JP6967726B2 - はんだペーストおよび実装構造体 - Google Patents
はんだペーストおよび実装構造体 Download PDFInfo
- Publication number
- JP6967726B2 JP6967726B2 JP2018015340A JP2018015340A JP6967726B2 JP 6967726 B2 JP6967726 B2 JP 6967726B2 JP 2018015340 A JP2018015340 A JP 2018015340A JP 2018015340 A JP2018015340 A JP 2018015340A JP 6967726 B2 JP6967726 B2 JP 6967726B2
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- epoxy resin
- solder
- solder paste
- reactive diluent
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- 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
- B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
- B23K35/362—Selection of compositions of fluxes
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- 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
- B23K35/02—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
- B23K35/025—Pastes, creams, slurries
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
- B23K35/3612—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest with organic compounds as principal constituents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
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- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
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- C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
- C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
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- C22C13/02—Alloys based on tin with antimony or bismuth as the next major constituent
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Description
本発明の実施の形態におけるはんだペースト中のフラックスには、エポキシ樹脂、反応性希釈剤、硬化剤、有機酸(活性剤)およびゴム変性エポキシ樹脂が含まれる。はんだペーストの全重量に対するフラックスの量は、好ましくは10重量%以上40重量%以下、より好ましくは15重量%以上25重量%以下、さらに好ましくは18重量%以上22重量%以下の範囲にある。本発明のはんだペーストにおけるフラックスの含有量が上記範囲にあることにより、接合部の高い接続信頼性とペーストの優れた印刷作業性および安定した導電性を効果的に実現することができる。以下に、フラックスに含まれる各必須成分についてさらに詳細に記載する。
エポキシ樹脂とは、一般に、構造内にエポキシ基を有することにより、加熱による硬化が可能である熱硬化性樹脂をいう。本発明の実施の形態においてフラックスに含まれるエポキシ樹脂(ベースエポキシ樹脂)は、常温で液状のものである。このようなエポキシ樹脂を配合することで、はんだ粒子などの他の成分を容易に分散することができる。本明細書において「常温で液状」とは、大気圧下での5℃〜28℃の温度範囲、特に室温20℃前後において流動性を持つことを意味する。常温で液状のエポキシ樹脂としては、1分子内にエポキシ基を2つ以上有するものであれば、その分子量および分子構造は特に限定されず、各種のものを用いることができる。具体的には、例えば、グリシジルエーテル型、グリシジルアミン型、グリシジルエステル型またはオレフィン酸化型(脂環式)などの各種の液状のエポキシ樹脂を用いることができる。さらに具体的には、例えば、ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂などのビスフェノール型エポキシ樹脂、水添ビスフェノールA型エポキシ樹脂、水添ビスフェノールF型エポキシ樹脂などの水添ビスフェノール型エポキシ樹脂、ビフェニル型エポキシ樹脂、ナフタレン環含有エポキシ樹脂、脂環式エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、トリフェニルメタン型エポキシ樹脂、脂肪族系エポキシ樹脂、トリグリシジルイソシアヌレートなどを用いることができる。これらは1種単独で用いてもよく、または2種以上を併用してもよい。これらの中でも、半導体封止用液状エポキシ樹脂組成物の低粘度化と硬化物の物性向上を考慮すると、常温で液状のエポキシ樹脂として、ビスフェノール型エポキシ樹脂、水添ビスフェノール型エポキシ樹脂が好ましい。また、常温で固形のエポキシ樹脂を併用することもできる。常温で固形のエポキシ樹脂としては、例えば、ビフェニル型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、トリアジン骨格エポキシ樹脂などを用いることができる。エポキシ樹脂の量は、フラックスの全重量に対して、好ましくは25重量%以上90重量%以下、より好ましくは35重量%以上70重量%以下、さらに好ましくは38重量%以上63重量%以下の範囲で使用されることが好ましい。本発明のフラックスにおけるエポキシ樹脂の含有量が上記範囲にあることにより、接合部の接続信頼性を効果的に向上させることができる。
本発明の実施の形態においてフラックスに含まれる反応性希釈剤は、化合物の末端または側鎖に2つ以上のエポキシ基を有する化合物を含む。より具体的には、反応性希釈剤は、実質的に、当該2つ以上のエポキシ基を有する化合物からなる。ここでいう反応性希釈剤における「実質的に」とは、反応性希釈剤の全重量に対して、好ましくは90重量%以上100重量%未満、より好ましくは95重量%以上100重量%未満、さらに好ましくは99重量%以上100重量%未満、よりさらに好ましくは99.5重量%以上100重量%未満の範囲の量で、反応性希釈剤中において当該2つ以上のエポキシ基を有する化合物が含まれることを意味する。残りは反応性希釈剤の製造過程などにおいて含有され得る不純物、例えば後述するハロゲンイオンなどである。反応性希釈剤の粘度は150mPa・s以上700mPa・s以下であり、当該反応性希釈剤中に含まれる全塩素量は0.5重量%以下である。反応性希釈剤は、主として、フラックス硬化物の物性を考慮すると、好ましくは、主骨格にベンゼン環またはシクロペンタジエン骨格などの剛直な骨格を有する化合物から実質的に構成される。
硬化剤としては、一般的なエポキシ樹脂硬化剤を使用することができる。例えば、酸無水物、フェノールノボラック、各種チオール化合物、各種アミン類、ジシアンジアミド、イミダゾール類、金属錯体およびそれらのアダクト化合物であって、例えばポリアミンのアダクト変性物などを使用することができるが、これらに限定されない。特に、各種イミダゾール類は、一液性とはんだ溶融性の両立に優れていることから好ましく使用され得る。イミダゾール類としては、例えば、2MZ、C11Z、2PZ、2E4MZ、2P4MZ、1B2MZ、1B2PZ、2MZ−CN、2E4MZ−CN、2PZ−CN、C11Z−CN、2PZ−CNS、C11Z−CNS、2MZ−A、C11Z−A、2E4MZ−A、2P4MHZ、2PHZ、2MA−OK、2PZ−OK(いずれも四国化成工業社製)や、これらのイミダゾール類をエポキシ樹脂と付加させた化合物を使用することができるが、これらに限定されない。また、これら硬化剤をポリウレタン系、ポリエステル系の高分子物質などで被覆してマイクロカプセル化したものを用いることもできる。
有機酸(活性剤)の種類は、特に限定されるものではなく、任意の有機化合物の酸を用いることができる。例えばアビエチン酸に代表されるロジン成分材料、各種アミンおよびその塩、セバシン塩、アジピン酸、グルタル酸、コハク酸、マロン酸、クエン酸、ピメリン酸、などを用いることができる。特に、有機酸は、優れたフラックス作用(ここで、フラックス作用とは、はんだペーストが塗布される金属表面に生じた酸化皮膜を除去するという還元作用、および、溶融はんだの表面張力を低下させて、はんだの接合金属表面への濡れ性を促進する作用を意味する)を有する。
本発明の実施の形態におけるはんだペーストのフラックスは、ゴム変性エポキシ樹脂を含む。一般的に、エポキシ樹脂は、高接着や絶縁性などのメリットから、接着剤、塗料、電気電子材料などに使用されているが、本質的な欠点として靭性の不足が挙げられる。剛直であるがために、機械的な加重によって、割れなどが起こり易い。具体的には、部品の接続部に機械的な加重がかかる場合に部品が剥がれてしまうため、信頼性寿命の短縮が起こっている。
相互侵入高分子網目)、つまり強靭な熱可塑性ポリマーを添加することによって形成された複数の異なるポリマーが入り混じった多成分系高分子)、海島構造の形成、各種ゴム骨格の導入などが挙げられる。
本発明のはんだペーストに含まれるはんだ粉末として、融点240℃以下のはんだ粉末が用いられることが好ましい。はんだ粒子の融点の下限は特に限定されるものではないが、130℃以上であることが好ましい。BGAまたはCSP半導体のはんだボールは、錫−銀−銅(SAC)はんだ粉末を用いるが、その融点(220℃)よりも融点が低いはんだ粉末がはんだペーストに用いられることで、SACはんだ粉末の再溶融を防ぐことができる。はんだ粉末の組成は、特に限定されないが、はんだ合金の形態であってもよい。例えば、Snをベースとした合金などを用いることができる。また、好ましくは、22重量%以上68重量%以下のBiと、0重量%以上2重量%以下のAgと、0重量%以上73重量%以下のInとを含み、残部がSnであるはんだ粉末を用いることができる。より好ましくは、SnBi系の42Sn−58Bi、42Sn−57Bi−1.0Ag、16Sn−56Bi−28Inなどが用いられる。本発明のはんだペーストの全質量に対するはんだ粉末の含有量は、好ましくは50重量%以上95重量%以下、より好ましくは60重量%以上90重量%以下、さらに好ましくは75重量%以上85重量%以下の範囲にある。本発明のはんだペーストにおけるはんだ粉末の含有量が上記範囲にあることにより、接合部の高い接続信頼性とペーストの優れた印刷作業性とを効果的に実現することができる。
はじめに、ベースエポキシ樹脂と、ゴム変性エポキシ樹脂と、反応性希釈剤と、有機酸と、硬化剤とを、はんだペーストにおいて以下の表1に記載の重量部を占めるような割合となるようにそれぞれ秤量し、プラネタリーミキサーに入れて各成分を混練し、エポキシ樹脂中に均一に分散させて、実施例1〜6および比較例1〜4のフラックスを調製した。ベースエポキシ樹脂には、ビスフェノールF型エポキシ樹脂(ジャパンエポキシレジン社製、jER806)を用いた。ゴム変性エポキシ樹脂には、ポリブタジエン変性エポキシ樹脂(ナガセケムテック社製、R−15EPT)と、ウレタン変性エポキシ樹脂(ADEKA社製、EPU−7N)とを、適宜用いた。有機酸には、グルタル酸(関東化学社製)を用いた。硬化剤には、四国化成工業社製のイミダゾール系硬化剤である2P4MHZ(2−フェニル−4−メチル−5−ヒドロキシメチルイミダゾール)を用いた。
上述のとおりに作成されたはんだペーストを、メタルマスクを用いて、厚さが0.1mmとなるように、回路基板(FR−4基板)上のAuメッキされた電極上に印刷して、はんだペースト印刷部を形成した。
実施例1〜6および比較例1〜4について、以下の項目について評価した。評価結果は、各例におけるはんだペーストの特性として表1に併せて示した。
メタルマスクを用いて印刷したはんだペーストの形状を観察することによって、はんだペーストの印刷性の評価を行った。観察は、目視にて、電極エリアへの収まり状態、ダレや尖がり形状に対して行った。印刷性の評価は、ペーストをマスクの貫通孔を通過させて回路基板の電極上に転写した時の形状で判定した。電極部に形状が保持できているものを○、形状に不具合(ダレや尖がりの発生)があるものを△、非常に形状が悪いものを×とした。
図4は、チップ部品のせん断密着力測定方法を示した断面模式図である。チップ部品10を加熱可能なホットプレートステージ12に固定し、せん断冶具11を用いて、水平に押すことで、密着強度を測定する。このような方法で測定がなされるボンドテスター装置(DAGE社製、Series4000)を用いて、上記のように作製した密着性の評価素子の室温20℃におけるせん断密着力を測定することによって、はんだペーストの室温密着性の評価を行った。室温密着性の評価は、接合部に掛かる荷重が15Kg/チップを越えても破損しなかった物を○、接合部に掛かる荷重が14Kg/チップ未満の範囲で破損を生じたものを×とした。
上記の室温密着性の評価と同様に、ボンドテスター装置(DAGE社製、Series4000)を用い、図4に示されるように評価素子がホットプレートステージ12に固定された状態でホットプレートを加熱し、評価素子を160℃まで加熱したうえで、上記と同様にせん断密着力を測定することによって、はんだペーストの高温密着性の評価を行った。高温密着性の評価は、接合部に掛かる荷重が5Kg/チップ以下で接合部を外すことができた場合を○、接合部に掛かる荷重が6Kg/チップ以上7Kg/チップ以下の範囲で接合部を外すことができたものを△、接合部に掛かる荷重が8Kg/チップ以上の荷重がかからないと接合部がはずれなかったものを×とした。
評価素子の作製において、メタルマスクを用いてはんだペーストを印刷した基板にチップ部品は搭載せずに、リフロー装置を用いて160℃で6分加熱した。この基板上のエポキシ樹脂硬化物の表層部に、ブリードがあるかどうかを顕微鏡観察にて判定した。ブリードが発生していないものを○、ブリードが発生しているものを×とした。
くし型パターン基板(導体幅0.3mm、導体間隔0.3mm)を有する回路基板に、はんだペーストを印刷塗布し、電極間をペーストの樹脂で被覆した基板を、85℃85%RHの高温高湿槽に1000時間入れて直流電圧50Vを印加した。その時の抵抗値を測定し、体積抵抗率に換算した。耐湿絶縁性の評価は、体積抵抗率が1×108Ω・cm以上のものを○、1×107Ω・cm以上1×108Ω・cm未満のものを△、1×107Ω・cm未満のものを×とした。
印刷性、室温密着性、高温密着性、ブリードの有無および耐湿絶縁性の5つの評価で、全項目が○のものを○、1個でも△があるものを△、1個でも×があるものを×として、総合的な評価を行った。
2 電極
3 回路基板
4 電極
5 はんだバンプ
6a エポキシ樹脂
6b 補強部
7 はんだペースト
8 乾燥機
9 導電部
10 チップ部品
11 せん断冶具
12 ホットプレートステージ
21 回路基板
22 電極
23 回路基板
24 電極
25 SACはんだバンプ
26b 補強部
27 はんだペースト
28 乾燥機
29 SnBi低温はんだ導電部
Claims (6)
- はんだ粉末とフラックスとを含み、
前記フラックスは、エポキシ樹脂、反応性希釈剤、硬化剤、有機酸およびゴム変性エポキシ樹脂を含み、
前記反応性希釈剤は、2つ以上のエポキシ基を有する化合物を含み、E型粘度計を使用して測定される粘度が150mPa・s以上700mPa・s以下であり、当該反応性希釈剤中に含まれる全塩素量が0.5重量%以下であり、前記フラックスの全重量に対して5重量%以上45重量%以下の割合で含まれる、
はんだペースト。 - 前記反応性希釈剤の2つ以上のエポキシ基を有する化合物は、2つまたは3つのエポキシ基を有する、請求項1に記載のはんだペースト。
- 前記反応性希釈剤の2つ以上のエポキシ基を有する化合物は、ジシクロペンタジエンジメタノールジグリシジルエーテル、1,3−ビス[(2,3エポキシプロピル)オキシ]ベンゼンおよびN,N−ビス(2,3−エポキシプロピル)−4−(2,3−エポキシプロポキシ)アニリンからなる群から選択される少なくとも1つを含む、請求項1または2に記載のはんだペースト。
- 前記反応性希釈剤は、前記フラックスの全重量に対して、5重量%以上30重量%以下の割合で含まれる、請求項1〜3のいずれか1項に記載のはんだペースト。
- 前記ゴム変性エポキシ樹脂は、ポリブタジエン骨格を有するエポキシ樹脂およびポリウレタン骨格を有するエポキシ樹脂からなる群から選択される少なくとも1つを含む、請求項1〜4のいずれか1項に記載のはんだペースト。
- 前記はんだ粉末は、22重量%以上68重量%以下のBiと、0重量%以上2重量%以下のAgと、0重量%以上73重量%以下のInとを含み、残部がSnである、請求項1〜5のいずれか1項に記載のはんだペースト。
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US11224132B2 (en) * | 2019-09-06 | 2022-01-11 | Advanced Semiconductor Engineering, Inc. | Semiconductor device package and method of manufacturing the same |
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