JPWO2011027659A1 - ソルダペースト、それを用いた接合方法、および接合構造 - Google Patents
ソルダペースト、それを用いた接合方法、および接合構造 Download PDFInfo
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- JPWO2011027659A1 JPWO2011027659A1 JP2011529863A JP2011529863A JPWO2011027659A1 JP WO2011027659 A1 JPWO2011027659 A1 JP WO2011027659A1 JP 2011529863 A JP2011529863 A JP 2011529863A JP 2011529863 A JP2011529863 A JP 2011529863A JP WO2011027659 A1 JPWO2011027659 A1 JP WO2011027659A1
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- solder paste
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- intermetallic compound
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
- B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
- B23K35/0244—Powders, particles or spheres; Preforms made therefrom
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- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
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- B23K1/0008—Soldering, e.g. brazing, or unsoldering specially adapted for particular articles or work
- B23K1/0016—Brazing of electronic components
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Abstract
Description
ところで、従来から広く用いられてきたSn−Pb系はんだにおいては、高温系はんだとして、例えばPbリッチのPb−5Sn(融点:314〜310℃)、Pb−10Sn(融点:302〜275℃)などを用いて330〜350℃の温度ではんだ付けし、その後、例えば、低温系はんだのSn−37Pb共晶(183℃)などを用いて、上記の高温系はんだの融点以下の温度ではんだ付けすることにより、先のはんだ付けに用いた高温系はんだを溶融させることなく、はんだ付けによる接続を行う温度階層接続の方法が広く適用されている。
また、この特許文献1には、はんだペーストを用いた接合方法や、電子機器の製造方法が開示されている。
第1金属粉末と、前記第1金属粉末よりも融点の高い第2金属粉末とからなる金属成分と、フラックス成分とを含むソルダペーストであって、
前記第1金属はSnまたはSnを含む合金であり、
前記第2金属は前記第1金属と、310℃以上の融点を示す金属間化合物を生成し、かつ、前記金属間化合物の格子定数と前記第2金属成分の格子定数との差である格子定数差が50%以上である金属または合金であること
を特徴としている。
(a)ロジン、重合ロジン、WW(water white)ロジン、水添ロジンからなるロジン群より選ばれる少なくとも1種、
(b)前記ロジン群より選ばれる少なくとも1種の誘導体を含むロジン系樹脂、
(c)硬化ヒマシ油、脂肪族アミド等のチキソ剤、有機酸、アミンのハロゲン化水素酸塩等の活性剤等の固体成分をエチレングリコールモノブチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテルからなる群より選ばれる少なくとも1種を溶剤で溶解してペースト状にしたもの
からなる群より選ばれる少なくとも1種を含むものであることが望ましい。
接合対象物を接合させている接合部は、前記ソルダペーストに由来する前記第2金属と、前記第2金属とSnとを含む金属間化合物とを主たる成分としており、前記ソルダペーストに由来する前記第1金属の金属成分全体に対する割合が30体積%以下であること
を特徴としている。
すなわち、この格子定数差は、第2金属との界面に新たに生成する金属間化合物の格子定数が、第2金属の格子定数に対してどれだけ差があるかを示すものであり、いずれの格子定数が大きいかを問わないものである。
なお、計算式で表すと以下のようになる。
格子定数差(%)={(金属間化合物の格子定数−第2金属の格子定数)/第2金属の格子定数}×100
第2金属には、第1金属との反応を阻害しない程度で、例えば、1重量%以下の割合で不純物が含まれていてもよい。不純物としては、Zn、Ge、Ti、Sn、Al、Be、Sb、In、Ga、Si、Ag、Mg、La、P、Pr、Th、Zr、B、Pd、Pt、Ni、Auなどが挙げられる。
また、接合性や反応性を考慮すると、第1および第2金属粉末中の酸素濃度は2000ppm以下であることが好ましく、特に10〜1000ppmが好ましい。
前記ビヒクルの具体的な例としては、ロジンおよびそれを変性した変性ロジンなどの誘導体からなるロジン系樹脂、合成樹脂、またはこれらの混合体などが挙げられる。
また、前記ロジンおよびそれを変性した変性ロジンなどの誘導体からなるロジン系樹脂の具体的な例としては、ガムロジン、トールロジン、ウッドロジン、重合ロジン、水素添加ロジン、ホルミル化ロジン、ロジンエステル、ロジン変性マレイン酸樹脂、ロジン変性フェノール樹脂、ロジン変性アルキド樹脂、その他各種ロジン誘導体などが挙げられる。
また、ロジンおよびそれを変性した変性ロジンなどの誘導体からなる合成樹脂の具体的な例としては、ポリエステル樹脂、ポリアミド樹脂、フェノキシ樹脂、テルペン樹脂などが挙げられる。
また、前記有機酸の具体的な例として、マロン酸、フマル酸、グリコール酸、クエン酸、リンゴ酸、コハク酸、フェニルコハク酸、マレイン酸、サルチル酸、アントラニル酸、グルタル酸、スベリン酸、アジピン酸、セバシン酸、ステアリン酸、アビエチン酸、安息香酸、トリメリット酸、ピロメリット酸、ドデカン酸などがあり、さらに有機アミンの具体的なものとして、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、トリブチルアミン、アニリン、ジエチルアニリンなどが挙げられる。
また、前記多価アルコールとしてはエリスリトール、ピロガロール、リビトールなどが例示される。
さらにソルダペースト中の金属配合比などを最適化することにより、完全に第1金属成分が残留しない設計を行うことができる。
すなわち、本発明のソルダペーストを用いることにより、例えば、半導体装置の製造工程において、はんだ付けを行う工程を経て半導体装置を製造した後、その半導体装置を、リフローはんだ付けの方法で基板に実装するような場合にも、先のはんだ付けの工程におけるはんだ付け部分は、耐熱強度に優れているため、リフローはんだ付けの工程で再溶融してしまうことがなく、信頼性の高い実装を行うことが可能になる。
なお、接合部中におけるソルダペーストに由来する前記第1金属は3体積%以下であることがさらに望ましい。
なお、上記の各材料の表記において、例えば、「Sn−3.5Ag」の数字3.5は当該成分(この場合はAg)の重量%の値を示しており、上記の他の材料および、以下の記載の場合も同様である。
また、フラックスの配合割合は、ソルダペースト全体に占めるフラックスの割合が10重量%となるような割合とした。
印刷したソルダペースト上に、NiめっきおよびAuめっきを施した黄銅端子(サイズ1.2mm×1.0mm×1.0mm)をマウントした後、リフロー装置を用いて、図2に示すリフロープロファイルで接合した。
上述のようにして作製した試料について、以下の方法で接合強度およびはんだ流れ出し不良発生率を測定し、特性を評価した。
得られた接合体のシアー強度を、ボンディングテスタを用いて測定し、評価した。
シアー強度の測定は、横押し速度:0.1mm・s-1、室温および260℃の条件下で行った。
そして、シアー強度が20Nmm-2以上のものを◎(優)、2Nmm-2以下のものを×(不可)と評価した。
表1に、第1金属および第2金属の組成、第2金属の格子定数、第1金属および第2金属の配合割合、第2金属粉末の表面に最初に生成した金属間化合物の種類とその格子定数、第2金属(Cu合金)と金属間化合物の格子定数差、各接合体の接合強度(室温、260℃)を示す。なお、格子定数はa軸を基に評価している。
得られた反応生成物を約7mg切り取り、測定温度30℃〜300℃、昇温速度5℃/min、N2雰囲気、リファレンスAl2O3の条件で示差走査熱量測定(DSC測定)を行った。得られたDSCチャートの第1金属成分の溶融温度における溶融吸熱ピークの吸熱量から、残留した第1金属成分量を定量化した。これから金属成分全体に対する第1金属成分の割合を残留第1金属成分率として評価した。残留第1金属成分率が0〜3体積%の場合を◎(優)、30体積%より大きいの場合を×(不可)と評価した。
表1に、残留第1金属成分率と判定結果を併せて示す。
プリント基板のCuランド(Cuランド寸法:0.7mm×0.4mm)に前記ソルダペーストを塗布し(厚さ100μm)、得られた塗布部に、長さ1mm、幅0.5mm、厚さ0.5mmサイズのチップ型セラミックコンデンサをマウントした。
ピーク温度250℃でリフローはんだ付後、プリント基板をエポキシ樹脂で封止して相対湿度85%の環境に放置し、ピーク温度260℃のリフロー条件で加熱してはんだが流れ出す割合を調べ、はんだ流れ出し不良発生率として評価した。
はんだ流れ出し不良率が0〜10%の場合を◎(優)、50%より大きい場合を×(不可)と評価した。
表1に、はんだ流れ出し不良発生率と判定結果を併せて示す。
一方、260℃における接合強度についてみると、比較例では2Nmm-2以下と接合強度が不十分であったのに対して、実施例は10Nmm-2以上を保持し、実用強度を備えていることが確認された。
また、実施例の試料においては、第1金属がSnをベースとするはんだ合金であれば、第1金属の種類に関係なく同様の高耐熱性を備えていることが確認された。
さらに、実施例の試料においては、第2金属がCu−Mnをベースとする金属(Cu−12Mn−4NiやCu−10Mn−1Pなど)である場合や、第2金属粉末が2種類以上(Cu−Mn、Cu-Ni混合粉末)である場合にも、同様に高耐熱性を備えていることが確認された。
また、第2金属粉末として、Cu、およびCu−10Mnの粉末を用意した。第2金属粉末の平均粒径は15μmとした。
フラックスとして、ロジン:74重量%、ジエチレングリコールモノブチルエーテル:22重量%、トリエタノールアミン:2重量%、および水素添加ヒマシ油2重量%の配合比率のものを用意した。
なお、配合比は、第1金属粉末/第2金属粉末の体積比が87/13〜57/43(すなわち、第2金属粉末が13〜43体積%)となるように調整した。
また、フラックスの配合割合は、ソルダペースト全体に占めるフラックスの割合が10重量%となるような割合とした。
なお、接合強度の評価にあたっては、シアー強度が20Nmm-2以上のものを◎(優)、2Nmm-2以上で20Nmm-2未満のものを○(良)、2Nmm-2以下のものを×(不可)と評価した。
一方、260℃における接合強度についてみると、比較例では0.1Nmm-2と、2Nmm-2を大きく下回っており、接合強度が不十分であったのに対して、実施例では7〜26Nmm-2と、2Nmm-2以上を保持し、実用強度を備えていることが確認された。特に、第2金属がCu−10Mnである場合、その割合が30%以上では、23Nmm-2以上の接合強度を示し、高い耐熱強度を備えていることが確認された。
また、第2金属粉末として、Mnの割合が5〜30重量%のCu−Mn合金の粉末、および、Niの割合が5〜20重量%のCu−Ni合金の粉末を用意した。第2金属粉末の平均粒径は15μmとした。
フラックスとして、ロジン:74重量%、ジエチレングリコールモノブチルエーテル:22重量%、トリエタノールアミン:2重量%、および水素添加ヒマシ油2重量%の配合比率のものを用意した。
また、フラックスの配合割合は、ソルダペースト全体に占めるフラックスの割合が10重量%となるような割合とした。
第1金属粉末と第2金属粉末の配合比は第1金属粉末/第2金属粉末の体積比が60/40(すなわち、第2金属粉末が40体積%)となるように調整した。
なお、接合強度の評価および、残留第1金属成分率、はんだ流れ出し不良率の評価にあたっては、実施例2の場合と同様の基準で評価した。
表3に、各接合体の接合強度(室温、260℃)、残留第1金属成分率、はんだ流れ出し不良率、およびそれらの評価結果を示す。
一方、260℃における接合強度についてみると、比較例では0.1Nmm-2と、2Nmm-2を大きく下回っており、接合強度が不十分であったのに対して、実施例では5〜26Nmm-2と、2Nmm-2以上を保持し、実用強度を備えていることが確認された。特に、第2金属がCu−10〜15Mnである場合、および、Cu−10〜15Niである場合、24〜26Nmm-2と高い接合強度を示し、耐熱強度に優れていることが確認された。
また、第2金属粉末として、Cu、Cu−10Mn合金の粉末を用意した。第2金属粉末の平均粒径は15μmとした。第2金属粉末は、その粒径を変化させて、比表面積が0.03〜0.06m2・g-1となるようにした。
また、フラックスとして、ロジン:74重量%、ジエチレングリコールモノブチルエーテル:22重量%、トリエタノールアミン:2重量%、および水素添加ヒマシ油2重量%の配合比率のものを用意した。
また、フラックスの配合割合は、ソルダペースト全体に占めるフラックスの割合が10重量%となるような割合とした。
第1金属粉末と第2金属粉末の配合比は、第1金属粉末/第2金属粉末の体積比が60/40(すなわち、第2金属粉末が40体積%)となるように調整した。
なお、接合強度の評価および、残留第1金属成分率、はんだ流れ出し不良率の評価にあたっては、上述の実施例2の場合と同様の基準で評価した。
表4に、各接合体の接合強度(室温、260℃)、残留第1金属成分率、はんだ流れ出し不良率、およびそれらの評価結果を示す。
一方、260℃における接合強度についてみると、比較例では0.1Nmm-2と、2Nmm-2を大きく下回っており、接合強度が不十分であったのに対して、実施例では14〜24Nmm-2と、2Nmm-2以上を保持し、実用強度を備えていることが確認された。さらに第二金属であるCu−10Mnの比表面積が0.05m2・g-1以上の場合に21Nmm-2以上を示し、特に高い耐熱強度を有した。
(b)SnめっきしたCu−10Mn合金とSn粉とCu−10Mn合金の混合体
(c)SnめっきしたCu−10Mn合金単体、
からなる金属粉とフラックスを混合することによりソルダペーストを作製した。
ただし、SnめっきしたCu−10Mn合金単体の場合は、Cu−Mn合金(第2金属)の合計比率を80%とした。
また、フラックスの配合割合は、ソルダペースト全体に占めるフラックスの割合が10重量%となるような割合とした。
なお、接合強度の評価、残留第1金属成分率、およびはんだ流れ出し不良率の評価にあたっては、上述の実施例2の場合と同様の基準で評価した。
表5に、各接合体の接合強度(室温、260℃)、残留第1金属成分率、はんだ流れ出し不良率、およびそれらの評価結果を示す。
一方、260℃における接合強度についてみると、比較例では0.1Nmm-2と、2Nmm-2を大きく下回っており、接合強度が不十分であったのに対して、実施例では24〜26Nmm-2と、2Nmm-2以上を保持し、実用強度を備えていることが確認された。このことから、第1金属が第2金属の表面にめっき(コート)されている場合にも、上記の各実施例の場合と同様に、高い耐熱強度が得られることが確認された。
また、第2金属粉末として、Cu−10Mn合金の粉末を用意した。第2金属粉末の平均粒径は15μmとした。
フラックスとして、樹脂を添加したものと、樹脂を添加しなかったものを用意した。
フラックスA :30重量%
熱硬化性樹脂 :40重量%
硬化剤 :30重量%
フラックスA :30重量%
熱可塑性樹脂(ポリアミド樹脂) :70重量%
(1)樹脂を添加していない上記フラックスAをソルダペースト全体に占めるフラックスの割合が10重量%となるような割合で配合したソルダペーストと、
(2)熱硬化性樹脂配合フラックスBをソルダペースト全体に占めるフラックスの割合が25重量%となるような割合で配合したソルダペーストと、
(3)熱可塑性樹脂配合フラックスCをソルダペースト全体に占めるフラックスの割合が25重量%となるような割合で配合したソルダペーストと
を作製した。
表6に、各接合体の接合強度(室温、260℃)、残留第1金属成分率、はんだ流れ出し不良率、およびそれらの評価結果を示す。
一方、260℃における接合強度についてみると、比較例では0.1Nmm-2と、2Nmm-2を大きく下回っており、接合強度が不十分であったのに対して、実施例では24〜33Nmm-2と、2Nmm-2以上を保持し、実用強度を備えていることが確認された。
2 第2金属
3 金属間化合物
4 接合部
11a,11b 一対の電極(接合対象物)
10 ソルダペースト
Claims (12)
- 第1金属粉末と、前記第1金属粉末よりも融点の高い第2金属粉末とからなる金属成分と、フラックス成分とを含むソルダペーストであって、
前記第1金属はSnまたはSnを含む合金であり、
前記第2金属は、前記第1金属と、310℃以上の融点を示す金属間化合物を生成し、かつ、前記金属間化合物の格子定数と前記第2金属成分の格子定数との差である格子定数差が50%以上の金属または合金であること
を特徴とするソルダペースト。 - 前記金属成分中に占める前記第2金属粉末の割合が、30体積%以上であることを特徴とする請求項1記載のソルダペースト。
- 前記第1金属は、Sn単体、または、Cu、Ni、Ag、Au、Sb、Zn、Bi、In、Ge、Al、Co、Mn、Fe、Cr、Mg、Mn、Pd、Si、Sr、Te、Pからなる群より選ばれる少なくとも1種と、Snとを含む合金であること
を特徴とする請求項1または2記載のソルダペースト。 - 前記第2金属は、Cu−Mn合金またはCu−Ni合金であることを特徴とする請求項1〜3のいずれかに記載のソルダペースト。
- 前記第2金属は、前記第2金属に占めるMnの割合が10〜15重量%であるCu−Mn合金、または、前記第2金属に占めるNiの割合が10〜15重量%であるCu−Ni合金であることを特徴とする請求項1〜4のいずれかに記載のソルダペースト。
- 前記第2金属粉末は、比表面積が0.05m2・g-1以上のものであることを特徴とする請求項1〜5のいずれかに記載のソルダペースト。
- 前記第1金属粉末のうち少なくとも一部が、前記第2金属粉末の周りにコートされていることを特徴とする請求項1〜6のいずれかに記載のソルダペースト。
- 前記フラックスが、
(a)ロジン、重合ロジン、WW(water white)ロジン、水添ロジンからなるロジン群より選ばれる少なくとも1種、
(b)前記ロジン群より選ばれる少なくとも1種の誘導体を含むロジン系樹脂、
(c)硬化ヒマシ油、脂肪族アミド等のチキソ剤、有機酸、アミンのハロゲン化水素酸塩等の活性剤等の固体成分をエチレングリコールモノブチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテルからなる群より選ばれる少なくとも1種を溶剤で溶解してペースト状にしたもの
からなる群より選ばれる少なくとも1種を含むものであることを特徴とする請求項1〜7のいずれかに記載のソルダペースト。 - 前記フラックスが、エポキシ樹脂、フェノール樹脂、ポリイミド樹脂、シリコン樹脂またはその変性樹脂、アクリル樹脂からなる熱硬化性樹脂群より選ばれる少なくとも1種、あるいは、ポリアミド樹脂、ポリスチレン樹脂、ポリメタクリル樹脂、ポリカーボネート樹脂、セルロース系樹脂からなる熱可塑性樹脂群から選ばれる少なくとも1種を含むものであることを特徴とする請求項1〜8のいずれかに記載のソルダペースト。
- ソルダペーストを用いて接合対象物を接合する方法において、請求項1〜9のいずれかに記載のソルダペーストを用い、加熱して前記ソルダペーストを構成する前記第1金属成分を、前記ソルダペーストを構成する前記第2金属との金属間化合物にして、接合対象物を接合させることを特徴とする接合方法。
- 接合対象物が、請求項1〜9のいずれかに記載のソルダペーストを用いて接合された接合構造であって、
接合対象物を接合させている接合部のはんだは、前記ソルダペーストに由来する前記第2金属と、前記第2金属とSnとを含む金属間化合物とを主たる成分としており、前記ソルダペーストに由来する前記第1金属の金属成分全体に対する割合が30体積%以下であること
を特徴とする接合構造。 - 前記金属間化合物が、前記ソルダペーストに由来する前記第2金属であるCu−Mn合金、または、Cu−Ni合金と、前記ソルダペーストに由来する前記第1金属である、Sn単体、または、Cu、Ni、Ag、Au、Sb、Zn、Bi、In、Ge、Al、Co、Mn、Fe、Cr、Mg、Mn、Pd、Si、Sr、Te、Pからなる群より選ばれる少なくとも1種と、Snとを含む合金との間に形成された金属間化合物であることを特徴とする請求項11記載の接合構造。
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