JP3968302B2 - Liquid epoxy resin composition for semiconductor encapsulation and semiconductor device - Google Patents
Liquid epoxy resin composition for semiconductor encapsulation and semiconductor device Download PDFInfo
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- JP3968302B2 JP3968302B2 JP2002377604A JP2002377604A JP3968302B2 JP 3968302 B2 JP3968302 B2 JP 3968302B2 JP 2002377604 A JP2002377604 A JP 2002377604A JP 2002377604 A JP2002377604 A JP 2002377604A JP 3968302 B2 JP3968302 B2 JP 3968302B2
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/10—Bump connectors; Manufacturing methods related thereto
- H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
- H01L2224/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
- H01L2224/161—Disposition
- H01L2224/16151—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/16221—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/16225—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
- H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
- H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
- H01L2224/321—Disposition
- H01L2224/32151—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/32221—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/32225—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
- H01L2224/732—Location after the connecting process
- H01L2224/73201—Location after the connecting process on the same surface
- H01L2224/73203—Bump and layer connectors
- H01L2224/73204—Bump and layer connectors the bump connector being embedded into the layer connector
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
- H01L2924/151—Die mounting substrate
- H01L2924/153—Connection portion
- H01L2924/1531—Connection portion the connection portion being formed only on the surface of the substrate opposite to the die mounting surface
- H01L2924/15311—Connection portion the connection portion being formed only on the surface of the substrate opposite to the die mounting surface being a ball array, e.g. BGA
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Description
【０００１】
【発明の属する技術分野】
本発明は高信頼性が要求される半導体装置に好適な半導体封止用液状エポキシ樹脂組成物に関する。
【０００２】
【従来の技術】
近年、半導体装置はICの高密度実装化、高集積化に伴い配線長が短く、高周波用、多ピン化に向いているフリップチップ実装方式の形態が多くなっている。この方式は実装面積がチップサイズとほぼ同じの大きさであること、プリント基板にチップを直接搭載できることから、小型、軽量、薄型化の点で有利である。このフリップチップ実装型の半導体を封止する封止材には液状タイプとフィルムタイプの封止材があるが液状タイプが多い。その材質はエポキシ樹脂が主流となっている。理由は電気特性、耐熱性、機械的特性、接着性、コスト面にバランスが取れているためである。
【０００３】
液状エポキシ樹脂による半導体封止法はセラミックによる気密封止法に比べ信頼性の点で劣る。しかしながら、例えば、チップを基板に直接熱などで圧着接続した接続部周辺をキャピラリーフロー方式で樹脂封止し半導体装置を得る方法は、工程が短く、コスト的に有利な方法のひとつである。
【０００４】
このようにして得られる半導体装置の最重要課題は信頼性である。半導体装置の信頼性を評価する試験としては、例えば、耐湿性を評価するためのプレッシャークッカーテスト（以下、ＰＣＴと略称する）や、耐熱衝撃性、耐熱性を評価するための温度サイクル試験や高温放置試験等がある。
【０００５】
半導体装置の信頼性と半導体封止用液状エポキシ樹脂組成物の特性（耐湿性や接着性）とは関連があり、半導体装置の高信頼性化のため、半導体封止用液状エポキシ樹脂組成物には高耐湿性化や高接着性化が求められている。半導体封止用液状エポキシ樹脂組成物には酸無水物硬化、アミン硬化や自己重合タイプ等とがあるが、耐湿性や接着性の点からアミン硬化タイプが有利である。しかし、アミン硬化タイプは保存安定性が悪いという問題がある。
【０００６】
また、半導体封止用液状エポキシ樹脂組成物の接着性を向上させるために、N-ブチルゴムやフッ素ゴム、アクリロニトリル-ブタジエンゴム等のゴム成分を配合したりエポキシ樹脂に結合させることなどが行われている。しかしながら、各種ゴム系を配合すると耐熱性が低下するという問題がある。
【０００７】
【特許文献１】
特開平１０−１５８３６６号公報（特許請求の範囲）
【０００８】
【発明が解決しようとする課題】
本発明は、上記の問題点を解決し、耐湿性、接着性及び保存安定性が良好な半導体封止用に適したエポキシ樹脂組成物を提供することを目的とする。
【０００９】
【課題を解決するための手段】
そこで本発明者らは半導体装置の信頼性向上を目的に、液状エポキシ樹脂材料の耐湿性、接着性を改良するため鋭意検討した結果、液状エポキシ樹脂と特定のアミン系硬化剤とを必須成分とする液状エポキシ樹脂組成物を用いて半導体を封止して製造された半導体装置は、ＰＣＴや温度サイクル試験等のストレス付与試験においても信頼性を大幅に向上できることを見出し、本発明を完成することにいたった。
【００１０】
即ち、本発明は以下の発明を包含する。
（１）液状エポキシ樹脂（ｃ）と一般式（１）：
【００１１】
【化２】
（２）２５℃において粘度が１０Ｐａ・ｓ以下の芳香族アミン化合物（ｂ）をさらに含有する前記（１）記載の半導体封止用液状エポキシ樹脂組成物。
【００１２】
（３）前記化合物（ａ）と前記化合物（ｂ）との当量比が、（ａ）：（ｂ）＝９９：１〜３０：７０である前記（１）又は（２）記載の半導体封止用液状エポキシ樹脂組成物。
（４）前記液状エポキシ樹脂（ｃ）と前記化合物（ａ）及び（ｂ）との当量比が、（ｃ）：（（ａ）+（ｂ））＝１００：８０〜１００：１１５である前記（２）記載の半導体封止用液状エポキシ樹脂組成物。
【００１３】
（５）前記化合物（ｂ）が2,5-ジアミノ-4,6-ジエチルトルエン又は3,3'-ジエチル-4,4'-ジアミノジフェニルメタンである前記（１）〜（４）のいずれかに記載の半導体封止用液状エポキシ樹脂組成物。
（６）前記（１）〜（５）のいずれかに記載の半導体封止用液状エポキシ樹脂組成物で封止した素子を備えた半導体装置。
【００１４】
【発明の実施の形態】
本発明で用いられるエポキシ樹脂（ｃ）は室温で液状であることが必要である。エポキシ樹脂が室温で液状でないと、半導体封止用液状エポキシ樹脂組成物の粘度が高くなる。エポキシ樹脂組成物の粘度が高いと、例えば、フリップチップ実装したチップと基板の隙間に半導体封止用液状エポキシ樹脂組成物をキャピラリーフローで注入封止する際、気泡を巻き込んだり、コーナー端部への充填不良が発生し、半導体装置の信頼性低下に繋がり好ましくない。この条件を満たすエポキシ樹脂であれば、特に限定されるものではないが、具体例を挙げるとビスフェノールAジグリシジルエーテル型エポキシ、ビスフェノールFジグリシジルエーテル型エポキシ、ビスフェノールSジグリシジルエーテル型エポキシ、ビスフェノールADジグリシジルエーテル型エポキシ、水添ビスフェノールAジグリシジルエーテル型エポキシ、フェノールノボラック型エポキシ、フタル酸、ダイマー酸等の多塩基酸とエピクロルヒドリンとの反応により得られるグリシジルエステル型エポキシ、ジアミノジフェニルメタン、イソシアヌル酸等のポリアミンとエピクロルヒドリンとの反応により得られるグリシジルアミン型エポキシ、オレフィン結合を過酢酸等の過酸により酸化して得られる脂肪エポキシ、脂環族エポキシ等がある。これらは単独でも、２種以上を混合してもさしつかえない。本発明の半導体封止用液状エポキシ樹脂組成物には、本発明の効果を達成する範囲内であれば、室温で固形のエポキシ樹脂も配合することができる。また、信頼性に優れた半導体封止用液状エポキシ樹脂組成物を得るため、エポキシ樹脂にはNa+、Cl-などのイオン性不純物はできるだけ少ないものが好ましく、500ppm以下であることが好ましい。
【００１５】
本発明に用いられる一般式（１）で示されるアミン化合物（ａ）は３つのベンゼン環を有し、硬化剤として作用する。
本発明に用いられる一般式（１）で示されるアミン化合物（ａ）は、具体的には、２つのアミノフェノキシ基がベンゼンに結合した化合物であり、アミノ基はフェノキシ基のどの位置に置換していてもよいが、３位又は４位が好ましく、また、アミノフェノキシ基はベンゼンのどの位置に置換していてもよいが、１,３-置換体又は１,４-置換体が好ましい。このような化合物の具体例としては、例えば、1,3-ビス(3-アミノフェノキシ)ベンゼン、1,4-ビス(3-アミノフェノキシ)ベンゼン、1,3-ビス(4-アミノフェモキシ)ベンゼンなどが挙げられる。
【００１６】
一般式（１）で示されるアミン化合物を配合した半導体封止用エポキシ樹脂組成物は接着性に優れるため、有機プリント配線基板を用いたフリップチップ実装型半導体装置の信頼性を大幅に向上させることができる。
一般式（１）に示すアミン化合物は芳香環をつなぐ結合基が電子吸引性のエーテル（-O-）基であるためアミノ基の窒素原子の電子密度が低い。即ちアミノ基の求核性が低くなり、室温付近ではエポキシ基との反応性が低下する。その結果、半導体封止用エポキシ樹脂組成物の室温での粘度変化が小さく、優れた保存安定性を示す。芳香環以外のアミン系硬化剤は耐熱性に乏しく、室温以下でも反応性に富むため、半導体封止用エポキシ樹脂組成物の耐熱性や保存安定性に劣る欠点があり、本発明には適さない。
【００１７】
フリップチップ実装した素子と基板との隙間に半導体封止用液状エポキシ樹脂組成物をキャピラリーフロー封入する場合、基板を加熱すると一般的な封止用エポキシ樹脂組成物は粘度が室温（25℃）の約1/100〜1/300に低下するので、短時間で封入することができる。従って、封入時間を短くすることができる粘度の低い封止用エポキシ樹脂組成物ほど有利である。
【００１８】
一般式（１）に示す芳香環が３つからなるアミン化合物（ａ）は室温で固体である。そのため液状エポキシ樹脂と混合した場合にアミン化合物（ａ）のエポキシ樹脂への溶解性が十分でなく、かつ半導体封止用エポキシ樹脂組成物の粘度が高まる傾向にある。本発明に用いられるアミン化合物（ａ）を液状エポキシ樹脂に混合して得られる半導体封止用液状エポキシ樹脂組成物の室温時の粘度は上昇するが、しかしながら、100℃の雰囲気下では室温時の粘度の約1/1000と大きく低下する。この大きく低下する理由は解明されてないが、一般式（１）に示すアミン系硬化剤の芳香環の数と骨格の影響と予想される。
【００１９】
本発明においては、室温でのアミン化合物（ａ）の液状エポキシ樹脂に対する溶解性の向上、及び得られる半導体封止用エポキシ樹脂組成物の粘度を低下させる目的で、低粘度の液状芳香族アミン化合物（ｂ）を一般式（１）に示すアミン系硬化剤（ａ）とともに用いてもよい。低粘度の液状芳香族アミン化合物（ｂ）としては、２５℃で１０Ｐａ・ｓ以下の粘度を有する液状芳香族アミン化合物であることが必要である。このような低粘度の液状芳香族アミンとしては、例えば、3,3'-ジエチル-4,4'-ジアミノジフェニルメタン、2,5-ジアミノ-4,6-ジエチルトルエン等が挙げられる。
【００２０】
上記液状芳香族アミン化合物（ｂ）と一般式（１）に示す芳香環を３つ含むアミン化合物（ａ）との混合物をエポキシ樹脂と組み合わせることによって、溶解性が改善され、また流動性に優れた半導体封止用液状エポキシ樹脂組成物を提供することができる。液状アミン化合物を用いる場合、一般式（１）に示すアミン化合物(a)と芳香族アミン化合物(b)との当量比は（ａ）：（ｂ）＝９９：１〜３０：７０とすることが好ましい。化合物（ａ）と化合物（ｂ）との全量に関して、化合物（ａ）が当量比で30％未満の場合、芳香族アミン化合物（ｂ）が過剰になるため保存安定性が低下する傾向にある。信頼性に優れた半導体封止用液状エポキシ樹脂組成物を得るため、一般式（１）で示される芳香族アミン化合物（ａ）及び（ｂ）はNa+、Cl-などのイオン性不純物はできるだけ少ないものが好ましく、500ppm以下が好ましい。
【００２１】
主剤である液状エポキシ樹脂(c)と、アミン化合物(a)及びアミン化合物(b)との当量比は(c)：（(a)+(b)）＝１００：８０〜１００：１１５とすることが好ましい。液状エポキシ樹脂(c)の当量に対するアミン化合物(a)及びアミン化合物(b)の当量比が１．１５（１００：１１５）を超えると、硬化剤としてのアミン化合物が過剰となって多くのアミノ基が存在するため耐湿性が低下する傾向にある。液状エポキシ樹脂(c)の当量に対するアミン化合物(a)及びアミン化合物(b)の当量比が０．８０（１００：８０）未満の場合は、エポキシ基が多くなるため樹脂の硬化が不十分となり、硬化物の耐熱性が低下する傾向にある。(c)：（(a)+(b)）＝１００：８０〜１００：１１５の範囲外の当量比の樹脂を用いた場合はいずれも半導体装置の信頼性の向上効果が不十分となる傾向にある。
【００２２】
本発明の半導体封止用液状エポキシ樹脂組成物は、一般的に用いられる無機充填剤を含有していてもよい。無機充填剤は吸湿性、熱膨張係数低減、熱伝導性の向上及び機械強度向上のため、エポキシ樹脂組成物に配合されるものである。具体的には溶融シリカ、結晶シリカ、アルミナ、ジルコン、珪酸カルシウム、炭酸カルシウム、チタン酸カリウム、炭化珪素、窒化珪素、窒化アルミ、窒化ホウ素、ベリリア、ジルコニア、ジルコン、フォステライト、ステアタイト、スピネル、ムライト、チタニア等の粉体、又これらを球形化したビーズ、ガラス繊維等が挙げられる。さらに難燃効果のある無機充填剤としては水酸化アルミニウム、水酸化マグネシウム、珪酸亜鉛、モリブデン酸亜鉛などが挙げられる。これらの無機充填剤は単体でも二種類以上を組み合わせてもよい。
【００２３】
この無機充填剤の中で、熱膨張係数低減の観点からは溶融シリカが、高熱伝導性の点から結晶シリカ及びアルミナが好ましい。無機充填剤の粒子形状は、微細間隙への流動性、浸透性の点から球状が好ましく、その平均粒径は0.1〜20μmが好ましい。平均粒径0.1μm未満では液状樹脂への分散性が劣る傾向にある。また、液状封止用エポキシ樹脂組成物にチキソトロピック性が付与され流動性が劣る傾向がある。平均粒径20μmを超えるとフィラ沈降がおきやすくなり、キャピラリーフローにより、フリップチップ実装した素子と基板の隙間に液状封止用エポキシ樹脂組成物を封入する場合、微細間隔への流動性、浸透性が劣る傾向にある。無機充填剤の配合割合は、本発明のエポキシ組成物に対して0〜90重量％の範囲で調整可能である。特に30〜85重量％の範囲が好ましく、40〜80重量％がさらに好ましい。無機充填剤の配合割合が30重量％未満では熱膨張係数低減効果が小さい傾向にあるが、無機充填剤の配合割合0重量％の場合でもチップサイズ、接続方法、接続用電極の種類やその形状及び大きさや素子を搭載する基板やレジストの材質等により実用上十分な信頼性を確保できる場合もある。無機充填剤の配合割合が90重量％を超えると半導体封止用液状エポキシ樹脂組成物が高粘度化して、封入時の流動性が大きく低下する傾向にある。
【００２４】
また、本発明の半導体封止用液状エポキシ樹脂組成物には、シクロアミジン化合物、３級アミン類、イミダゾール類、有機ホスフィン類等のリン化合物、及びこれらの誘導体、又はそれらのテトラフェニルボロン塩など、一般的に使用されている公知の硬化促進剤を、単体または二種類以上を組み合わせて、必要に応じて配合することができる。硬化促進剤の配合量は硬化促進効果が達成される量であれば特に限定されるものではない。
【００２５】
本発明の半導体封止用液状エポキシ樹脂組成物には、エポキシシラン、アミノシラン、ウレイドシラン、ビニルシラン、アルキルシラン、有機チタネート、アルミニウムアルキレート等の公知のカップリング剤を、単独、あるいは二種類以上組み合わせて、必要に応じて配合することができる。また、赤燐、燐酸エステル、メラミン、メラミン誘導体、トリアジン環を有する化合物、シアヌル酸誘導体、イソシアヌル酸誘導体の窒素含有化合物、シクロホスファゼン等の燐窒素含有化合物、酸化亜鉛、酸化鉄、酸化モリブデン、フェロセン等の金属化合物、三酸化アンチモン、四酸化アンチモン、五酸化アンチモン等の酸化アンチモン、ブロム化エポキシ樹脂等の難燃剤を、単独あるいは二種以上を組み合わせて配合することができる。
【００２６】
本発明の半導体封止用液状エポキシ樹脂組成物には、半導体素子の耐湿性、高温放置特性を向上させる、イオントラッパー剤も配合することができる。イオントラッパー剤としては特に制限はなく、これまで公知のものを用いることができる。具体的にはハイドロタルサイト類、マグネシウム、アルミニウム、チタン、ジルコニウム、ビスマス等の元素の含水酸化物などが挙げられる。これらを、単独あるいは二種以上を組み合わせて配合することができる。
さらに本発明の半導体封止用液状エポキシ樹脂組成物には、その他の添加剤として、シリコーンゴム粉末等の応力緩和剤、染料、カーボンブラック等の着色剤、レベリング剤、消泡剤等を必要に応じて配合することができる。
【００２７】
本発明の半導体封止用液状エポキシ樹脂組成物は上記各種成分を均一に分散混合できるものであればいかなる手法を用いても調整できる。一般的には所定量を秤量した後、三本ロールや真空らいかい機、ハイブリッドミキサー（KEYENCE社製、MH-500型）等によって分散混合をおこなう方法が挙げられる。
本発明の半導体封止用液状エポキシ樹脂組成物を用いて素子を封止する方法としては、ディスペンス方式、注型方式、印刷方式等がある。
本発明で得られる半導体封止用液状エポキシ樹脂組成物により素子を封止して得られる半導体装置としては、例えば以下のものが挙げられる。
【００２８】
裏面に配線板接続用の端子を形成した有機基板又は無機基板の表面に素子を搭載し、バンプやワイヤボンディングにより素子と有機基板に形成された配線を接続した後、本発明の半導体封止用液状エポキシ樹脂組成物で素子を封止したＢＧＡ、ＣＳＰ(チップサイズパッケージ)等が挙げられる。さらに具体的には、素子の回路形成面と素子を搭載する有機又は無機基板の回路形成面を対向させ、素子の電極と基板の回路をバンプを介して電気的に接続し、素子と基板の隙間に本発明の半導体封止用エポキシ樹脂組成物を含浸させたフリップチップ実装型半導体装置等が挙げられる。
【００２９】
【実施例】
次に実施例により本発明を具体的に説明するが、本発明の範囲はこれらの実施例に限定されるものではない。まず、実施例及び比較例で用いた樹脂類を示す。これらは以後商品名又は略号で示す。
【００３０】
イ） 液状エポキシ樹脂＝ビスフェノールFエポキシ樹脂（ジャパンエポキシ株式会社製、エポキシ当量160、略号BF）
ロ） 液状エポキシ樹脂＝ビスフェノールAエポキシ樹脂（ジャパンエポキシ株式会社製、商品名＝エピコート828、エポキシ当量195、略号BA）
ハ） 硬化剤＝1,3-ビス(3-アミノフェノキシ)ベンゼン（三井化学株会社製、略号APB）
ニ） 硬化剤＝1,4-ビス(4-アミノフェノキシ)ベンゼン（ 和歌山精化式会社製、略号APOB）
ホ） 硬化剤＝3,3'-ジエチル-4,4'-ジアミノジフェニルメタン（日本化薬株式会社製、商品名＝カヤハードA-A、略号A-A、25℃での粘度＝3.0 Pa・s）
ヘ） 硬化剤＝2,2-ビス(4-(4-アミノフェノキシ)フェニル)プロパン（Aldrich社製、略号BAPP、m.p.＝127℃）
ト） 硬化剤＝4,4'-ジアミノジフェニルメタン（和光純薬株式会社製、略号DDM、m.p.＝90℃）
チ） カップリング剤＝3-グリシドキシプロピル-トリメトキシシラン（信越化学株式会社製、商品名＝KBM403）
リ） 無機充填剤 ＝平均粒径4.4μmの球状溶融シリカ（略号Ｅ）
【００３１】
これらを用いて表１に示す組成で配合し、三本ロールで混合分散した後、真空らいかい機で混合脱気を行い、実施例１〜６及び比較例１〜４の半導体封止用液状エポキシ樹脂組成物を作製した。
半導体封止用液状エポキシ樹脂組成物で封止する素子を備えた半導体装置の一例として、フリップチップ実装型のＢＧＡを下記（3）の方法で作製した。これを100℃のホットプレートに置き、実施例１〜６及び比較例１〜４の半導体封止用液状エポキシ樹脂組成物をディスペンサを用いてチップの一端辺に滴下し、毛細管現象（キャピラリーフロー）により素子と基板の隙間に封入し、更に160℃で2時間硬化して樹脂封止したフリップチップ実装型のＢＧＡを得た。それぞれの実施例及び比較例について10個ずつ作製した。
【００３２】
本発明の半導体封止用液状エポキシ樹脂組成物の保存安定性や素子のパッシベーション膜（ポリイミド）とのせん断接着力評価、本発明の材料を用いて素子を封止した半導体装置の耐熱衝撃性や耐湿性等を以下の試験により評価した。
（１）保存安定性
本発明の半導体封止用液状エポキシ樹脂組成物と比較例のエポキシ樹脂成形材料のそれぞれについて、25℃における初期粘度と20時間後の25℃における粘度から粘度増加率を求めた。粘度増加率の低いものほど保存安定性に優れる。粘度は、測定は回転粘度計（HAKKE社製、RS100型）で25℃、ずり速度10（1/ｓ）の値を示す。その結果を表１に示す。
【００３３】
（２）ポリイミドとのせん断接着力評価
シリコンウエハ上にパッシベーション膜としてネガ型感光性ポリイミド（日立化成デュポンマイクロシステムズ株式会社製、ＰＬ-Ｈ708）を日立化成デュポンマイクロシステムズ推奨のパターン形成プロセス法に従い、スピンコート、プリベーク、フォトマスクを用いずにi線露光、露光後加熱を行い、現像液(日立化成デュポンマイクロシステムズ株式会社製、PL-2N)で現像、水でリンスを行った後、窒素雰囲気下の温風乾燥機で350℃で60分加熱し、 本発明の液状封止用エポキシ樹脂成形材料とのせん断接着力を評価するポリイミド膜を塗布したシリコンウエハを得た。ポリイミドは膜厚約10μmである。このシリコンウエハをサイズ2cm×2cmに切断し、4mm×4mm四方の穴を開けた厚さ約1mmのシリコンゴムシート（サイズ2cm×2cm）を重ね、更に4mm×4mmの穴を開けた厚さ約1mmのテトラフルオロエチレンシート（サイズ2cm×2cm）を重ね、四方よりクリップで挟み固定した。シリコンゴムシートとテトラフルオロエチレンシートに開けた4mm×4mm四方の穴の中に本発明の半導体封止用液状エポキシ樹脂組成物を、気泡を巻き込まないようにディスペンサーを用いて厚さ約0.5〜１mm入れ、温風乾燥機で160℃で2時間加熱硬化した。その後、シリコンゴムシート、テトラフルオロエチレンシートをポリイミド膜を塗布したシリコンウエハからはずし、ポリイミド塗布シリコンウエハ上に4mm×4mm×約0.5〜1mmの硬化物を有するサンプルを得た。これを万能ボンドテスター（デイジ社製、PC2400型）を用いてポリイミドと本発明の半導体封止用液状エポキシ樹脂組成物から成る硬化物とのせん断接着強さを測定し、接着性を評価した。せん断強度の大きいものほど接着性に優れる。測定条件は硬化物ブロックにせん断治具を用いてポリイミドから50μmの高さを300μm/秒の速度で歪を加えながら測定した。実施例では初期値と耐湿試験の一環としてPCT試験による168時間後の値を示した。その結果を表１に示す。
【００３４】
【表１】
（３）フリップチップ実装型ＢＧＡの作製
図１に示すように複数の接続用電極部（金メッキ）２が設けられた配線回路基板１に接続用電極部（金バンプ）３が設けられた半導体素子４を配置し、２と３とを接続位置に配置し、１と４とを加圧及び加熱（260℃）することにより両接続用電極部２と３とを当接して、ボンダーを用いて電気的接続を行い、本発明の半導体封止用液状エポキシ樹脂組成物が未封入のフリップチップ実装型のＢＧＡを作製した。ギャップは60μmである。用いたＢＧＡはデイジーチェーン回路であるので、両末端端子間の接続抵抗をテスターで測定し初期値とした。各種試験後も測定し、それぞれの抵抗値の変化からアンダーフィル材の信頼性を評価した。
【００３６】
（４）ストレス付与試験
上記（３）に従って製造したフリップチップ実装型のＢＧＡの素子と基板の隙間に本発明の半導体封止用液状エポキシ樹脂組成物６を注入して素子を封止した。封止したＢＧＡ全てに初期導通試験を25℃で行い、さらにその半導体装置を各5個ずつ用いて、耐熱衝撃性評価試験の一環として温度サイクル試験を500サイクル行った。温度サイクル試験の1サイクルは-55℃×5分次いで125℃×5分である。その後、再度、通電試験及び半導体装置のクラックの有無検査を行った。その結果を表２に示す。
【００３７】
また、上記温度サイクル試験を行わなかった各5個の半導体装置について耐湿試験としてＰＣＴを168時間行った。ＰＣＴは圧力容器中で半導体装置を121℃、2気圧、100％RHの環境下に曝すものである。その後、再度通電試験を行った。その結果を表２に示す。
【００３８】
【表２】
以上、実施例と比較例に示したように、本発明の半導体封止用液状エポキシ樹脂組成物は接着性、耐湿性、及び保存安定性に優れている。また、本発明の液状封止用エポキシ樹脂組成物を封入した半導体装置は、初期通電試験や温度サイクル試験及びＰＣＴのストレス付与試験に対して安定した通電を確保しており、信頼性の高い半導体装置が得られる。
【００４０】
【発明の効果】
本発明の半導体封止用液状エポキシ樹脂組成物は、一般式（１）に示す芳香族アミンを用いているためＰＣＴによるせん断強度の低下もなく、また粘度増加率も小さい。そのため複数の接続用電極部を介して接続された配線回路基板と半導体素子の空隙に、キャピラリーフローにより封入された本発明の半導体封止用液状エポキシ樹脂組成物によって樹脂封止層が形成された半導体装置は初期通電試験や温度サイクル試験及びＰＣＴのストレス付与試験に対して安定した通電を確保する。
【図面の簡単な説明】
【図１】実施例で用いたＢＧＡの模式断面図である。
【符号の説明】
１… 配線回路基板
２… 接続用電極部（金メッキ）
３… 接続用電極部（金バンプ）
４… 半導体素子
５… はんだボール
６… 半導体封止用エポキシ樹脂組成物[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a liquid epoxy resin composition for semiconductor encapsulation suitable for a semiconductor device requiring high reliability.
[0002]
[Prior art]
2. Description of the Related Art In recent years, with the increase in IC density and integration, semiconductor devices have a short wiring length, and the number of flip chip mounting methods suitable for high frequency use and high pin count is increasing. This method is advantageous in terms of small size, light weight, and thinning because the mounting area is almost the same as the chip size and the chip can be directly mounted on the printed circuit board. There are liquid type and film type sealing materials for sealing the flip chip mounting type semiconductor, but there are many liquid types. The material is mainly epoxy resin. The reason is that the electrical characteristics, heat resistance, mechanical characteristics, adhesion, and cost are balanced.
[0003]
The semiconductor sealing method using liquid epoxy resin is inferior in terms of reliability as compared with the hermetic sealing method using ceramic. However, for example, a method of obtaining a semiconductor device by sealing the periphery of a connection portion in which a chip is directly bonded to a substrate by heat or the like by a capillary flow method is a short method and advantageous in terms of cost.
[0004]
The most important issue of the semiconductor device thus obtained is reliability. As a test for evaluating the reliability of a semiconductor device, for example, a pressure cooker test (hereinafter abbreviated as PCT) for evaluating moisture resistance, a temperature cycle test for evaluating thermal shock resistance and heat resistance, or a high temperature There are neglect tests.
[0005]
The reliability of semiconductor devices and the properties (moisture resistance and adhesiveness) of liquid epoxy resin compositions for semiconductor encapsulation are related. To improve the reliability of semiconductor devices, liquid epoxy resin compositions for semiconductor encapsulation are used. Is required to have high moisture resistance and high adhesion. The liquid epoxy resin composition for semiconductor encapsulation includes acid anhydride curing, amine curing, self-polymerization type, and the like, but the amine curing type is advantageous from the viewpoint of moisture resistance and adhesiveness. However, the amine curing type has a problem that the storage stability is poor.
[0006]
In addition, in order to improve the adhesion of the liquid epoxy resin composition for semiconductor encapsulation, a rubber component such as N-butyl rubber, fluorine rubber, acrylonitrile-butadiene rubber or the like is compounded or bonded to the epoxy resin. Yes. However, when various rubber systems are blended, there is a problem that heat resistance is lowered.
[0007]
[Patent Document 1]
JP-A-10-158366 (Claims)
[0008]
[Problems to be solved by the invention]
The object of the present invention is to solve the above-mentioned problems and to provide an epoxy resin composition suitable for semiconductor encapsulation having good moisture resistance, adhesion and storage stability.
[0009]
[Means for Solving the Problems]
Therefore, the present inventors have made extensive studies to improve the moisture resistance and adhesion of the liquid epoxy resin material for the purpose of improving the reliability of the semiconductor device. As a result, the liquid epoxy resin and a specific amine curing agent are included as essential components. A semiconductor device manufactured by encapsulating a semiconductor using a liquid epoxy resin composition to be found can greatly improve reliability even in a stress application test such as a PCT or a temperature cycle test, and the present invention is completed. I went to.
[0010]
That is, the present invention includes the following inventions.
(1) Liquid epoxy resin (c) and general formula (1):
[0011]
[Chemical 2]
(2) The liquid epoxy resin composition for semiconductor encapsulation according to (1), further containing an aromatic amine compound (b) having a viscosity of 10 Pa · s or less at 25 ° C.
[0012]
(3) The semiconductor encapsulation according to (1) or (2), wherein the equivalent ratio of the compound (a) to the compound (b) is (a) :( b) = 99: 1 to 30:70 Liquid epoxy resin composition.
(4) The equivalent ratio of the liquid epoxy resin (c) to the compounds (a) and (b) is (c): ((a) + (b)) = 100: 80 to 100: 115 (2) Liquid epoxy resin composition for semiconductor encapsulation as described in (2).
[0013]
(5) In any one of the above (1) to (4), wherein the compound (b) is 2,5-diamino-4,6-diethyltoluene or 3,3′-diethyl-4,4′-diaminodiphenylmethane The liquid epoxy resin composition for semiconductor sealing of description.
(6) A semiconductor device comprising an element encapsulated with the liquid epoxy resin composition for encapsulating a semiconductor according to any one of (1) to (5).
[0014]
DETAILED DESCRIPTION OF THE INVENTION
The epoxy resin (c) used in the present invention needs to be liquid at room temperature. When the epoxy resin is not liquid at room temperature, the viscosity of the liquid epoxy resin composition for semiconductor encapsulation becomes high. When the viscosity of the epoxy resin composition is high, for example, when the liquid epoxy resin composition for semiconductor sealing is injected and sealed in the gap between the chip mounted on the flip chip and the substrate by capillary flow, air bubbles are involved, and the corner ends. Inadequate filling, which leads to a decrease in the reliability of the semiconductor device. Any epoxy resin that satisfies this condition is not particularly limited, but specific examples include bisphenol A diglycidyl ether type epoxy, bisphenol F diglycidyl ether type epoxy, bisphenol S diglycidyl ether type epoxy, bisphenol AD. Diglycidyl ether type epoxy, hydrogenated bisphenol A diglycidyl ether type epoxy, phenol novolac type epoxy, phthalic acid, dimer acid and other polybasic acids and glycidyl ester type epoxy obtained by reaction with epichlorohydrin, diaminodiphenylmethane, isocyanuric acid, etc. Glycidylamine-type epoxy obtained by the reaction of polyamine and epichlorohydrin, fatty epoxy obtained by oxidizing olefinic bonds with peracid such as peracetic acid, alicyclic epoxy, etc. That. These may be used alone or in combination of two or more. If it is in the range which achieves the effect of this invention, the solid epoxy resin at room temperature can also be mix | blended with the liquid epoxy resin composition for semiconductor sealing of this invention. Further, in order to obtain a semiconductor sealing liquid epoxy resin composition excellent in reliability, the epoxy resin Na +, Cl - ionic impurities things as small as possible is preferred such as is preferably 500ppm or less.
[0015]
The amine compound (a) represented by the general formula (1) used in the present invention has three benzene rings and acts as a curing agent.
The amine compound (a) represented by the general formula (1) used in the present invention is specifically a compound in which two aminophenoxy groups are bonded to benzene, and the amino group is substituted at any position of the phenoxy group. However, the 3-position or 4-position is preferred, and the aminophenoxy group may be substituted at any position of benzene, but a 1,3-substituted product or a 1,4-substituted product is preferred. Specific examples of such compounds include, for example, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) Examples include benzene.
[0016]
Since the epoxy resin composition for semiconductor encapsulation containing the amine compound represented by the general formula (1) has excellent adhesiveness, the reliability of the flip chip mounting type semiconductor device using the organic printed wiring board is greatly improved. Can do.
In the amine compound represented by the general formula (1), since the bonding group that connects the aromatic rings is an electron-withdrawing ether (—O—) group, the electron density of the nitrogen atom of the amino group is low. That is, the nucleophilicity of the amino group is lowered, and the reactivity with the epoxy group is lowered near room temperature. As a result, the viscosity change at room temperature of the epoxy resin composition for semiconductor encapsulation is small, and excellent storage stability is exhibited. Amine-based curing agents other than aromatic rings have poor heat resistance and are highly reactive even at room temperature or lower, so there are disadvantages inferior in heat resistance and storage stability of the epoxy resin composition for semiconductor encapsulation, and are not suitable for the present invention. .
[0017]
When encapsulating a liquid epoxy resin composition for semiconductor encapsulation in a gap between a flip-chip mounted device and a substrate, a general epoxy resin composition for sealing has a viscosity of room temperature (25 ° C) when the substrate is heated. Since it drops to about 1/100 to 1/300, it can be sealed in a short time. Therefore, an epoxy resin composition for sealing having a low viscosity that can shorten the encapsulation time is more advantageous.
[0018]
The amine compound (a) having three aromatic rings represented by the general formula (1) is solid at room temperature. Therefore, when mixed with a liquid epoxy resin, the solubility of the amine compound (a) in the epoxy resin is not sufficient, and the viscosity of the epoxy resin composition for semiconductor encapsulation tends to increase. The viscosity at room temperature of the liquid epoxy resin composition for semiconductor encapsulation obtained by mixing the amine compound (a) used in the present invention with a liquid epoxy resin is increased, however, at room temperature in an atmosphere of 100 ° C. The viscosity is greatly reduced to about 1/1000 of the viscosity. The reason for this large decrease has not been elucidated, but it is expected to be the influence of the number of aromatic rings and the skeleton of the amine curing agent represented by the general formula (1).
[0019]
In the present invention, a low-viscosity liquid aromatic amine compound is used for the purpose of improving the solubility of the amine compound (a) in a liquid epoxy resin at room temperature and reducing the viscosity of the resulting epoxy resin composition for semiconductor encapsulation. (B) may be used together with the amine curing agent (a) represented by the general formula (1). The low-viscosity liquid aromatic amine compound (b) needs to be a liquid aromatic amine compound having a viscosity of 10 Pa · s or less at 25 ° C. Examples of such low-viscosity liquid aromatic amines include 3,3′-diethyl-4,4′-diaminodiphenylmethane and 2,5-diamino-4,6-diethyltoluene.
[0020]
By combining a mixture of the liquid aromatic amine compound (b) and the amine compound (a) containing three aromatic rings represented by the general formula (1) with an epoxy resin, the solubility is improved and the fluidity is excellent. A liquid epoxy resin composition for semiconductor encapsulation can be provided. When using a liquid amine compound, the equivalent ratio of the amine compound (a) and the aromatic amine compound (b) represented by the general formula (1) should be (a) :( b) = 99: 1 to 30:70. Is preferred. With respect to the total amount of the compound (a) and the compound (b), when the compound (a) is less than 30% in an equivalent ratio, the aromatic amine compound (b) becomes excessive and the storage stability tends to be lowered. In order to obtain a highly reliable liquid epoxy resin composition for semiconductor encapsulation, the aromatic amine compounds (a) and (b) represented by the general formula (1) can contain ionic impurities such as Na + and Cl − as much as possible. A small amount is preferable, and 500 ppm or less is preferable.
[0021]
The equivalent ratio of the liquid epoxy resin (c) as the main component to the amine compound (a) and the amine compound (b) is (c): ((a) + (b)) = 100: 80 to 100: 115 It is preferable. When the equivalent ratio of the amine compound (a) and the amine compound (b) to the equivalent of the liquid epoxy resin (c) exceeds 1.15 (100: 115), the amine compound as a curing agent becomes excessive and many amino compounds Due to the presence of groups, the moisture resistance tends to decrease. When the equivalent ratio of the amine compound (a) and the amine compound (b) to the equivalent of the liquid epoxy resin (c) is less than 0.80 (100: 80), the epoxy resin is increased, resulting in insufficient curing of the resin. The heat resistance of the cured product tends to decrease. (c): ((a) + (b)) = When a resin having an equivalent ratio outside the range of 100: 80 to 100: 115 is used, the reliability improvement effect of the semiconductor device tends to be insufficient. It is in.
[0022]
The liquid epoxy resin composition for semiconductor encapsulation of the present invention may contain a commonly used inorganic filler. The inorganic filler is blended in the epoxy resin composition for hygroscopicity, reduction of thermal expansion coefficient, improvement of thermal conductivity and improvement of mechanical strength. Specifically, fused silica, crystalline silica, alumina, zircon, calcium silicate, calcium carbonate, potassium titanate, silicon carbide, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, steatite, spinel, Examples thereof include powders such as mullite and titania, beads formed by spheroidizing these, and glass fibers. Furthermore, examples of the inorganic filler having a flame retardant effect include aluminum hydroxide, magnesium hydroxide, zinc silicate, and zinc molybdate. These inorganic fillers may be used alone or in combination of two or more.
[0023]
Among these inorganic fillers, fused silica is preferable from the viewpoint of reducing the thermal expansion coefficient, and crystalline silica and alumina are preferable from the viewpoint of high thermal conductivity. The particle shape of the inorganic filler is preferably spherical from the viewpoint of fluidity and penetrability into the fine gaps, and the average particle size is preferably from 0.1 to 20 μm. If the average particle size is less than 0.1 μm, the dispersibility in the liquid resin tends to be poor. In addition, thixotropic properties are imparted to the liquid sealing epoxy resin composition and the fluidity tends to be inferior. When the average particle size exceeds 20 μm, filler sedimentation is likely to occur, and when encapsulating the epoxy resin composition for liquid sealing in the gap between the flip chip mounted device and the substrate by capillary flow, fluidity and permeability to fine intervals Tend to be inferior. The blending ratio of the inorganic filler can be adjusted in the range of 0 to 90% by weight with respect to the epoxy composition of the present invention. The range of 30 to 85% by weight is particularly preferable, and 40 to 80% by weight is more preferable. If the blending ratio of the inorganic filler is less than 30% by weight, the effect of reducing the thermal expansion coefficient tends to be small, but even when the blending ratio of the inorganic filler is 0% by weight, the chip size, connection method, type of connection electrode and its shape In some cases, sufficient reliability can be ensured in practice depending on the size, the substrate on which the element is mounted, the material of the resist, and the like. If the blending ratio of the inorganic filler exceeds 90% by weight, the liquid epoxy resin composition for semiconductor encapsulation tends to have a high viscosity, and the fluidity at the time of encapsulation tends to be greatly reduced.
[0024]
In addition, the liquid epoxy resin composition for semiconductor encapsulation of the present invention includes cycloamidine compounds, tertiary amines, imidazoles, phosphorus compounds such as organic phosphines, and derivatives thereof, or tetraphenylboron salts thereof. Well-known curing accelerators that are generally used can be blended as required, alone or in combination of two or more. The blending amount of the curing accelerator is not particularly limited as long as the curing acceleration effect is achieved.
[0025]
In the liquid epoxy resin composition for semiconductor encapsulation of the present invention, known coupling agents such as epoxy silane, amino silane, ureido silane, vinyl silane, alkyl silane, organic titanate, aluminum alkylate, etc. are used alone or in combination of two or more. And can be blended as necessary. Also, red phosphorus, phosphate ester, melamine, melamine derivative, compound having triazine ring, cyanuric acid derivative, nitrogen-containing compound of isocyanuric acid derivative, phosphorus nitrogen-containing compound such as cyclophosphazene, zinc oxide, iron oxide, molybdenum oxide, ferrocene And the like, flame retardants such as antimony oxide such as antimony trioxide, antimony tetroxide, and antimony pentoxide, and brominated epoxy resin can be used alone or in combination of two or more.
[0026]
The liquid epoxy resin composition for semiconductor encapsulation of the present invention may also contain an ion trapper agent that improves the moisture resistance and high temperature storage characteristics of the semiconductor element. There is no restriction | limiting in particular as an ion trapper agent, A conventionally well-known thing can be used. Specific examples include hydrotalcites, hydrous oxides of elements such as magnesium, aluminum, titanium, zirconium and bismuth. These can be blended alone or in combination of two or more.
Furthermore, the liquid epoxy resin composition for semiconductor encapsulation of the present invention requires other additives such as stress relieving agents such as silicone rubber powder, coloring agents such as dyes and carbon black, leveling agents, antifoaming agents, and the like. It can be blended accordingly.
[0027]
The liquid epoxy resin composition for semiconductor encapsulation of the present invention can be adjusted by any method as long as the above various components can be uniformly dispersed and mixed. In general, there is a method in which a predetermined amount is weighed and then dispersed and mixed using a three roll, vacuum separator, hybrid mixer (manufactured by KEYENCE, model MH-500) or the like.
As a method of sealing an element using the liquid epoxy resin composition for semiconductor sealing of the present invention, there are a dispensing method, a casting method, a printing method, and the like.
As a semiconductor device obtained by sealing an element with the liquid epoxy resin composition for semiconductor sealing obtained by this invention, the following are mentioned, for example.
[0028]
A device is mounted on the surface of an organic substrate or an inorganic substrate on which a wiring board connection terminal is formed on the back surface, and the device and the wiring formed on the organic substrate are connected by bumps or wire bonding. BGA, CSP (chip size package) etc. which sealed the element with the liquid epoxy resin composition are mentioned. More specifically, the circuit forming surface of the element and the circuit forming surface of the organic or inorganic substrate on which the element is mounted are opposed to each other, and the electrode of the element and the circuit of the substrate are electrically connected via the bumps. Examples include a flip chip mounting type semiconductor device in which the gap is impregnated with the epoxy resin composition for semiconductor encapsulation of the present invention.
[0029]
【Example】
EXAMPLES Next, although an Example demonstrates this invention concretely, the scope of the present invention is not limited to these Examples. First, resins used in Examples and Comparative Examples are shown. These are hereinafter indicated by trade names or abbreviations.
[0030]
B) Liquid epoxy resin = bisphenol F epoxy resin (manufactured by Japan Epoxy Co., Ltd., epoxy equivalent 160, abbreviation BF)
B) Liquid epoxy resin = bisphenol A epoxy resin (manufactured by Japan Epoxy Co., Ltd., trade name = Epicoat 828, epoxy equivalent 195, abbreviation BA)
C) Curing agent = 1,3-bis (3-aminophenoxy) benzene (Mitsui Chemicals, abbreviation APB)
D) Curing agent = 1,4-bis (4-aminophenoxy) benzene (Wakayama Seika Chemicals Company, abbreviation APOB)
E) Curing agent = 3,3'-diethyl-4,4'-diaminodiphenylmethane (manufactured by Nippon Kayaku Co., Ltd., trade name = Kayahard AA, abbreviation AA, viscosity at 25 ° C = 3.0 Pa · s)
F) Curing agent = 2,2-bis (4- (4-aminophenoxy) phenyl) propane (Aldrich, abbreviation BAPP, mp = 127 ° C)
G) Curing agent = 4,4'-diaminodiphenylmethane (Wako Pure Chemical Industries, abbreviation DDM, mp = 90 ° C)
H) Coupling agent = 3-glycidoxypropyl-trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name = KBM403)
B) Inorganic filler = Spherical fused silica with an average particle size of 4.4 μm (abbreviation E)
[0031]
These are blended in the composition shown in Table 1 and mixed and dispersed with three rolls, then mixed and degassed with a vacuum breaker, and the liquids for semiconductor encapsulation of Examples 1 to 6 and Comparative Examples 1 to 4 are used. An epoxy resin composition was prepared.
As an example of a semiconductor device provided with an element to be sealed with a liquid epoxy resin composition for semiconductor sealing, a flip-chip mounting type BGA was produced by the following method (3). This was put on a 100 degreeC hotplate, and the liquid epoxy resin composition for semiconductor sealing of Examples 1-6 and Comparative Examples 1-4 was dripped at the one end side of a chip using a dispenser, and a capillary phenomenon (capillary flow) Thus, a flip-chip mounting type BGA sealed with resin by sealing at a gap between the element and the substrate and further curing at 160 ° C. for 2 hours was obtained. Ten pieces were produced for each example and comparative example.
[0032]
Storage stability of the liquid epoxy resin composition for semiconductor encapsulation of the present invention, evaluation of shear adhesive strength with the element passivation film (polyimide), thermal shock resistance of the semiconductor device encapsulating the element using the material of the present invention The moisture resistance and the like were evaluated by the following test.
(1) Storage stability About each of the liquid epoxy resin composition for semiconductor encapsulation of this invention, and the epoxy resin molding material of a comparative example, the viscosity increase rate is calculated | required from the initial viscosity in 25 degreeC, and the viscosity in 25 degreeC after 20 hours. It was. The lower the viscosity increase rate, the better the storage stability. The viscosity is measured with a rotational viscometer (manufactured by HAKKE, model RS100) at 25 ° C. and a shear rate of 10 (1 / s). The results are shown in Table 1.
[0033]
(2) Evaluation of shear adhesive strength with polyimide Negative photosensitive polyimide (manufactured by Hitachi Chemical DuPont Microsystems, Inc., PL-H708) as a passivation film on a silicon wafer, in accordance with the pattern formation process recommended by Hitachi Chemical DuPont Microsystems, I-line exposure without using spin coat, pre-bake, photomask, post-exposure heating, development with developer (PL-2N, manufactured by Hitachi Chemical DuPont Microsystems Co., Ltd.), rinse with water, nitrogen atmosphere A silicon wafer coated with a polyimide film for evaluating the shear adhesive force with the liquid sealing epoxy resin molding material of the present invention was obtained by heating at 350 ° C. for 60 minutes with the lower hot air dryer. Polyimide has a film thickness of about 10 μm. This silicon wafer is cut into a size of 2cm x 2cm, stacked with a 1mm thick silicon rubber sheet (size 2cm x 2cm) with 4mm x 4mm square holes, and a thickness of about 4mm x 4mm. A 1mm tetrafluoroethylene sheet (size 2cm x 2cm) was piled up, and was clamped from four sides and fixed. The liquid epoxy resin composition for semiconductor encapsulation of the present invention is about 0.5 to 1 mm in thickness using a dispenser so as not to entrap air bubbles in a 4 mm × 4 mm square hole formed in a silicon rubber sheet and a tetrafluoroethylene sheet. And heated and cured at 160 ° C. for 2 hours in a hot air dryer. Thereafter, the silicon rubber sheet and the tetrafluoroethylene sheet were removed from the silicon wafer coated with the polyimide film to obtain a sample having a cured product of 4 mm × 4 mm × about 0.5 to 1 mm on the polyimide coated silicon wafer. Using a universal bond tester (manufactured by Daisy, PC2400 type), the shear bond strength between the polyimide and the cured product comprising the liquid epoxy resin composition for semiconductor encapsulation of the present invention was measured, and the adhesion was evaluated. The higher the shear strength, the better the adhesion. Measurement conditions were measured by applying a strain at a speed of 300 μm / second to a height of 50 μm from the polyimide using a shear jig on the cured product block. In the examples, the initial value and the value after 168 hours by the PCT test were shown as part of the moisture resistance test. The results are shown in Table 1.
[0034]
[Table 1]
(3) Fabrication of flip-chip mounting type BGA As shown in FIG. 1, a semiconductor element in which connection electrode portions (gold bumps) 3 are provided on a printed
[0036]
(4) Stress application test The device was sealed by injecting the liquid
[0037]
Further, PCT was performed for 168 hours as a moisture resistance test for each of the five semiconductor devices that were not subjected to the temperature cycle test. PCT exposes a semiconductor device to an environment of 121 ° C., 2 atm, and 100% RH in a pressure vessel. Thereafter, the energization test was performed again. The results are shown in Table 2.
[0038]
[Table 2]
As described above, as shown in Examples and Comparative Examples, the liquid epoxy resin composition for semiconductor encapsulation of the present invention is excellent in adhesiveness, moisture resistance, and storage stability. In addition, the semiconductor device encapsulating the liquid sealing epoxy resin composition of the present invention ensures stable energization for the initial energization test, temperature cycle test and PCT stress application test, and is a highly reliable semiconductor. A device is obtained.
[0040]
【The invention's effect】
Since the liquid epoxy resin composition for semiconductor encapsulation of the present invention uses the aromatic amine represented by the general formula (1), there is no decrease in shear strength due to PCT and the viscosity increase rate is small. Therefore, a resin sealing layer is formed by the liquid epoxy resin composition for semiconductor sealing of the present invention sealed by capillary flow in the gap between the printed circuit board and the semiconductor element connected via the plurality of connection electrode portions. The semiconductor device ensures stable energization for the initial energization test, temperature cycle test, and PCT stress application test.
[Brief description of the drawings]
FIG. 1 is a schematic cross-sectional view of a BGA used in an example.
[Explanation of symbols]
DESCRIPTION OF
3. Connection electrode part (gold bump)
4 ...
Claims (5)
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| JP5297425B2 (en) * | 2010-08-26 | 2013-09-25 | パナソニック株式会社 | Epoxy resin composition for semiconductor encapsulation and semiconductor device using the same |
| JP5958799B2 (en) * | 2012-03-08 | 2016-08-02 | パナソニックＩｐマネジメント株式会社 | Liquid epoxy resin composition for semiconductor encapsulation and semiconductor device using the same |
| JP6943945B2 (en) * | 2016-07-25 | 2021-10-06 | ザ・ボーイング・カンパニーＴｈｅ Ｂｏｅｉｎｇ Ｃｏｍｐａｎｙ | Epoxy resin |
| KR102093860B1 (en) * | 2018-10-18 | 2020-03-26 | 주식회사 아이에스시 | Test connector and manufacturing method of the test connector |
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