JP2003211283A - Lead-free solder material - Google Patents

Lead-free solder material

Info

Publication number
JP2003211283A
JP2003211283A JP2002012446A JP2002012446A JP2003211283A JP 2003211283 A JP2003211283 A JP 2003211283A JP 2002012446 A JP2002012446 A JP 2002012446A JP 2002012446 A JP2002012446 A JP 2002012446A JP 2003211283 A JP2003211283 A JP 2003211283A
Authority
JP
Japan
Prior art keywords
alloy
phase
lead
composition
eutectic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP2002012446A
Other languages
Japanese (ja)
Inventor
Toshio Narita
敏夫 成田
Junichi Tanaka
順一 田中
Daiki Kobayashi
大樹 小林
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Japan Science and Technology Agency
Original Assignee
Japan Science and Technology Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Japan Science and Technology Corp filed Critical Japan Science and Technology Corp
Priority to JP2002012446A priority Critical patent/JP2003211283A/en
Priority to TW92101105A priority patent/TW200302147A/en
Priority to PCT/JP2003/000470 priority patent/WO2003061897A1/en
Publication of JP2003211283A publication Critical patent/JP2003211283A/en
Pending legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
    • B23K35/262—Sn as the principal constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
    • B23K35/264—Bi as the principal constituent

Abstract

<P>PROBLEM TO BE SOLVED: To provide an Sn-Ag binary lead-free solder alloy material which is made finer in the solidified structure not depending upon a cooling rate during packaging and is reduced in the consumption of Ag by subjecting a rough and large primary crystal β-Sn phase to grain refining. <P>SOLUTION: Al is added to the Sn-Ag binary alloy to induce crystal formation in a manner of multiple acts by solidification accompanied by heteronucleation, by which the grain refining of the material structure is performed. As the more specific composition, 0.1 to 5 wt.% Al is incorporated into the alloy consisting of 1 to 5 wt.% Ag and the balance Sn. Further, 40 to 60 wt.% Bi or 40 to 50 wt.% In is incorporated in addition to the above composition into the alloy. The above composition is otherwise formed of 0.1 to 3 wt.% Cu and further, 0.5 to 5 wt.% one or 2 kinds or more of the elements selected from In, Bi, Ni, Au, Sb, Zn, Mg, La, and Ce are incorporated into the alloy. In the structure of Figure (a), the primary crystal β-Sn phase is made finer in the grains and the gaps thereof are packed with fine eutectic structures but in a comparison example not containing Al of (b) and (c), the rough and large primary crystal β-Sn phase occupies much thereof. <P>COPYRIGHT: (C)2003,JPO

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【発明が属する技術分野】エレクトロニクス産業におけ
る電気・電子部品の回路接続や金属部材の接合に用いる
軟ろう材、いわゆるはんだ材料であって、特に鉛を排し
たいわゆる鉛フリーはんだ材料に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a so-called solder material, which is a soft brazing material used for circuit connection of electric / electronic parts and joining of metal members in the electronics industry, and more particularly to a so-called lead-free solder material from which lead is eliminated.

【０００２】[0002]

【従来の技術】はんだ材料は、エレクトロニクス産業に
おける電子部品の接続・固定などの実装を始めとし、電
気的接続、機械的固着手段として広く用いられている
が、従来からはんだとして用いられているＳｎ−Ｐｂ系
合金は、その含有する鉛のため作業環境はもとより、使
用済みの製品の廃棄・回収に際して毒性が問題とされ、
近年、これらの環境に対する負荷を低減或いは解消する
ため、これらの代替材料として鉛を含まない、いわゆる
鉛フリーはんだ材料の開発が進められている。これらの
はんだ材料は、エレクトロニクス実装時にその対象とす
る電子部品やレジスト材などへ熱損傷を生じない、或い
は樹脂類を含有する基板などの歪を生じないことなどが
要求され、このためＳｎ−Ｐｂ系はんだと同様に低融点
であること、接続・固定部位の強度、信頼性などが求め
られる。特に、最近のエレクトロニクス実装では、部品
などの微細化、高密度表面実装化の進展に伴い、これら
の要請は一層厳しいものとなっている。このため、新た
な鉛フリーはんだ材料では、これらの条件に適合する融
点降下と結晶組織微細化を狙って、Ｓｎを主成分とし、
Ａｇ及びさらに他の成分元素を加えた共晶合金系の組成
が選択される。これらのはんだ材料として、Ｓｎ−Ａｇ
共晶及び更にこれらにＣｕ、Ｂｉ、Ｉｎを個別に或いは
組み合わせて添加して、融点を降下させ、機械的特性な
どを向上したものが日米欧各国で報告されている。（特
開２００-９４１８１号公報、特開平７-５１８８３号公
報など参照。）2. Description of the Related Art A solder material has been widely used as a means for electrical connection and mechanical fixing, such as mounting and connecting electronic parts in the electronics industry. -Pb-based alloys contain lead, which poses a toxicity problem not only in the working environment but also in the disposal and recovery of used products.
In recent years, in order to reduce or eliminate the load on the environment, development of so-called lead-free solder material containing no lead as an alternative material for these materials has been under way. These solder materials are required not to cause heat damage to the electronic components, resist materials, etc. targeted for the electronic mounting, or to prevent distortion of a substrate containing resins, etc., and therefore Sn-Pb. Similar to solders, it must have a low melting point and the strength and reliability of the connecting / fixing parts. Particularly, in recent electronic packaging, these requirements have become more severe with the progress of miniaturization of parts and the like and high density surface mounting. Therefore, in the new lead-free solder material, Sn is the main component with the aim of lowering the melting point and refining the crystal structure that meet these conditions,
The composition of the eutectic alloy system containing Ag and other constituent elements is selected. As these solder materials, Sn-Ag
It has been reported in Japan, the United States and Europe that the eutectic and further Cu, Bi and In are added individually or in combination to lower the melting point and improve the mechanical properties. (See JP-A-200-94181 and JP-A-7-51883.)

【０００３】しかし、これらのＳｎ系はんだ合金は、一
般に電子部品の実装におけるはんだ付けに適用すると、
共晶組成であるにもかかわらず、実際に形成された金属
組織は微細な共晶組織となり難く、通常粗大な初晶β―
Ｓｎ相が発達してこれと共晶相との２相混合組織とな
り、材料強度などの機械的特性の低下を来たすことが問
題となっている。また、このような状況下で、有力な代
替はんだ材料として実用化が進められているＳｎ-３．
０Ａｇ-０．５Cu合金などにおいても、高価なＡｇの含
有量が多く、原価コストが著しく高くなることが避けら
れないため、含有Ａｇ量の低減が望まれているが、これ
らの組成を変えて当初の共晶組成を外れると、意図した
微細な共晶組織が得られず、所期の機械的特性が得られ
ない。However, when these Sn-based solder alloys are generally applied to soldering in mounting electronic parts,
Despite the eutectic composition, the actually formed metallographic structure is unlikely to be a fine eutectic structure and is usually coarse primary β-
There is a problem that the Sn phase develops to form a two-phase mixed structure of the Sn phase and the eutectic phase, resulting in deterioration of mechanical properties such as material strength. In addition, under such circumstances, Sn-3.
Even in 0Ag-0.5Cu alloy and the like, it is unavoidable that the content of expensive Ag is large and the cost cost becomes significantly high. Therefore, it is desired to reduce the content of Ag. If the initial eutectic composition is deviated, the intended fine eutectic structure cannot be obtained, and desired mechanical properties cannot be obtained.

【０００４】そしてこのような事情から、これらのはん
だ合金材料を電子部品の実装に適用するに際しては、フ
ロー法、リフロー法いずれにおいても搭載した電子部品
や基板も含めて加熱され、その後冷却若しくは放冷され
る過程ではんだ材料の溶解・凝固が進行するが、この冷
却速度は実装部品や工程によって著しく異なり、このた
め、実装条件下の冷却速度ではいずれも目論見とおりの
共晶組織が得られず、得られた金属組織は必ずしも均質
一様な組織とならないため、品質も安定しない。Under these circumstances, when applying these solder alloy materials to the mounting of electronic parts, both the flow method and the reflow method are heated including the mounted electronic parts and substrate, and then cooled or released. Although the melting and solidification of the solder material progresses during the cooling process, this cooling rate varies significantly depending on the mounting components and process, and therefore the eutectic structure as intended cannot be obtained at any cooling rate under the mounting conditions. The quality of the obtained metal structure is not stable because it does not always have a uniform structure.

【０００５】[0005]

【発明が解決しようとする課題】Ｓｎ系鉛フリーはんだ
材料において、材料組織の微細化とそれによる機械的特
性の向上、特に、実装条件下などの冷却速度に影響され
ない、微細材料組織の形成と機械的特性の向上を図ると
共に、Ａｇ含有量を低減した亜共晶組成を含む広い成分
組成範囲における、機械的特性を維持・向上する。In the Sn-based lead-free solder material, the fineness of the material structure and the improvement of the mechanical properties due to it, in particular, the formation of the fine material structure which is not affected by the cooling rate under the mounting conditions and the like. The mechanical properties are improved, and the mechanical properties are maintained / improved in a wide range of component compositions including a hypoeutectic composition with a reduced Ag content.

【０００６】[0006]

【課題を解決するための手段】本発明は、Ｓｎ−Ａｇ二
元系合金において、Ａｌを添加し、異質核生成を伴う凝
固によって、材料組織を微細化した鉛フリーはんだ材料
であり、さらに上記Ａｇを１wt％〜５wt％、同じくＣ
ｕ：0.1〜３wt％、残部Ｓｎとした合金に、Ａｌ：0.1〜
５wt％含有せしめてなる鉛フリーはんだ合金材料であ
る。また、上記組成に加え、Ｂｉ：４０〜６０wt％又は
Ｉｎ：４０〜５０wt％を含有せしめ、或いは、さらに上
記組成において、Ｃｕ：0.1〜３wt％とし、さらにＩ
ｎ，Ｂｉ，Ｎｉ，Ａｕ，Ｓｂ，Ｚｎ，Ｍｇ，Ｌａ，Ｃｅ
から選択した元素のいずれか1乃至２以上を0.1〜５ｗｔ
％ 含有せしめてなる鉛フリーはんだ材料である。The present invention is a lead-free solder material in which a Sn—Ag binary alloy is added with Al and the material structure is refined by solidification accompanied by heterogeneous nucleation. 1 wt% to 5 wt% Ag, also C
u: 0.1 to 3 wt%, with the balance being Sn, Al: 0.1 to
This is a lead-free solder alloy material containing 5 wt%. In addition to the above composition, Bi: 40 to 60 wt% or In: 40 to 50 wt% is added, or in the above composition, Cu: 0.1 to 3 wt%, and I:
n, Bi, Ni, Au, Sb, Zn, Mg, La, Ce
0.1 to 5 wt% of any one or more of the elements selected from
% This is a lead-free solder material that contains all the elements.

【０００７】本発明の合金組成は、粗大な初晶β―Ｓｎ
相が晶出する範囲にあるが、Ａｌが少量添加されている
ことにより、冷却速度に影響されず、はんだ実装条件下
の冷却速度において金属組織の微細化を達成できる。そ
の機構について、本発明者らは、これらのＳｎ系はんだ
合金が共晶組織であるにもかかわらず、実装条件下では
材料組織の微細化がなされず、粗大な初晶β―Ｓｎ相が
晶出する原因について検討し、これらの合金は平衡条件
下での凝固過程と異なり、ある冷却速度を与えると共晶
組成が高Ａｇ側にシフトして実際の凝固組織は共晶組成
とはならないことに着目した。その組織は、初晶β-Ｓ
ｎ相とβ-Ｓｎ相及びＡｇ3Ｓｎ金属間化合物の共晶が晶
出し、初晶で晶出するβ-Ｓｎ相は、共晶相に比較して
柔らかく、粒径も大きいために材料強度の低下を来たし
ていた。従って、初晶で晶出するβ-Ｓｎ相を微細化し
て均一な組織が得られると材料強度も向上するが、従来
のＳｎ−Ａｇ系合金では共晶の組成領域をコントロール
して組織として全面共晶相とすることは困難であること
から、本発明者らは、溶湯中に異質核を形成し、凝固過
程で同時多発的に結晶を晶出させることを着想した。The alloy composition of the present invention has a coarse primary crystal β-Sn.
Although the phase is in the range where it crystallizes, a small amount of Al is added, so that the cooling rate is not affected and the refinement of the metal structure can be achieved at the cooling rate under the solder mounting condition. Regarding the mechanism, the inventors of the present invention did not refine the material structure under the mounting conditions even though these Sn-based solder alloys had a eutectic structure, and formed a coarse primary crystal β-Sn phase. The cause of this is examined, and unlike the solidification process under equilibrium conditions, when given a certain cooling rate, the eutectic composition shifts to the high Ag side and the actual solidification structure does not become the eutectic composition. I focused on. Its structure is primary β-S
The eutectic of the n-phase, β-Sn phase and Ag 3 Sn intermetallic compound crystallizes out, and the β-Sn phase that crystallizes in the primary crystal is softer than the eutectic phase and has a large grain size, so the material strength is high. Was coming of decline. Therefore, if the β-Sn phase that crystallizes in the primary crystal is refined and a uniform structure is obtained, the material strength is also improved, but in the conventional Sn-Ag based alloy, the composition region of the eutectic is controlled to form the entire structure. Since it is difficult to form a eutectic phase, the present inventors have conceived that heterogeneous nuclei are formed in the molten metal and crystals are crystallized simultaneously in the solidification process.

【０００８】すなわち、Ｓｎ−Ａｇ合金溶湯に大気中で
Ａｌを添加すると一部がＡｌ2Ｏ3に変化するが、Ａｌ2
Ｏ3は一般に強力な異質核として機能することが知られ
ていることから、Ｓｎ系合金において異質核として機能
するかを考察した。その根拠として、ＳｎとＡｌ2Ｏ3結
晶面での不整合度をみると、その不整合性は大きく、Ｓ
ｎに対してＡｌ2Ｏ3が強力な異質核として機能すること
が期待される。実際に、Ｓｎ-Ａｇ合金にＡｌを添加し
て溶湯から凝固させると、Ｓｎ-Ａｇ二元系合金で得ら
れた冷却曲線では大きな過冷却を伴って均質核生成する
ために冷却曲線に潜熱現象（による段差）が現れるのに
対し、Ｓｎ-Ａｇ合金にＡｌを添加した試料では、過冷
却が抑制され、初晶の晶出変態点も現われなかった。こ
のことから、Ａｌが異質核として機能し、同時多発的に
核生成が行われたことが解った。Namely, a part the addition of Al in air to Sn-Ag alloy melt is changed to Al 2 O 3, Al 2
Since O 3 is generally known to function as a strong heterogeneous nucleus, it was considered whether it functions as a heterogeneous nucleus in a Sn-based alloy. As a basis for this, when looking at the degree of mismatch between the Sn and Al 2 O 3 crystal planes, the mismatch is large, and
It is expected that Al 2 O 3 will function as a strong foreign nucleus for n. In fact, when Al is added to the Sn-Ag alloy and solidified from the molten metal, the cooling curve obtained for the Sn-Ag binary alloy shows a latent heat phenomenon in the cooling curve because homogeneous nucleation occurs with large supercooling. However, in the sample in which Al was added to the Sn—Ag alloy, supercooling was suppressed and the crystallization transformation point of the primary crystal did not appear. From this, it was found that Al functions as a heterogeneous nucleus and nucleation is performed simultaneously.

【０００９】Ｓｎ-Ａｇ合金は、このように凝固時に異
質核が存在しないことから大きな過冷却を伴うことが特
徴であるが、このため実際のはんだ付け操業において
は、はんだが凝固する冷却速度がそれぞれの条件下であ
るとき、平衡状態図に示される組成から高合金側にシフ
トし、共晶組成であっても亜共晶組織を示して、粒径の
大きい初晶β-Ｓｎ相と微細な共晶との混在組織となる
のである。本発明においてはＳｎ-Ａｇ二元系合金にＡ
ｌを添加することで、溶融中にＡｌが一部酸素と結合し
てＡｌ2Ｏ3となり、このＡｌ2Ｏ3が異質核として機能す
ることで、凝固時において同時多発的に結晶を晶出さ
せ、組織を微細化するのであって、このため、これらの
Ｓｎ-Ａｇ二元系合金の過共晶から亜共晶までの広い組
成範囲にわたって、初晶として晶出するβ-Ｓｎ相を微
細化し、材料強度などの機械的特性を向上させることが
できる。このことは、同時にこれらのＳｎ系共晶合金に
おいて、冷却速度に依存することなく材料組織の微細化
が達成できること及び合金組成においてもＡｇの過共晶
組成から亜共晶組成までの広い組成範囲にわたって、結
晶組織を微細に制御できることを意味する。従って、本
発明において、実装条件下における広い冷却速度条件に
おいて材料組織を微細化することができ、また、その機
械的特性を低下させることなくＡｇ含有量を低減するこ
とができることとなる。The Sn-Ag alloy is characterized by a large amount of supercooling due to the absence of heterogeneous nuclei during solidification as described above. Therefore, in the actual soldering operation, the cooling rate at which the solder solidifies is Under each condition, the composition shown in the equilibrium diagram shifts to the high alloy side, and even if it is a eutectic composition, it shows a hypoeutectic structure, and the primary grain β-Sn phase with a large grain size and fine grains It has a mixed structure with various eutectic crystals. In the present invention, the Sn-Ag binary alloy is A
The addition of 1 part of Al combines with oxygen during melting to form Al 2 O 3 , and this Al 2 O 3 functions as a heterogeneous nucleus to simultaneously crystallize crystals during solidification. Therefore, the structure is made finer. Therefore, the β-Sn phase crystallized as a primary crystal is finely divided over a wide composition range from hypereutectic to hypoeutectic of these Sn-Ag binary alloys. And mechanical properties such as material strength can be improved. This means that at the same time, in these Sn-based eutectic alloys, the refinement of the material structure can be achieved without depending on the cooling rate, and the alloy composition has a wide composition range from Ag hypereutectic composition to hypoeutectic composition. It means that the crystal structure can be finely controlled. Therefore, in the present invention, the material structure can be refined under a wide cooling rate condition under the mounting condition, and the Ag content can be reduced without lowering the mechanical characteristics.

【００１０】[0010]

【発明の実施の形態】以下本発明の態様を具体的に説明
する。本発明においては、Ｓｎを基本組成として、Ａｇ
含有量を１．０wt％から５wt％、Ａｌ含有量を０．１wt
％から５wt％、の範囲とすることで達成される。ここ
で、請求項２において、 （１）Ａｇ含有量を０．１wt％から５wt％とした根拠、
最低含有量の０．１wt％は、はんだ材料の強度を保つ最
低の条件であり、また、最高含有量の５wt％は、実装な
どにおいて冷却速度が加速された場合の亜共晶組成から
共晶組成に変態する範囲の境界組成である。 （２）Ｃｕ含有量について 最低含有量の０．１wt％は、Ｃｕの添加能力、即ち濡れ
性の改善や材料強度を保つ最低の条件であり、最高含有
量の３wt％は材料強度を保ち、なお溶融温度の急激な上
昇が抑えられる限界領域である。 （３）Ａｌ含有量について、最低含有量の０．１wt％
は、大気中でＡｌがＡｌ2Ｏ3に変化し、異質核として機
能する最低の条件であり、最高含有量の５wt％は異質核
として余剰に生ずるＡｌ2Ｏ3が材料の濡れ性を損なわな
い限界領域である。さらに、請求項３において、Ｂｉ及
びＩｎの含有量を限定した根拠について、 （４）Ｂｉ含有量について 最低含有量の４０wt％は、共晶が４３wt％から初晶が晶
出し、材料強度を低下させることから実用上定まる限界
濃度であり、６０wt％は、融点の急激な上昇を抑制する
限界点である。 （５）Ｉｎ含有量について 最低含有量の４０wt％は、相構造が変化する最低の条件
であり、５０wt％は融点の上昇を抑制する最低の限界組
成である。 （６）その他の合金元素について 更に、請求項４の各添加元素については、融点低下の効
果と濡れ性を改善するという役目がある。Ｉｎ、Ｂｉ、
Ｓｂ、Ｚｎは融点を低下させる元素で、０．１wt％以下
では効果が発揮できず、また、５wt％以上ではそれ以下
の濃度より顕著な効果が期待できない。また、５wt％以
上の添加では濡れ性が劣る。Ｎｉ、Ｃｕ、Ａｕは、実装
時の電子部品基板材料として使用されている関係から実
装時に溶湯に混入されたりする。これらの元素の効果
は、濡れ性を改善することである。従って、最低含有量
の０．１wt％はその効果が発揮できる最低の条件であ
り、５wt％は効果が継続する限界濃度である。５wt％以
上の添加では逆に濡れ性を損なうことと材料強度の低下
を招く。Ｍｇ、Ｌａ、Ｃｅは、材料組織の粒界間隙部を
強化し、材料強度を高める元素として添加する。従って
最低濃度の０．１wt％はその効果が発揮できる最低の含
有量で、５wt％は効果が発揮できる限界濃度である。こ
れ以上の添加では、逆に金属間化合物が粗大化し。材料
強度の低下を招く。BEST MODE FOR CARRYING OUT THE INVENTION Aspects of the present invention will be specifically described below. In the present invention, as a basic composition of Sn, Ag
Content from 1.0wt% to 5wt%, Al content 0.1wt%
% To 5 wt%, which is achieved. Here, in claim 2, (1) the basis for setting the Ag content from 0.1 wt% to 5 wt%,
The minimum content of 0.1 wt% is the minimum condition for maintaining the strength of the solder material, and the maximum content of 5 wt% is eutectic from the hypoeutectic composition when the cooling rate is accelerated during mounting. It is the boundary composition within the range of transformation into composition. (2) Cu content The minimum content of 0.1 wt% is the minimum condition for maintaining Cu addition ability, that is, improvement of wettability and material strength, and the maximum content of 3 wt% maintains material strength, Note that this is a limit region in which a rapid increase in melting temperature can be suppressed. (3) Regarding the Al content, 0.1 wt% of the minimum content
Is the minimum condition that Al changes into Al 2 O 3 in the atmosphere and functions as a heterogeneous nucleus, and the maximum content of 5 wt% is excessive Al 2 O 3 generated as a heterogeneous nucleus, which impairs the wettability of the material. There is no marginal area. Further, the reason for limiting the contents of Bi and In in claim 3 is as follows: (4) Regarding the minimum Bi content of 40 wt%, the primary crystal is crystallized from 43 wt% of the eutectic to lower the material strength. Therefore, it is a practically determined limit concentration, and 60 wt% is a limit point for suppressing a sharp rise in melting point. (5) Regarding the In content The minimum content of 40 wt% is the minimum condition for changing the phase structure, and 50 wt% is the minimum limit composition for suppressing the rise of the melting point. (6) Other alloying elements Furthermore, the additive elements of claim 4 have the role of lowering the melting point and improving the wettability. In, Bi,
Sb and Zn are elements that lower the melting point, and if the concentration is 0.1 wt% or less, the effect cannot be exhibited, and if the concentration is 5 wt% or more, a remarkable effect cannot be expected with a concentration lower than that. In addition, if added in an amount of 5 wt% or more, the wettability is poor. Ni, Cu, and Au are mixed in the molten metal during mounting because they are used as electronic component substrate materials during mounting. The effect of these elements is to improve wettability. Therefore, the minimum content of 0.1 wt% is the minimum condition under which the effect can be exhibited, and 5 wt% is the limit concentration at which the effect continues. On the other hand, addition of 5 wt% or more adversely affects the wettability and lowers the material strength. Mg, La, and Ce are added as elements that strengthen the grain boundary gap portion of the material structure and enhance the material strength. Therefore, the minimum concentration of 0.1 wt% is the minimum content at which the effect can be exhibited, and 5 wt% is the limit concentration at which the effect can be exhibited. On the contrary, with the addition of more than this, the intermetallic compound becomes coarser. This leads to a decrease in material strength.

【００１１】[0011]

【実施例】以下、具体的データによって説明する。試料
重量が合計２００ｇになるように（ａ）Ｓｎ−２．０wt
％Ａｇ亜共晶合金を調製し、５７３Kで１．８ｋｓ保持
後、溶湯中にＡｌを含有量０．１wt％となるよう添加撹
拌しながら０．９ｋｓ保持し、冷却速度１０Ｋ／ｓから
１３０K/sを与えて凝固させた。比較資料として、同じ
く合計２００ｇとなるように、（ｂ）Ｓｎ-２．０wt％
Ａｇ及び（ｃ）Ｓｎ−３．５wt％Ａｇ共晶合金を調製し
て上記と同様の条件で凝固させた。[Examples] Specific data will be described below. (A) Sn-2.0wt so that the total sample weight is 200g
% Ag hypoeutectic alloy was prepared and held at 573 K for 1.8 ks, then 0.9 ks was added while stirring while adding and stirring Al so that the content of Al in the molten metal was 0.1 wt%, and the cooling rate was from 10 K / s to 130 K / s. s was given to solidify. As a comparison material, (b) Sn-2.0 wt% so that the total amount is 200 g.
Ag and (c) Sn-3.5 wt% Ag eutectic alloys were prepared and solidified under the same conditions as above.

【００１２】図１（ａ）、（ｂ）、（ｃ）は、上記の冷
却速度１０Ｋ／ｓで凝固させた実施例（ａ）及び比較例
（ｂ）、（ｃ）の組織写真である。図中表記の都合上各
含有元素の組成がmass％ で表記されているが、実質上
wt％と変わりはない。（ａ）のＡｌを０．１mass％添加
して作成した本発明Ｓｎ−２．０mass％Ａｇ亜共晶合金
においては、初晶β―Ｓｎ相が一律的に微細に形成され
ていることが解る。これに対して（ｂ）及び（ｃ）の比
較例においては、Ｓｎ−２．０mass％Ａｇ、及びSｎ−
３．５mass％Ag共晶合金の組織は、初晶β―Ｓｎ相が粗
大化して形成され、その間に共晶組織が微細に晶出して
いる。これらの組織における初晶β―Sn相の粒径はその
図中に挿入した１０μｍ及び５０μmのスケールから明
らかなように、本発明の初晶β―Ｓｎ相に比較して１０
倍以上に及び、顕著な相違が見られる。このように、初
晶β-Ｓｎ相間の間隙部にはβ-Ｓｎ相とＡｇ3Ｓｎ相の
共晶組織が密に形成していた。この結果より、初晶β−
Ｓｎ相と共晶相がお互いに一定のエリアを持つ組織形態
ではなく、初晶β−Ｓｎ相粒径が微細化したことによっ
て、共晶相が粒界分布を補強した組織形成となっている
ことが明らかとなった。このことは、材料強度の向上に
とって大きな意味を有する。FIGS. 1 (a), (b) and (c) are micrographs of Example (a) and Comparative Examples (b) and (c) solidified at the cooling rate of 10 K / s. The composition of each contained element is shown in mass% for convenience of notation in the figure, but in reality
It is no different from wt%. It is understood that in the Sn-2.0 mass% Ag hypoeutectic alloy of the present invention prepared by adding 0.1 mass% of Al of (a), the primary crystal β-Sn phase is uniformly finely formed. . On the other hand, in the comparative examples of (b) and (c), Sn-2.0 mass% Ag and Sn-
The structure of the 3.5 mass% Ag eutectic alloy is formed by coarsening of the primary crystal β-Sn phase, during which the eutectic structure is finely crystallized. As can be seen from the scales of 10 μm and 50 μm inserted in the figure, the grain size of the primary β-Sn phase in these structures is 10 compared with the primary β-Sn phase of the present invention.
It is more than doubled and noticeable differences are seen. Thus, the eutectic structure of the β-Sn phase and the Ag 3 Sn phase was densely formed in the gap between the primary crystal β-Sn phases. From this result, the primary crystal β-
The Sn-phase and eutectic phase do not have a structure morphology having a certain area, but the grain size of the primary crystal β-Sn phase is refined, so that the eutectic phase forms a structure in which the grain boundary distribution is reinforced. It became clear. This has great significance for improving the material strength.

【００１３】図２に上記の本発明及び比較例の合金の初
晶β―Ｓｎ相の粒径と冷却速度の関係を示す。比較例の
(b)Ｓｎ−2.0mass％Ａｇ亜共晶合金、及び(c)のＳｎ-3.
5mass％Ａｇ共晶合金では、いずれも冷却速度が１０K/s
から１３０K/sへと大きくなるにつれて４０μｍから
２０μｍ程度へと粒径が微細化する傾向が表れている
が、本発明の合金においては冷却速度が１０K/s から
１３０K/sの範囲でも６〜７μｍ程度の極めて微細な粒
径を維持し、殆ど冷却速度に依存しないことが解る。こ
の図において、実装条件下で見られる冷却速度（２ｋ／
ｓから１０Ｋ／ｓ）においては、本発明の合金の粒径は
比較例合金のものの１／７であり、著しく微細化され
た。FIG. 2 shows the relationship between the grain size of the primary β-Sn phase and the cooling rate in the alloys of the present invention and comparative examples. Comparative example
(b) Sn-2.0 mass% Ag hypoeutectic alloy, and (c) Sn-3.
With 5 mass% Ag eutectic alloy, the cooling rate was 10 K / s in all cases.
There is a tendency for the grain size to become finer from 40 μm to about 20 μm as it increases from 10 K / s to 130 K / s. In the alloy of the present invention, the cooling rate is 6 to 7 μm even in the range of 10 K / s to 130 K / s. It can be seen that the particle size remains extremely fine and the cooling rate is almost independent. In this figure, the cooling rate (2k /
s to 10 K / s), the grain size of the alloy of the present invention was 1/7 of that of the comparative alloy, and it was remarkably refined.

【００１４】図３に、Ｓｎ‐２．０wt％Ａｇの亜共晶合
金にＡｌ０．１ｗｔ％添加した本発明合金の組織内の濃
度分布を測定した結果を示す。この図の主眼は、濃度分
布を測定することによって初晶β-Ｓｎ相の粒径や粒界
間隙部に存在する金属間化合物の粒径や相構造を把握で
きる。Ｓｎ相の濃度組成を見ると濃度が急激に低下して
いる場所が粒界間隙部に対応し、濃度が高い部分が初晶
β-Ｓｎ相である。Ａｇ及びＡｌの濃度分布からＳｎ濃
度が変化した場所でＡｇおよびＡｌの濃度が上昇してい
る。また、Ａｇ及びＡｌの濃度変化は同じ推移を示して
いる。従って、粒界間隙部に存在する相は、初晶β-Ｓ
ｎ相とは違った金属間化合物であることが解る。なぜな
ら、初晶β-Ｓｎ相中にはＡｇ及びＡｌは溶解していな
いので、このことからも上記のことが解る。以上のこと
から、Ｓｎ−Ａｇ合金にＡｌを添加するとＡｌはＳｎ中
に溶解度がなく、Ａｇと結合して粒界間隙部に金属間化
合物を形成するか、大気中の空気と接してＡｌ2Ｏ3に変
化することが推察できる。FIG. 3 shows the results of measuring the concentration distribution in the structure of the alloy of the present invention in which 0.1 wt% of Al was added to the hypoeutectic alloy of Sn-2.0 wt% Ag. The main point of this figure is to grasp the grain size of the primary crystal β-Sn phase and the grain size and phase structure of the intermetallic compound existing in the intergranular gap by measuring the concentration distribution. Looking at the concentration composition of the Sn phase, the place where the concentration sharply decreases corresponds to the grain boundary gap portion, and the high concentration portion is the primary β-Sn phase. From the Ag and Al concentration distributions, the Ag and Al concentrations are increased where the Sn concentration changes. Further, the changes in the concentrations of Ag and Al show the same transition. Therefore, the phase existing in the intergranular space is the primary crystal β-S.
It is understood that it is an intermetallic compound different from the n phase. Because Ag and Al are not dissolved in the primary crystal β-Sn phase, the above fact can be understood from this fact as well. From the above, when Al is added to the Sn-Ag alloy, Al has no solubility in Sn and forms an intermetallic compound in the intergranular intergranular part by combining with Ag, or by contacting with air in the atmosphere to form Al 2 It can be inferred that it changes to O 3 .

【００１５】本発明の合金は、Ｓｎ系はんだ合金におい
て、Ａｌ添加によって形成されたＡｌ2Ｏ3により溶湯中
に異質核を形成して凝固過程で同時多発的に結晶を晶出
させることによって組織を微細化するものであるから、
Ｓｎに対するＡｇ含有量が亜共晶組成から過共晶組成ま
での広い範囲においてその効果を発揮できる。また、そ
の他の含有成分についても、従来からＳｎ系はんだ合金
に対して融点降下やはんだ材料としての濡れ性の向上や
材料強度を保つために添加されたＣｕ、Ｂｉ、Ｉｎ、或
いは、Ｎｉ、Ａｕ、Ｓｂ、Ｚｎ、Ｍｇ、Ｌａ、Ｃｅなど
の元素を含むはんだ合金に対しても同じメカニズムによ
って初晶β―Ｓｎ相の粗大化を抑制して、組織の微細化
を達成できるのであって、上記の成分範囲であればこれ
らの元素を１又は２以上を含有するはんだ合金におい
て、これらの含有成分による特性向上と併せて本発明の
作用効果を発揮することができる。The alloy of the present invention has a structure in which Sn-based solder alloy has a structure in which heterogeneous nuclei are formed in a molten metal by Al 2 O 3 formed by addition of Al, and crystals are simultaneously crystallized during solidification process. Is to be miniaturized,
The effect can be exhibited in a wide range of Ag content with respect to Sn, from a hypoeutectic composition to a hypereutectic composition. In addition, as for other components, Cu, Bi, In, Ni, Au, etc., which have been conventionally added to the Sn-based solder alloy in order to lower the melting point, improve the wettability as a solder material, and maintain the material strength. It is possible to suppress the coarsening of the primary crystal β-Sn phase and achieve the refinement of the structure by the same mechanism for solder alloys containing elements such as Al, Sb, Zn, Mg, La, and Ce. Within the range of the above component, in the solder alloy containing one or more of these elements, it is possible to exert the action and effect of the present invention together with the characteristic improvement due to these contained components.

【００１６】[0016]

【発明の効果】以上のとおり、本発明の鉛フリーはんだ
合金材料は、従来のＳｎ−Ａｇ二元系鉛フリーはんだ材
料における機械的特性を向上すると共に、はんだ冷却速
度の変化に対して影響されずに材料組織の微細化・機械
的特性の向上を発揮することができるため、高密度化、
部品の微細化の著しいエレクトロニクスはんだ実装に寄
与するものであり、また、高価なＡｇ含有量を低減でき
るためコスト低減などを通して、その普及を図り、これ
らの産業の発展に寄与するものである。As described above, the lead-free solder alloy material of the present invention improves the mechanical properties of the conventional Sn-Ag binary lead-free solder material and is affected by changes in the solder cooling rate. Since the material structure can be made finer and the mechanical properties can be improved without increasing the density,
The present invention contributes to electronic solder mounting, in which the miniaturization of components is remarkable, and also contributes to the development of these industries by promoting the spread of the components by reducing the cost because the expensive Ag content can be reduced.

【図面の簡単な説明】[Brief description of drawings]

【図１】本発明はんだ合金(a)と比較例合金(b),(c)の顕
微鏡写真に基づく組織拡大図。FIG. 1 is an enlarged view of microstructures of a solder alloy of the present invention (a) and comparative alloys (b) and (c) based on micrographs.

【図２】本発明はんだ合金と比較例合金における冷却速
度と結晶粒径との関係図。FIG. 2 is a graph showing the relationship between the cooling rate and the crystal grain size of the solder alloy of the present invention and the alloy of Comparative Example.

【図３】本発明はんだ合金における各含有元素の濃度分
布図。FIG. 3 is a concentration distribution diagram of each contained element in the solder alloy of the present invention.

───────────────────────────────────────────────────── フロントページの続き (72)発明者 小林 大樹 北海道札幌市北区北13条西８丁目 北海道 大学大学院工学研究科 Ｆターム(参考） 5E319 BB08 GG11    ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Taiki Kobayashi             Hokkaido, Sapporo, Kita-ku, Kita 13-jo Nishi 8-chome, Hokkaido             University Graduate School of Engineering F-term (reference) 5E319 BB08 GG11

Claims (4)

【特許請求の範囲】[Claims] 【請求項１】 Ｓｎ−Ａｇ二元系合金において、Ａｌを
添加し、異質核生成を伴う凝固によって、材料組織を微
細化した鉛フリーはんだ材料。1. A lead-free solder material in which a material structure is refined by solidification with heterogeneous nucleation in an Sn-Ag binary alloy. 【請求項２】 上記Ａｇ：１wt％〜５wt％、同じくＣ
ｕ：0.1〜３wt％、残部Ｓｎからなる合金に、Ａｌ：0.1
〜５wt％含有せしめてなる請求項１記載の鉛フリーはん
だ合金。2. The above Ag: 1 wt% to 5 wt%, also C
u: 0.1 to 3 wt%, Al: 0.1 to the alloy consisting of the balance Sn
The lead-free solder alloy according to claim 1, wherein the lead-free solder alloy contains 5 to 5 wt%. 【請求項３】 上記組成に加え、Ｂｉ：４０〜６０wt％
又はＩｎ：４０〜５０wt％を含有せしめてなる、請求項
１乃至２記載の鉛フリーはんだ材料。3. In addition to the above composition, Bi: 40-60 wt%
Alternatively, the lead-free solder material according to claim 1 or 2, wherein In: 40 to 50 wt% is contained. 【請求項４】 上記組成において、Ｃｕ：0.1〜５wt％
とし、さらにＩｎ，Ｂｉ，Ｎｉ，Ａｕ，Ｓｂ，Ｚｎ，Ｍ
ｇ，Ｌａ，Ｃｅから選択した元素のいずれか１乃至２以
上を0.1〜５wt％含有せしめてなる請求項１乃至２記載
の鉛フリーはんだ材料。4. In the above composition, Cu: 0.1-5 wt%
And In, Bi, Ni, Au, Sb, Zn, M
3. The lead-free solder material according to claim 1, which contains 0.1 to 5 wt% of one or more elements selected from g, La, and Ce.
JP2002012446A 2002-01-22 2002-01-22 Lead-free solder material Pending JP2003211283A (en)

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TW92101105A TW200302147A (en) 2002-01-22 2003-01-20 Lead-free solder alloy
PCT/JP2003/000470 WO2003061897A1 (en) 2002-01-22 2003-01-21 Lead-free solder material

Applications Claiming Priority (1)

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JP2002012446A JP2003211283A (en) 2002-01-22 2002-01-22 Lead-free solder material

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CN100366376C (en) * 2005-12-23 2008-02-06 南京航空航天大学 Leadless brazing filler metal containing cerium
JP2008031550A (en) * 2006-06-26 2008-02-14 Hitachi Cable Ltd Pb-FREE Sn-BASED MATERIAL, AND CONDUCTOR FOR ELECTRIC WIRING, TERMINAL-CONNECTING SECTION AND Pb-FREE SOLDER ALLOY
JP2008137018A (en) * 2006-11-30 2008-06-19 Mitsubishi Materials Corp Au-Sn ALLOY SOLDER PASTE HAVING EXCELLENT VOID GENERATION RESISTANCE
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JP2008161913A (en) * 2006-12-28 2008-07-17 Mitsubishi Materials Corp Sn-Au ALLOY SOLDER PASTE HAVING REDUCED PRODUCTION OF VOID
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US20100147926A1 (en) * 2005-07-14 2010-06-17 Sophia Product Co. Method for oxide bonding using solder alloy
US7749340B2 (en) * 2005-10-24 2010-07-06 Indium Corporation Of America Technique for increasing the compliance of lead-free solders containing silver
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JP2012500493A (en) * 2008-08-21 2012-01-05 アギア システムズ インコーポレーテッド Reduction of whiskers in Sn film
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US20100147926A1 (en) * 2005-07-14 2010-06-17 Sophia Product Co. Method for oxide bonding using solder alloy
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