｃｕ‐Ｓｎ金属間化合物は混在層中に均等に配置される。表層のＳｎめっきがそのままの厚みで残存することになり、制御が大変容易である。 In the case of Sn-Cu plating, even if the ratio of Sn and Cu and the thickness of Sn-Cu plating vary, plating is performed as a layer in which Sn and Cu are dispersed, so that a Cu-Sn intermetallic compound is used. Are evenly distributed in the mixed layer. The Sn plating on the surface layer remains with the same thickness, which is very easy to control.
Ｓｎ‐Ｃｕめっきの厚さが０．３μｍ未満の場合、生成されるＣｕ‐Ｓｎ金属間化合物の量が十分ではなく、下層のＮｉと混在層内のＳｎによって生じた金属間化合物が最表層まで達し、接触抵抗が上昇しはんだ濡れ性が低下する。
Ｓｎ‐Ｃｕめっきの厚さが５．０μｍを超える場合、生産効率が悪い。加えて、その金属間化合物は硬度が高いため材料としての加工性が低下する。
When the thickness of Sn-Cu plating is less than 0.3 μm, the amount of Cu-Sn intermetallic compound produced is not sufficient, and the intermetallic compound generated by Ni in the lower layer and Sn in the mixed layer reaches the outermost layer. When it reaches, the contact resistance increases and the solder wettability decreases.
If the thickness of Sn-Cu plating exceeds 5.0 μm, the production efficiency is poor. In addition, since the intermetallic compound has a high hardness, the processability as a material is lowered.
「Ｎｉ層２」について
Ｎｉめっきの厚さが０．２μｍ未満の場合、拡散防止層としての役割を果たせない。Ｎｉめっきの厚さが３．０μｍを超える場合、生産効率が悪い。加えて硬度が高いため、材料としての加工性が低下する。
About "
図１および図２は、被膜構成の例示となるもので、実施例１〜実施例７は、本発明の要件を満たす被膜構成である。 1 and 2 are examples of a coating structure, and Examples 1 to 7 are coating configurations that satisfy the requirements of the present invention.
図１に示す試験片作成にあたり、母材にはりん青銅（Ｃ５２１０）を用いた。アルカリ電解脱脂は３０秒、酸活性は５Ｖｏｌ％硫酸を用い３０秒とし、Ｎｉめっき、Ｓｎ‐Ｃｕめっき、Ｓｎめっきは目的とする厚さおよび金属比率が得られるように電流値および時間を調整した。リフロー処理は３００℃にて５秒間とした。また、各工程間の水洗は１０秒とした。 Phosphor bronze (C5210) was used as the base material in preparing the test piece shown in FIG. Alkaline electrolytic degreasing was performed for 30 seconds, acid activity was set to 30 seconds using 5 Vol% sulfuric acid, and the current value and time were adjusted for Ni plating, Sn-Cu plating, and Sn plating so that the desired thickness and metal ratio could be obtained. .. The reflow treatment was performed at 300 ° C. for 5 seconds. In addition, washing with water between each step was set to 10 seconds.
図２に示すように、実施例１〜実施例７では、摩擦係数、はんだ濡れ性、接触抵抗のいずれについても優れた特性が得られた。また、実施例２および実施例６において、微摺動摩耗特性においても、一般的に用いられている被膜構成である比較例１に対し、接触抵抗が１０ｍΩを超えるまでの摺動回数が倍程度となっており、良好な特性が得られたことを示す。 As shown in FIG. 2, in Examples 1 to 7, excellent characteristics were obtained in terms of friction coefficient, solder wettability, and contact resistance. Further, in Examples 2 and 6, the number of times of sliding until the contact resistance exceeds 10 mΩ is about twice as much as that of Comparative Example 1, which is a generally used coating structure, in terms of fine sliding wear characteristics. It indicates that good characteristics were obtained.
一方、比較例１では、最表層のＳｎめっきが厚く、摩擦係数が高くなった。また、熱処理４８０ｈでは、Ｓｎ中へのＮｉ拡散防止のバリア層が存在しないため、接触抵抗が高くなった。
比較例２では、ブランクは最表層に残存するＳｎめっきの厚さを制御しているため、摩擦係数、はんだ濡れ性、接触抵抗について良好な結果が得られているものの、熱処理後に接触抵抗が高くなった。
比較例３では、めっき後に溶融凝固処理を実施していないため、経時変化および加熱によって、はんだ濡れ性が悪くなり熱処理４８０ｈ後の接触抵抗が高くなった。
On the other hand, in Comparative Example 1, the Sn plating on the outermost layer was thick and the friction coefficient was high. Further, in the heat treatment 480h, the contact resistance became high because the barrier layer for preventing the diffusion of Ni into Sn did not exist.
In Comparative Example 2, since the blank controls the thickness of the Sn plating remaining on the outermost layer, good results are obtained in terms of friction coefficient, solder wettability, and contact resistance, but the contact resistance is high after the heat treatment. became.
In Comparative Example 3, since the melt solidification treatment was not performed after plating, the solder wettability deteriorated due to aging and heating, and the contact resistance after 480 hours of heat treatment increased.
比較例４では、最表層のＳｎめっきが薄く、はんだ濡れ性が悪くなった。
比較例５では、最表層のＳｎめっきが厚く、摩擦係数が高くなった。
比較例６では、Ｓｎ‐Ｃｕめっきが薄く、熱処理後の接触抵抗が高くなった。
比較例７では、Ｎｉめっきが薄く、熱処理４８０ｈ後の接触抵抗が高くなった。
比較例８では、Ｓｎ‐Ｃｕめっき中のＣｕ含有率が低く、熱処理後の接触抵抗が高くなった。
比較例９では、Ｓｎ‐Ｃｕめっきの中のＣｕ含有率が高く、はんだ濡れ性が悪くなり接触抵抗が高くなった。
In Comparative Example 4, the Sn plating on the outermost layer was thin, and the solder wettability was deteriorated.
In Comparative Example 5, the Sn plating on the outermost layer was thick and the friction coefficient was high.
In Comparative Example 6, the Sn—Cu plating was thin and the contact resistance after the heat treatment was high.
In Comparative Example 7, the Ni plating was thin and the contact resistance after 480 hours of heat treatment was high.
In Comparative Example 8, the Cu content in Sn-Cu plating was low, and the contact resistance after the heat treatment was high.
In Comparative Example 9, the Cu content in the Sn-Cu plating was high, the solder wettability was poor, and the contact resistance was high.
以上のような表式図中の試験片に対する各種の測定方法については、次の通りである。 The various measurement methods for the test pieces in the above-mentioned schematic diagram are as follows.
＜めっき厚測定方法＞
集束イオンビーム加工観察装置 ＪＩＢ-４０００(日本電子（株）)を用いて試験片を板厚方向に切断し、露出した断面を付属の走査イオン顕微鏡により１００００倍で観察した。
＜合金層中のＣｕ含有量測定方法＞
Ｓｎめっき前の試験片に対し、エネルギー分散型Ｘ線分析装置ＪＥＤ-２３００(日本電子（株））を用いて定量分析を実施した。
＜摩擦係数測定試験＞
平板状試験片（雄端子としての試験片）および内径φ１ｍｍの半球状加工を施したインデント付き試験片（雌端子としての試験片）を用いて評価を実施した。まず、平板状試験片を水平なステージ上に固定し、その試験片にインデント付き試験片のインデント部が接触するよう、上方にインデント付き試験片を設置した。続いて、インデント試験片に３００ｇｆの荷重をかけて平板状試験片に押し付けた状態で、平板状試験片を固定したステージを水平方向に８０ｍｍ／ｍｉｎの速度で移動させ、摺動距離２０ｍｍまでの平均摩擦力を測定した。測定した摩擦力より摩擦係数を算出した。
＜はんだ濡れ性試験＞
平板状試験片に対し打ち抜き加工を行い、３ｍｍ×１５ｍｍの試験片を作成した。試験装置はソルダーチッカＳＡＴ５２００型（レスカ（株））を用い、ＪＩＳＣ６００６８‐２‐５４に基づいて試験を実施した。
＜接触抵抗測定試験＞
平板状試験片に対し、熱処理を行っていないもの、大気中にて１６０℃×１２０ｈの熱処理を行ったもの、大気中にて１６０℃×４８０ｈの熱処理を行ったもの、を作成した。試験装置は、電気接点シミュレータＣＲＳ‐１１２‐ＭＵ型（（株）山崎精機研究所）を用いて評価を実施した。四端子法により、荷重１００ｇｆの条件で測定した。
＜微摺動摩耗試験＞
精密摺動試験装置ＣＲＳ−Ｇ２０５０型（（株）山崎精機研究所）を用い、平板状試験片（雄端子としての試験片）および内径φ１ｍｍの半球状加工を施したインデント付き試験片（雌端子としての試験片）を用いて評価を実施した。荷重３Ｎ 振幅０．０５ｍｍ、速度０．１ｍｍ／ｓｅｃとして、１００００往復まで繰り返し振動させた際の接触抵抗の変化を四端子法により測定した。
<Plating thickness measurement method>
The test piece was cut in the plate thickness direction using a focused ion beam processing observation device JIB-4000 (JEOL Ltd.), and the exposed cross section was observed at 10000 times with the attached scanning ion microscope.
<Method for measuring Cu content in alloy layer>
Quantitative analysis was performed on the test piece before Sn plating using the energy dispersive X-ray analyzer JED-2300 (JEOL Ltd.).
<Friction coefficient measurement test>
Evaluation was carried out using a flat plate-shaped test piece (test piece as a male terminal) and an indented test piece (test piece as a female terminal) having a hemispherical shape with an inner diameter of φ1 mm. First, the flat plate-shaped test piece was fixed on a horizontal stage, and the indented test piece was installed above the test piece so that the indented portion of the indented test piece was in contact with the test piece. Subsequently, with a load of 300 gf applied to the indented test piece and pressed against the flat plate-shaped test piece, the stage on which the flat plate-shaped test piece is fixed is moved horizontally at a speed of 80 mm / min to a sliding distance of up to 20 mm. The average frictional force was measured. The friction coefficient was calculated from the measured frictional force.
<Solder wettability test>
A flat plate-shaped test piece was punched to prepare a 3 mm × 15 mm test piece. The test apparatus was Solder Chica SAT5200 (Reska Co., Ltd.), and the test was carried out based on JISC6000068-2-54.
<Contact resistance measurement test>
The flat plate-shaped test piece was prepared, one that was not heat-treated, one that was heat-treated at 160 ° C. × 120 h in the air, and one that was heat-treated at 160 ° C. × 480 h in the air. The test device was evaluated using an electrical contact simulator CRS-112-MU type (Yamasaki Seiki Laboratory Co., Ltd.). It was measured by the four-terminal method under the condition of a load of 100 gf.
<Slight sliding wear test>
Using the precision sliding test device CRS-G2050 (Yamasaki Seiki Laboratory Co., Ltd.), a flat plate-shaped test piece (test piece as a male terminal) and an indented test piece (female terminal) with an inner diameter of φ1 mm. The evaluation was carried out using the test piece). The change in contact resistance when repeatedly vibrated up to 10,000 reciprocations was measured by the four-terminal method under a load of 3N amplitude of 0.05 mm and a speed of 0.1 mm / sec.
１ 母材
２ Ｎｉ層
３ Ｃｕ‐Ｎｉ‐Ｓｎ合金層
４ 混在層
４‐１ Ｓｎ
４‐２ Ｃｕ６Ｓｎ５金属間化合物
５ Ｓｎ溶融凝固層
1
4-2 Cu 6 Sn 5 Intermetallic compound 5 Sn Molten solidification layer
Claims (3)
前記混在層は、断面視にて、Ｃｕ ６ Ｓｎ ５ 金属間化合物と、Ｃｕ ６ Ｓｎ ５ 金属間化合物に囲まれたＳｎと、を含む、
ことを特徴とする電子部品用導電材料。 In a conductive material for electronic parts in which a Cu or Cu alloy base material is used as a base material and a Sn surface layer is provided on the outermost surface, Sn alone having a thickness of 0.2 to 0.8 μm is formed by temporarily melting the Sn plating layer on the surface layer. The lower layer formed as a solidified layer has a Cu content of 10.0 to 54.5 at% with respect to the total amount of Sn and Cu, and a layer thickness of a mixture of Sn and Cu 6 Sn 5 intermetallic compound is 0. It is formed as a mixed layer of 3 to 5.0 μm, and a Ni layer having a layer thickness of 0.2 to 3.0 μm is further provided between the base material and the mixed layer .
The mixed layer contains, in cross-sectional view, a Cu 6 Sn 5 intermetallic compound and a Sn surrounded by a Cu 6 Sn 5 intermetallic compound.
A conductive material for electronic components.
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