JP5618537B2 - チップ積層並びにチップ・ウェハ接合に有用な方法及び材料 - Google Patents
チップ積層並びにチップ・ウェハ接合に有用な方法及び材料 Download PDFInfo
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- JP5618537B2 JP5618537B2 JP2009501543A JP2009501543A JP5618537B2 JP 5618537 B2 JP5618537 B2 JP 5618537B2 JP 2009501543 A JP2009501543 A JP 2009501543A JP 2009501543 A JP2009501543 A JP 2009501543A JP 5618537 B2 JP5618537 B2 JP 5618537B2
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Description
本出願は、出典明示によりここに援用する2006年3月21日出願の米国仮特許出願第60/784187号の優先権を主張する。
本発明は一般にチップ積層構造(チップスタッキング)、チップ・ウェハ接合構造(チップ・ウェハボンディング)並びに該チップ積層構造(チップスタック)及びチップ又はウェハ接合構造(チップ又はウェハボンディング)の形成に有用な材料に係り、より詳細には、本発明は、材料が強固な接合をもたらすと同時に残渣がないか殆どない状態に直ぐに除去され、よって該材料の再加工が可能になる方法及び材料に関する。
歴史的に、半導体の製造においては、単一の半導体ダイ(又はチップ)を封止パッケージ内に実装した後、該パッケージを例えば回路基板に更に実装していた。このようにして、様々な機能又は容量増加がコンピュータや携帯電話などの高位機器に対して実現することができた。かかるパッケージ、例えばデュアルインラインパッケージ(DIP)又はシングルインラインパッケージ(SIP)は、収容されたダイを物理的損耗、周りの環境中の汚染から保護し、ダイの他の電気回路に対する電気接続をもたらすように作用するが、かかるパッケージはまた嵩張ってしまうので、回路基板又はモジュールのサイズを複数のかかるパッケージを収容するのに十分に大きくすることを要する。
本発明の実施態様を、次の添付図面を参照しながら以下に説明する。
実施例における以外、又は別の定義がなされていない場合は、明細書及び特許請求の範囲において使用される成分の量、反応条件等々を指すあらゆる数値、値及び/又は表現は全ての例において「約」なる用語によって修飾されているものと理解されなければならない。
ここで、第一の異なる種類の繰返し単位は、少なくとも一つのグリシジルエーテル官能性ペンダント基を含み、第二の異なる種類の繰返し単位は、少なくとも一つのアラルキルペンダント基を含み、X,m,R1,R2,R3,及びR4は以下の定義の通りである。ポリマー組成物を含むかかるポリマーを利用し、かつ内部応力が小さく、300℃超の処理温度に曝すことができ、感光してパターン形成することができる成膜方法では、信頼度の高い接合部を電子デバイス間又は光電子デバイス間に、あるいはかかるデバイスと基板の間に形成することができ、かかる組成は、シクロペンタノンのような市販の感光現像液であり、メチルn-アミルケトン(2-ヘプタノン)(「MAK」)を感光プロセスに用いることができる。
CH2=CH-O-R10-O-CH=CH2 (VI)
CH2=CH-O-R11 (VII)
実施例1
フェネチルノルボルネン(PENB)、グリシジルメチルエーテルノルボルネン(MGENB)及びデシルノルボルネン(デシルNB)から誘導されるフェネチル、グリシジルメチルエーテル、及びデシル繰返し単位を含むポリマーを以下のようにして調製した: 適切な容量の反応容器を110℃で18時間に亘って乾燥させた後、窒素をパージしたグローブボックスに移した。次に容器に酢酸エチル(230g)、シクロヘキサン(230 g)、PENB(14.17g、0.071モル);MGENB(14.0g 、0.100モル)及びデシルNB(39.50g、0.168モル)を充填した。反応媒質から酸素を、乾燥N2流をこの溶液に30分に亘って流し込むことによって除去した。除去が完了した後、8mlのトルエンに溶解した1.50g(3.10ミリモル)のビス(トルエン)ビス(ペルフルオロフェニル)ニッケル(NiARF)を反応器に注入した。反応混合物を大気温度で18時間に亘って撹拌し、次に過酢酸溶液(ニッケル触媒基準で50モル当量-約130mlの脱イオン水で希釈した57mlの氷酢酸を、約100mlの脱イオン水で希釈した115mlの30重量%過酸化水素水と混合することにより調製された150ミリモル)で処理し、更に追加の18時間に亘って撹拌した。
PENB、MGENB、及びドデシルノルボルネン(ドデシルNB)から誘導されるフェネチル、グリシジルメチルエーテル及びデシル繰返し単位を含むポリマーを以下のようにして調製した: 適切な容量の反応容器に、トルエン(118.5g);メチルエチルケトン(MEK)(23.0g);ドデシルNB(11.9g;0.045モル);MGENB(4.1g;0.023モル);及びPENB(9.0g;0.045モル)を充填した。モノマー溶液を撹拌して溶存酸素を除去しながらモノマー溶液にN2ガスを30分に亘って吹き込んだ。吹き込んだ後、次にトルエン(12.0g)に溶解したNiARF触媒(0.845g;0.0018モル)を反応容器にカニューレを使用して加えた。重合反応を大気温度で6時間に亘って行ない、次に脱イオン水(100g)、過酸化水素水(50.0g)及び酢酸(25.0g)の溶液で処理して重合反応を停止した。得られた2相反応混合物を大気温度で更に18時間に亘って撹拌して残留触媒を除去した。撹拌を停止して、有機相及び水性相の相分離を可能にし、水性相を取り除き、有機相を200mLの脱イオン水で3回洗浄し、50mLのTHFを1回目の洗浄時に加えて水性相及び有機相の相分離を容易にした。
実施例5に類似する形で、PENB、エポキシオクチルノルボネン(EONB)、及びデシルNBから誘導されるフェネチル、エポキシオクチル及びデシル繰返し単位を含むポリマーをそれぞれ40/30/30のモノマー比を使用して調製した。203.4g(収率96.0%)の固形ポリマーを回収した(Mn=29892;Mw=76260;PDI=2.55)。組成を1H-NMRを使用して求めたところ、PENB/EONB/デシルNBが40/30/30であることが判明した。
別のプロセスでは、300ガロンのPFA内張ステンレス鋼製反応容器に、25.4キログラム(kg)のPENB、17.0kgのMGENB、22.8kgのデシルNB、261.0kgのシクロヘキサン及び261.0kgの酢酸エチルを充填した。次に、反応混合物を撹拌しながら30℃+/−1℃ に温めた。温度が安定した後、29.48kgの無水トルエンに溶解した1.228kgのNiARF溶液を加え、発熱反応によって反応容器の温度を45℃まで上昇させることができ、この温度を5時間の更なる時間に亘って維持した。次に、反応混合物を、33kgの酢酸、62.3kgの30%過酸化水素水及び71.8kgの脱イオン水の溶液で撹拌しながら処理し、その後、混合物を水性相及び溶媒相に分離することができた。水性相は除去し、溶媒相は、反応混合物温度を50℃に維持しながら水及びエタノールの混合物(129.3kgの水及び55.4kgのエタノール)で3回洗浄した。次に、得られたポリマーリッチな溶媒相をアルコール類の混合物で処理して未反応モノマーを除去し、4℃にまで冷却し、上部アルコール層を除去した。次に、溶媒を交換することにより、生成物を2-ヘプタノン(MAK)に溶解して得た溶液として回収し、真空蒸留によって約50%ポリマーに濃縮した。61.5kgのポリマー(理論収率94%)が得られた。1H NMR分析によって、ポリマーの組成として:41モル%のPENB、29モル%のMGENB、及び30モル%のデシルNBが含まれていることが判明した。分子量については、Mn=33137、Mw=70697、及び多分散性インデックス(PDI)=2.13であることが判明した。
適切な容量の反応容器に、シクロヘキサン(403.7g)、酢酸エチル(403.7g)、デシルNB(54.80g;0.234モル);MGENB(29.74g;0.165モル);PENB(21.78g;0.110モル)及びトリメトキシシリルノルボルネン(TMSNB)(8.84g;0.041モル)を充填した。モノマー溶液にN2ガスを30分に亘って吹き込んで溶存酸素を除去した。
実施例6の手順を、以下の表2に示す量の幾つかのモノマーを使用して繰り返した。適切な量の溶媒及び触媒も用い、表に示すように、別のシリルエーテルノルボネンモノマーを実施例7及び9の各実施例において、表に続く注記に特定されているように使用した。
表2
別のシリルエーテルノルボルネンに関する注記
*トリメトキシシリルノルボルネン(TMSNB)
**トリエトキシシリルノルボルネン(TESNB)
***トリメトキシシリルエチルノルボルネン(TMSENB)
実施例A
首の広い琥珀色のビンに、実施例5で調製した101.0gのポリマー溶液と50gの2-ヘプタノン(MAK)を充填した。溶液を、固形ポリマーが完全に溶解するまで混合し、次に0.45ミクロンフィルターで濾過し微粒子を除去した。この溶液に2.00g(1.97ミリモル)のRhodorsil(登録商標)PI2074光開始剤、0.60g(1.97ミリモル)のSpeedcure(登録商標)CTPX(Lambson Group社)、0.137g(0.688ミリモル)のフェノチアジン(Aldrich)及び2.657gのIrganox1076(5.00ミリモル)を加えた。この溶液を18時間に亘って混合し、光活性化合物を完全に分散させた。
首の広い琥珀色のビンに、実施例1で調製した191.25gのポリマー材料及び191gの2-ヘプタノン(MAK)を充填した。溶液を、固形ポリマーが完全に溶解するまで混合し、次に0.45ミクロンフィルターで濾過し微粒子を除去した。この溶液に、3.825g(3.77ミリモル)のRhodorsil(登録商標)PI2074光開始剤、1.148g(3.77ミリモル)のSpeedcure(登録商標)CTPX(Lambson Group社)、0.262g(1.32ミリモル)のフェノチアジン(Aldrich)、及び3.73g(7.03ミリモル)のIrganox 1076(Ciba)を加えた。この溶液を18時間に亘って混合し、光活性化合物を完全に分散させた。
首の広い琥珀色のビンに、実施例1で調製した37.5gのポリマー材料及び37.5gの2-ヘプタノン(MAK)を充填した。この溶液を、固形ポリマーが完全に溶解するまで混合し、次に0.45ミクロンフィルターで濾過し微粒子を除去した。この溶液に、0.9840g(0.97ミリモル)のRhodorsil(登録商標)PI2074光開始剤、0.297g(0.97ミリモル)のSpeedcure(登録商標)CTPX(Lambson Group社)、0.070g(0.35ミリモル)のフェノチアジン(Aldrich)、及び0.73g(1.38ミリモル)のIrganox1076(Ciba Fine Chemicals)、2.46g(10.4ミリモル)の3-グリシドキシルプロピルトリメトキシシラン(Aldrich)、及び1.25g(6.36ミリモル)の1,4-シクロヘキサンジメタノールジビニルエーテルを加えた。この溶液を18時間に亘って混合し、光活性化合物を完全に分散させた。
首の広い琥珀色のビンに、実施例4で調製した33.2gのポリマー材料及び47.6gの2-ヘプタノン(MAK)を充填した。この溶液を、固形ポリマーが完全に溶解するまで混合し、次に0.45ミクロンフィルターで濾過し微粒子を除去した。この溶液に、0.664g(0.65ミリモル)のRhodorsil(登録商標)PI2074光開始剤、0.203g(0.668ミリモル)のSpeedcure(登録商標)CTPX(Lambson Group Ltd.)、0.051g(0.256ミリモル)のフェノチアジン(Aldrich)、及び0.499g(1.38ミリモル)のIrganox1076(0.939ミリモル)、1.667g(7.2ミリモル)の3-グリシドキシルプロピルトリメトキシシラン(Aldrich)、及び0.831g(4.23ミリモル)の1,4-シクロヘキサンジメタノールジビニルエーテルを加えた。この溶液を18時間に亘って混合し、光活性化合物を完全に分散させた。
以下の表3は、かかる測定のために調製された試験サンプルの測定済みダイ剪断強度を示している。実施例E〜Nのこれらのポリマー組成物の各々は、実施例Aで説明したようにして調製したが、使用する特定のポリマーが、表に示すように変わり、また使用する特定量のRhodosil,CTPX,フェノチアジン,Irganoxがポリマーに占める割合が、百分率でそれぞれ、2.0,0.6,0.14,及び1.5であった点が異なっている。他の添加剤を何れの組成物にも含有させた場合、このような材料及び使用する量は、以下の表3の「更なる添加剤」欄に表示される(これらの添加剤の化学構造は、前に示したこのような構造のリストに与える)。ダイ剪断強度の測定は、前に記載したように、0.1MPaの低接合圧力と、0.7MPaの高接合圧力を使用して行なわれた。両方の圧力に関して、試験サンプルを170℃で熱処理し、圧力を2分に亘って加えた。測定は、試験サンプルを大気温度に戻した後に行なった。
表3
Claims (35)
- 半導体デバイスを製造する方法において、
第1基板の表面を覆う熱分解可能なポリマー層を形成し;
場合によっては該層を紫外線、可視光線、X線又は電子ビームに露光させ;
第2基板を提供し;
該第2基板をポリマー層に接触させることであって、当該接触させることが熱圧着接合を含んでなることを含む方法であって、
前記熱分解可能なポリマーがノルボルネン型モノマーから誘導されるポリマーである方法。 - 前記層の紫外線、可視光線、X線又は電子ビームへの露光が像様露光を含む、請求項1に記載の方法。
- 前記層の紫外線、可視光線、X線又は電子ビームへの露光が全面露光を含む、請求項1に記載の方法。
- 第1基板の表面を覆う熱分解可能なポリマー層の形成が複数の非個片化ダイを含みうる半導体ウェハ基板の活性表面を覆う当該層の形成を含む、請求項1、2又は3に記載の方法。
- 半導体ウェハ基板の活性表面が複数の非個片化ダイを含む、請求項4に記載の方法。
- 半導体ウェハ基板の活性表面の反対面を所望の厚みの半導体ウェハ基板が得られるまで薄厚化プロセスにかけることを更に含む、請求項5に記載の方法。
- 第1基板の表面を覆う熱分解可能なポリマー層の形成が半導体ウェハ基板の活性表面の
反対面の形成を更に含む、請求項1、2又は3に記載の方法。 - 所望の平坦度が得られるまで半導体ウェハ基板の活性表面をケミカルメカニカルポリッシングすることを更に含む、請求項7に記載の方法。
- 第1基板の表面を覆う熱分解可能なポリマーの層の形成が支持基板の表面を覆う当該層の形成を含む、請求項1、2又は3に記載の方法。
- 第2基板を接触させることが半導体ウェハ基板の活性表面を接触させることを含む、請求項9に記載の方法。
- 所望の厚みの半導体ウェハ基板が得られるまで、半導体ウェハ基板の活性表面の反対面をラッピング又は研磨することを更に含む、請求項10に記載の方法。
- 第2基板を接触させることが半導体ウェハ基板の活性表面の反対表面を接触させることを含む、請求項9に記載の方法。
- 所望の平坦度が得られるまで半導体ウェハ基板の活性面をケミカルメカニカルポリッシングすることを更に含む、請求項12に記載の方法。
- 像様露光が前記ダイの間にボンディングパッドとダイシングレーンを決める、請求項5に記載の方法。
- 第1基板の表面を覆う熱分解可能なポリマーの層の形成が半導体ウェハ基板の活性表面を覆う前記層の形成を含む、請求項14に記載の方法。
- 半導体ウェハ基板の活性表面が複数の非個片化ダイを含む、請求項15に記載の方法。
- 熱圧着接合の前にダイの個片化することを更に含む、請求項16に記載の方法。
- 第2基板が個片化ダイを含む、請求項17に記載の方法。
- 前記ポリマーが
第1ノルボルネン型モノマーから誘導される第1繰返し単位、第2ノルボルネン型モノマーから誘導される第2繰返し単位及び第3ノルボルネン型モノマーから誘導される第3繰返し単位を含むビニル付加ポリマー;および
感光剤成分、光開始剤成分、反応性及び非反応性の溶媒、触媒捕捉剤、酸性捕捉剤、塩基性捕捉剤、接着促進剤及び抗酸化剤から選択される一又は複数の添加剤
を含む、請求項1に記載の方法。 - 第1ノルボルネン型モノマーがエポキシ官能基を有する少なくとも1つのペンダント基を有し、第2ノルボルネン型モノマーがアラルキルペンダント基を有する少なくとも1つのペンダント基を有し、及び第3ノルボルネン型モノマーがアルキルペンダント基を有する少なくとも1つのペンダント基を有する、請求項19に記載の方法。
- 第1ノルボルネン型モノマーがグリシジルメチルエーテルノルボルネン(MGENB)又はエポキシオクチルノルボネン(EONB)であり、第2ノルボルネン型モノマーがフェネチルノルボルネン(PENB)であり、及び第3ノルボルネン型モノマーがデシルノルボルネン(デシルNB)又はドデシルノルボルネン(ドデシルNB)である、請求項20に記載の方法。
- 非反応性溶媒が2-ヘプタノン(MAK)であり、感光剤が4-メチルフェニル-4-(1-メチルエチル)フェニルヨードニウムテトラキス(ペンタフルオロフェニル)ボレートであり、光開始剤が1-クロロ-4-プロポキシ-9H-チオキサントンであり、抗酸化剤が3,5-ジ-tert-ブチル-4-ヒドロキシヒドロシンナメートであり、酸性捕捉剤がフェノチアジンであり、接着促進剤がビス[3-(トリエトキシシリル)プロピル]ジスルフィドである、請求項21に記載の方法。
- 接着促進剤が更に3-グリシドキシルプロピルトリメトキシシランを更に含む、請求項22に記載の方法。
- 第1基板及び第2基板の少なくとも1つが、複数のマイクロ電子デバイスダイ、電子デバイスダイ、光電子デバイスダイ、マイクロエレクトロメカニカルシステム(MEMS)デバイスダイ又はマイクロオプトエレクトロメカニカルシステム(MOEMS)デバイスダイを含む半導体ウェハ基板である、請求項2に記載の方法。
- マイクロ電子デバイスダイが、マイクロプロセッサ、特定用途向け集積回路(ASIC)、個別半導体デバイス、半導体メモリを更に含む、請求項24に記載の方法。
- 光電子デバイスダイが画像センシング部分を有する半導体画像センサを含む、請求項24に記載の方法。
- 像様露光が画像センシング部分周辺に置かれた構造を決める、請求項26に記載の方法。
- 半導体画像センサデバイスが電荷結合素子(CCD)又はCMOS画像センサ(CIS)デバイスである、請求項26に記載の方法。
- 熱圧着接合された第1基板及び第2基板を熱分解性ポリマーが分解を生じるために十分な温度まで加熱することを更に含む方法であって、第1基板と第2基板が非接合化される、請求項1に記載の方法。
- 所望の厚みの半導体ウェハ基板が得られるまで、半導体ウェハ基板の活性表面の反対面をラッピング又は研磨することを更に含む、請求項6に記載の方法。
- ポリマー層の形成が半導体基板の活性表面上に熱分解可能なポリマーの第1厚みを有する当該層の形成を含み、前記活性表面が複数のボンディングパッドを含む、請求項2に記載の方法。
- 第1基板を覆うポリマー層の前記像様露光が、前記複数のボンディングパッドのそれぞれの上にボンディングパッド開口部のパターンを提供する請求項31に記載の方法。
- 第2基板の提供が、第2の複数のボンディングパッドを含む第2活性表面を有する第2半導体基板の提供を含む請求項32に記載の方法。
- 第1基板のボンディングパッドに接続された半田バンプであって、各半田バンプが第1厚みのポリマー層より厚い第2厚みを有する半田バンプを提供すること;及び
第1基板を第2基板に熱圧着接合し、第1基板の半田バンプの各々が第2基板のボンディングパッドと接触すること
を含む請求項33に記載の方法。 - 前記第2基板が、前記第2の複数のボンディングパッドのそれぞれの上にボンディングパッド開口部の第2パターンを有する第2熱分解可能なポリマーを更に含む請求項34に記載の方法。
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PCT/US2007/007029 WO2007109326A2 (en) | 2006-03-21 | 2007-03-21 | Methods and materials useful for chip stacking, chip and wafer bonding |
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CN101432867B (zh) | 2013-10-23 |
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EP1997138A2 (en) | 2008-12-03 |
TWI443783B (zh) | 2014-07-01 |
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US20070232026A1 (en) | 2007-10-04 |
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