JP2013163207A - Sn-Bi-BASED SOLDER ALLOY - Google Patents

Sn-Bi-BASED SOLDER ALLOY Download PDF

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JP2013163207A
JP2013163207A JP2012027827A JP2012027827A JP2013163207A JP 2013163207 A JP2013163207 A JP 2013163207A JP 2012027827 A JP2012027827 A JP 2012027827A JP 2012027827 A JP2012027827 A JP 2012027827A JP 2013163207 A JP2013163207 A JP 2013163207A
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solder alloy
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free solder
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Tetsuro Nishimura
西村哲郎
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Nihon Superior Sha Co Ltd
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Abstract

PROBLEM TO BE SOLVED: To provide a ball type and powder type Sn-Bi-based lead-free solder alloy, which has the characteristics of Sn-Bi composition solder, and a higher melting rate.SOLUTION: In a solidification process of a lead-free solder alloy basically consisting of Sn-Bi by adding one or more selected among Ni, Pd and Pt to the lead-free solder alloy basically consisting of Sn-Bi, an intermetallic compound (IMC) between Bi as one of the components and the additive element is generated, a fine crystalline structure of Sn and Bi is formed with the intermetallic compound serving as a nucleus, and the melting rate of the solder alloy consisting of the solder structure is increased compared with the melting rate of the lead-free solder alloy consisting of the conventional Sn-Bi composition. Further, by setting the blending quantity of Bi to be ≤30 wt.%, peeling or cracking which is caused by insufficient mechanical stress generated when joining an electronic component to a base material consisting of a copper sheet or the like can be controlled.

Description

本発明は、Ｓｎ-Ｂｉを基本組成とした低温鉛フリーはんだ合金に関する。 The present invention relates to a low-temperature lead-free solder alloy having Sn—Bi as a basic composition.

電子部品のはんだ付けにおいて、人体や環境に配慮した鉛を含まない鉛フリーはんだが用いられており、はんだ合金の融点により、高温はんだ、低温はんだに分類されている。
低温はんだとしては、Ｓｎ-Ｂｉ共晶はんだ、Ｓｎ-Ｉｎ等が知られており、なかでもＳｎ-Ｂｉ共晶はんだは、延展性が良い低温はんだとして用いられていた。
また、近年、電子部品等の小型化、実装密度の高密度化に伴い、低温はんだの形状もＢＧＡ等のボールタイプやペーストタイプが多く用いられるようになっている。 In soldering electronic components, lead-free solder that does not contain lead in consideration of the human body and the environment is used, and is classified into high-temperature solder and low-temperature solder according to the melting point of the solder alloy.
As the low-temperature solder, Sn—Bi eutectic solder, Sn—In, and the like are known. Among them, Sn—Bi eutectic solder has been used as a low-temperature solder having good extensibility.
In recent years, with the miniaturization of electronic parts and the like and the increase in mounting density, a ball type such as BGA and a paste type are often used as the shape of the low-temperature solder.

しかしながら、Ｓｎ-Ｂｉ共晶はんだは、１４０℃以上の温度域に於いて、Ｂｉの粗大化が生じて脆くなることが知られ、改良が検討されており、発明者もＳｂ、Ａｇ、及びＺｎを添加した組成の鉛フリーはんだ合金（特許文献１）を提案している。
また、特許文献２では、Ｓｎ-Ｂｉからなる基本組成にＡｌを添加したはんだ合金が提案されている。 However, it is known that Sn—Bi eutectic solder becomes brittle due to coarsening of Bi in a temperature range of 140 ° C. or higher, and improvements have been studied. The inventors have also studied Sb, Ag, and Zn. A lead-free solder alloy (Patent Document 1) having a composition to which is added is proposed.
Patent Document 2 proposes a solder alloy in which Al is added to a basic composition made of Sn-Bi.

このように、Ｓｎ-Ｂｉ共晶はんだの問題点を改善したはんだ合金が提案されているが、何れのはんだ合金も融点が１８０℃〜２００℃付近となり、Ｓｎ-Ｂｉ共晶はんだに比べて融点がかなり上昇するため、溶融速度が速いタイプのＳｎ-Ｂｉを基本組成とする鉛フリーはんだ合金が求められていた。 Thus, solder alloys that have improved the problems of Sn—Bi eutectic solder have been proposed, but each solder alloy has a melting point of 180 ° C. to 200 ° C., which is higher than that of Sn—Bi eutectic solder. Therefore, a lead-free solder alloy whose basic composition is Sn-Bi, which has a high melting rate, has been demanded.

特許第３３４６８４８号公報Japanese Patent No. 3346848 特開２００１−３４７３９４号公報JP 2001-347394 A

本発明の目的は、Ｓｎ-Ｂｉ組成はんだの特性を有し、且つ溶解速度を早くしたボールタイプ及び粉末タイプのＳｎ-Ｂｉ系鉛フリーはんだ合金を提供することである。 An object of the present invention is to provide a ball-type and powder-type Sn-Bi-based lead-free solder alloy having characteristics of Sn-Bi composition solder and having a high melting rate.

本発明の課題を解決すべく発明者は鋭意検討した結果、Ｓｎ-Ｂｉを基本組成とする鉛フリーはんだ合金にＮｉ、Ｐｄ、Ｐｔから選択される１種又は２種以上を添加することにより、当該Ｓｎ-Ｂｉを基本組成とする鉛フリーはんだ合金の凝固過程に於いて、構成成分の一つであるＢｉと添加元素の金属間化合物（ＩＭＣ）を生成させ、当該金属間化合物が核となり、微細なＳｎ及びＢｉの結晶組織を形成させること、そのはんだ構造からなる当該はんだ合金が、従来のＳｎ-Ｂｉ組成からなる鉛フリーはんだ合金に比べ、溶解速度が速まることを見出し、本発明の完成に至った。
即ち、本発明は、Ｓｎ-Ｂｉを基本組成とする鉛フリーはんだ合金にＮｉ、Ｐｄ、Ｐｔから選択される１種又は２種以上を特定量添加することにより、はんだ合金が凝固する過程に於いて、生成する金属間化合物がＳｎ-Ｂｉ組成に積極的に働き、結晶を微細化することを可能にし、その結果として溶解速度が向上したのである。 As a result of intensive studies by the inventors to solve the problems of the present invention, by adding one or more selected from Ni, Pd, and Pt to a lead-free solder alloy having a basic composition of Sn-Bi, In the solidification process of the lead-free solder alloy having the basic composition of Sn-Bi, Bi, which is one of the constituent components, and an intermetallic compound (IMC) of an additive element are generated, and the intermetallic compound serves as a nucleus, Forming a fine Sn and Bi crystal structure and finding that the solder alloy comprising the solder structure has a higher dissolution rate than the conventional lead-free solder alloy comprising the Sn-Bi composition was completed. It came to.
That is, the present invention is a process in which a solder alloy solidifies by adding a specific amount of one or more selected from Ni, Pd, and Pt to a lead-free solder alloy having a basic composition of Sn-Bi. Thus, the generated intermetallic compound works positively on the Sn—Bi composition, making it possible to refine the crystal, and as a result, the dissolution rate is improved.

更に、Ｂｉの配合量を３０重量％以下にすることにより、銅板等からなる母材に電子部品を接合した場合に発生する機械的応力不足による剥離や割れの抑制を可能とした。 Further, by making the blending amount of Bi 30% by weight or less, it is possible to suppress peeling and cracking due to insufficient mechanical stress generated when an electronic component is joined to a base material made of a copper plate or the like.

本発明のＳｎ-Ｂｉを基本組成とし、Ｎｉ、Ｐｄ、Ｐｔから選択される１種又は２種以上が配合された鉛フリーはんだ合金は、Ｓｎ-Ｂｉ共晶はんだ合金と比較して、機械的応力不足による剥離等の不具合が改善され、また、従来のＳｎ-Ｂｉ組成からなる鉛フリーはんだ合金と比較して、溶融速度が速くなるという効果を有する。 The lead-free solder alloy containing Sn-Bi of the present invention as a basic composition and containing one or more selected from Ni, Pd, and Pt is mechanical compared to the Sn-Bi eutectic solder alloy. Problems such as exfoliation due to insufficient stress are improved, and the melting rate is increased compared to a conventional lead-free solder alloy having a Sn—Bi composition.

図１は、Ｂｉ−Ｓｎの２成分状態図。FIG. 1 is a two-component state diagram of Bi-Sn. 図２は、Ｂｉ−Ｎｉの２成分状態図。FIG. 2 is a two-component state diagram of Bi-Ni. 図３は、Ｂｉ−Ｐｄの２成分状態図。FIG. 3 is a two-component state diagram of Bi-Pd. 図４は、Ｂｉ−Ｐｔの２成分状態図。FIG. 4 is a two-component state diagram of Bi-Pt. 図５は、凝固時の結晶粒径状態を示す概念図。FIG. 5 is a conceptual diagram showing a crystal grain size state during solidification.

以下に、本発明のＳｎ-Ｂｉを基本組成とする鉛フリーはんだ合金について詳細に説明する。
本発明のＳｎ-Ｂｉを基本組成とする鉛フリーはんだ合金は、Ｂｉの配合量が１０〜６０重量％、残部Ｓｎより構成され、その基本組成に、Ｎｉ、Ｐｄ、Ｐｔから選択される１種又は２種以上を特定量添加した鉛フリーはんだ合金である。
そして、本発明のＳｎ-Ｂｉを基本組成とする鉛フリーはんだ合金のＢｉの配合量は、３０重量％以下が更に好ましい。 Hereinafter, the lead-free solder alloy having the basic composition of Sn-Bi of the present invention will be described in detail.
The lead-free solder alloy based on Sn-Bi of the present invention is composed of 10 to 60% by weight of Bi and the balance of Sn, and the basic composition is selected from Ni, Pd, and Pt. Or it is a lead free solder alloy which added 2 or more types by specific amount.
And the compounding quantity of Bi of the lead-free solder alloy which has Sn-Bi as a basic composition of the present invention is more preferably 30% by weight or less.

図１の状態図が示すように、ＳｎとＢｉは、Ｓｎ４３重量％Ｂｉ５７重量％の割合付近で共晶となり、全域に於いて金属間化合物を形成しないため、凝固過程に於いて、粗大な結晶粒子が成長し、合金が形成される。
このように、金属間化合物を形成しないＳｎ-Ｂｉ共晶組成や、ＳｎとＢｉの配合比率を変化させたＳｎ-Ｂｉ組成からなる鉛フリーはんだ合金や、Ｂｉと金属間化合物を形成しない元素、例えば、ＳｂやＰｂを含有したＳｎ-Ｂｉを基本組成とするはんだ合金も同様の状態を示す。
また、このような粗大な結晶粒子が成長することは、はんだ合金の形態をボールタイプや粉末タイプに成型した場合でも同様に起こる。 As shown in the phase diagram of FIG. 1, Sn and Bi are eutectic in the vicinity of a ratio of Sn 43 wt% Bi 57 wt% and do not form an intermetallic compound in the entire region. Particles grow and an alloy is formed.
Thus, a Sn-Bi eutectic composition that does not form an intermetallic compound, a lead-free solder alloy having a Sn-Bi composition in which the mixing ratio of Sn and Bi is changed, an element that does not form an intermetallic compound with Bi, For example, a solder alloy containing Sn—Bi containing Sb or Pb as a basic composition shows the same state.
In addition, the growth of such coarse crystal particles occurs similarly even when the solder alloy is molded into a ball type or a powder type.

ところで、金属に於いては、同組成であっても結晶状態が微細になるに従い、溶解を始める温度が低下することは知られている。例えば、同じ金属組成のボールを製造した場合、ボールを製造過程で、急冷工程により製造した場合の結晶粒子は比較的微細な粒径からなるのに対して、製造工程が徐冷の場合は結晶が成長して粗大化した結晶粒子からなることが多く、溶解し始める温度も急冷工程により微細粒子からなるボールの方が低いことが知られている。 By the way, it is known that the temperature at which melting starts at a metal decreases as the crystal state becomes finer even with the same composition. For example, when a ball having the same metal composition is manufactured, the crystal particles when the ball is manufactured by the rapid cooling process in the manufacturing process have a relatively fine particle size, whereas when the manufacturing process is slowly cooled, the crystal is crystallized. It is known that the ball is often composed of crystal grains grown and coarsened, and the temperature at which dissolution starts is lower in the ball composed of fine particles by the rapid cooling process.

本発明のＳｎ-Ｂｉを基本組成とする鉛フリーはんだ合金は、Ｓｎ-Ｂｉ合金組成に、図２〜図４に示すようにＢｉと金属間化合物を形成する元素を添加することによって、はんだ合金が凝固する過程に於いて、当該添加元素とＢｉが金属間化合物を形成することでＳｎ-Ｂｉ合金組成中に核となるように形成され、核化した金属間化合物が、はんだ合金組成の凝固過程の結晶粒界へ積極的に働き、図５のＡに示す概念図ように、Ｓｎ及びＢｉの結晶粒径を微細化して、本発明のはんだボール並びにはんだ粉末が、微細化された結晶粒径が有することになる。
従って、本発明のＳｎ-Ｂｉを基本組成とし、Ｎｉ、Ｐｄ、Ｐｔから選択される１種又は２種以上を特定量添加した鉛フリーはんだ合金は、図５のＢに示す概念図ような状態の従来のＳｎ-Ｂｉ組成からなるはんだ合金の結晶構造に比べ微細になるため、溶融速度が速くなる。 The lead-free solder alloy based on Sn-Bi of the present invention is obtained by adding an element that forms an intermetallic compound with Bi to the Sn-Bi alloy composition as shown in FIGS. In the process of solidifying, the additive element and Bi are formed to form nuclei in the Sn—Bi alloy composition by forming an intermetallic compound, and the nucleated intermetallic compound is solidified into the solder alloy composition. Actively acting on the crystal grain boundaries in the process, as shown in the conceptual diagram of FIG. 5A, the crystal grains of Sn and Bi are refined, and the solder balls and solder powder of the present invention are refined. The diameter will have.
Accordingly, the lead-free solder alloy having the basic composition of Sn-Bi of the present invention and one or more selected from Ni, Pd, and Pt added thereto is in a state as shown in the conceptual diagram of FIG. 5B. Since it becomes finer than the crystal structure of a solder alloy having a conventional Sn—Bi composition, the melting rate is increased.

そして、本発明のＳｎ-Ｂｉを基本とする鉛フリーはんだ合金組成により製造されたはんだボール並びにはんだ粉末を用いたはんだペーストは、はんだ接合時に、Ｓｎ-Ｂｉ組成からなる鉛フリーはんだ合金と比較して、溶解開始温度が低く、溶解速度が速くなるのである。 And the solder paste using the lead-free solder alloy composition based on Sn-Bi of the present invention and the solder paste using the solder powder are compared with the lead-free solder alloy having the Sn-Bi composition at the time of soldering. Thus, the dissolution start temperature is low and the dissolution rate is increased.

本発明Ｓｎ-Ｂｉを基本組成とする鉛フリーはんだ合金に添加されるＮｉの配合量は、本発明の効果を有する範囲に於いて制限はないが、２重量％を超えて配合すると、はんだ合金の融点が上昇するため、２重量％以下が好ましい。 The amount of Ni added to the lead-free solder alloy having the basic composition of the present invention Sn-Bi is not limited within the range having the effect of the present invention, but if it exceeds 2% by weight, the solder alloy In this case, the content is preferably 2% by weight or less.

本発明Ｓｎ-Ｂｉを基本組成とする鉛フリーはんだ合金に添加されるＰｄの配合量は、本発明の効果を有する範囲に於いて制限はないが、２重量％を超えて配合すると、はんだ合金の融点が上昇するため、２重量％以下が好ましい。 The amount of Pd added to the lead-free solder alloy having the basic composition of the present invention Sn-Bi is not limited within the range having the effect of the present invention. In this case, the content is preferably 2% by weight or less.

本発明Ｓｎ-Ｂｉを基本組成とする鉛フリーはんだ合金に添加されるＰｔの配合量は、本発明の効果を有する範囲に於いて制限はないが、２重量％を超えて配合すると、はんだ合金の融点が上昇するため、２重量％以下が好ましい。 The amount of Pt added to the lead-free solder alloy having the basic composition of the present invention Sn-Bi is not limited in the range having the effect of the present invention, but if it exceeds 2% by weight, the solder alloy In this case, the content is preferably 2% by weight or less.

本発明Ｓｎ-Ｂｉを基本組成とする鉛フリーはんだ合金を用いて、ボールタイプや粉末タイプに加工する場合、本発明の効果を有する範囲に於いて、加工方法に制限はなく、ボールタイプの場合、アトマイズ法や滴下法が例示でき、粉末タイプの場合は、ディスクアトマイズ法やガスアトマイズ法が例示できる。 In the case of processing into a ball type or a powder type using a lead-free solder alloy having the basic composition of the present invention Sn-Bi, the processing method is not limited within the range having the effect of the present invention. An atomizing method and a dropping method can be exemplified, and in the case of a powder type, a disk atomizing method and a gas atomizing method can be exemplified.

本発明Ｓｎ-Ｂｉを基本組成とする鉛フリーはんだ合金の粉末を用いたはんだペーストは、本発明の効果を有する範囲に於いて、はんだペーストを構成する組成に特に制限はなく、従来の鉛フリーはんだペーストに用いられるフラックス組成を用いることも可能である。 The solder paste using the lead-free solder alloy powder having the basic composition of the present invention Sn-Bi is not particularly limited in the composition of the solder paste within the range having the effect of the present invention. It is also possible to use the flux composition used for the solder paste.

本発明Ｓｎ-Ｂｉを基本組成とする鉛フリーはんだ合金に添加されるＮｉ、Ｐｄ、及びＰｔ以外の元素に関して、本発明の効果を有する範囲に於いて、元素の種類、配合量共に任意に可能である。 With respect to elements other than Ni, Pd, and Pt added to the lead-free solder alloy having the basic composition of the present invention Sn-Bi, any kind of element and blending amount can be arbitrarily selected within the range having the effect of the present invention. It is.

１Ａ 本発明のＳｎ-Ｂｉを基本とする鉛フリーはんだ合金の結晶概念
１Ｂ 従来のＳｎ-Ｂｉ共晶組成の鉛フリーはんだ合金の結晶概念
２ 本発明のＳｎ-Ｂｉを基本組成とする鉛フリーはんだ合金に形成された金属間化合物の結晶概念



1A Crystal concept of lead-free solder alloy based on Sn-Bi of the present invention 1B Crystal concept of lead-free solder alloy of conventional Sn-Bi eutectic composition 2 Lead-free solder based on Sn-Bi of the present invention Crystal concept of intermetallic compounds formed in alloys



Claims (6)

Ｓｎ-Ｂｉを基本組成とする鉛フリーはんだ合金に、Ｎｉ、Ｐｄ、Ｐｔから選択される１種又は２種以上を配合したことを特徴とする鉛フリーはんだ合金。 A lead-free solder alloy comprising one or more selected from Ni, Pd and Pt in a lead-free solder alloy having a basic composition of Sn-Bi. Ｂｉの配合量が１０重量％乃至３０重量％以下であることを特徴とする請求項１記載の鉛フリーはんだ合金。 The lead-free solder alloy according to claim 1, wherein the amount of Bi is 10 wt% to 30 wt%. Ｂｉの配合量が１０重量％乃至３０重量％であることを特徴とする請求項１記載の鉛フリーはんだ合金。 The lead-free solder alloy according to claim 1, wherein the amount of Bi is 10 wt% to 30 wt%. Ｎｉ、Ｐｄ、及びＰｔの配合量が２重量％以下であることを特徴とする請求項１乃至請求項３記載の鉛フリーはんだ合金。 The lead-free solder alloy according to any one of claims 1 to 3, wherein the blending amount of Ni, Pd, and Pt is 2% by weight or less. はんだ形状がボール又は粉末であることを特徴とする請求項１乃至請求項４記載の鉛フリーはんだ合金。 5. The lead-free solder alloy according to claim 1, wherein the solder shape is a ball or powder. 請求項５記載のはんだ粉末を配合したはんだペースト。


The solder paste which mix | blended the solder powder of Claim 5.


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