JP2013206765A - ダイボンド用導電性ペースト及び該導電性ペーストによるダイボンド方法 - Google Patents

ダイボンド用導電性ペースト及び該導電性ペーストによるダイボンド方法 Download PDF

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JP2013206765A
JP2013206765A JP2012075525A JP2012075525A JP2013206765A JP 2013206765 A JP2013206765 A JP 2013206765A JP 2012075525 A JP2012075525 A JP 2012075525A JP 2012075525 A JP2012075525 A JP 2012075525A JP 2013206765 A JP2013206765 A JP 2013206765A
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Prior art keywords
bonding
conductive paste
die
powder
metal particles
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JP2012075525A
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English (en)
Inventor
Toshinori Kogashiwa
俊典 小柏
Akikazu Shioya
晶和 塩屋
Masayuki Miyairi
正幸 宮入
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Tanaka Kikinzoku Kogyo KK
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Tanaka Kikinzoku Kogyo KK
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Priority to JP2012075525A priority Critical patent/JP2013206765A/ja
Priority to TW102108594A priority patent/TW201351437A/zh
Priority to EP13767655.7A priority patent/EP2833393A4/en
Priority to PCT/JP2013/057985 priority patent/WO2013146504A1/ja
Priority to KR1020147030165A priority patent/KR20140139104A/ko
Priority to CN201380017110.2A priority patent/CN104205312A/zh
Priority to US14/375,362 priority patent/US20150014399A1/en
Publication of JP2013206765A publication Critical patent/JP2013206765A/ja
Pending legal-status Critical Current

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    • B22—CASTING; POWDER METALLURGY
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    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/107—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing organic material comprising solvents, e.g. for slip casting
    • B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract


【課題】半導体素子等を基板へダイボンドするための導電性ペーストについて、接合部において生じるボイドのような欠陥発生を抑制することのできるものを提供する。
【解決手段】本発明は、金属粉末と有機溶剤とからなるダイボンド用の導電性ペーストであって、前記金属粉末は、純度９９．９質量％以上、平均粒径０．０１μｍ〜１．０μｍである銀粉、パラジウム粉、銅粉から選択される一種以上の金属粒子と、前記金属粒子の少なくとも一部を覆う金からなる被覆層と、からなる導電性ペーストである。
【選択図】図２

Description

本発明は、半導体チップの基板へのダイボンド、フリップチップ接合に適用される導電性ペースト及びこれを用いた接合方法に関する。特に、高温下で長時間経過しても接合部内にボイドを生じさせない耐久性にすぐれた導電性ペーストに関する。
各種半導体チップの基板へのダイボンド方法としては、従来からろう材を用いたものが広く知られている。このダイボンド法においては、半導体チップ又は基板のいずれかにろう材を融着した後に半導体チップを基板に載置して、ろう材の融点以上の温度に加熱してろう材を溶融・凝固させている。このときの加熱温度（接合温度）は、使用するろう材の融点を考慮して設定される。例えば、近年ダイボンドで一般的に用いられているろう材として、ＡｕＳｎ系ろう材が知られているが、その融点は約２８０℃であることから、接合温度は３００℃以上の温度に設定されることが多い。
ダイボンドの際の接合温度は低温とすることが好ましい。これは、接合温度を高温とすると、接合後の冷却時に生じる熱応力が大きくなり半導体チップの電気的特性に変動が生じるおそれがあることによる。また、接合時の加熱そのものが半導体チップの特性に影響を及ぼすおそれもある。そこで、半導体チップのダイボンディングの低温化を図るため、従来のろう付けによるダイボンド法に替わる方法として、銀等の導電性金属からなる金属粉末を含有する導電性ペーストを使用するダイボンド法が知られている（特許文献１、２）。
特開平１１−２６４８０号公報 特開２００２−１５８３９０号公報
これらの導電性ペーストによるダイボンド法は、従来のろう材によるダイボンド法よりも低温で接合が可能であり接合強度も十分であることに加え、ペーストの取扱い性も良好であることから、近年より広く利用されつつある方法である。
しかし、本発明者等の検討によると、上記従来の導電性ペーストを用いたダイボンド法においては、高温環境で接合部に欠陥が生じることがある。この欠陥とは、被接合材間の接合部である硬化後の導電性ペーストにおいて生じるボイドである。このボイドは、特に、被接合部材が高温に晒される環境で発生する傾向があり、経時的に成長し最終的には剥離に繋がるおそれもある。かかる欠陥は常に生じるものではないが、当然に排除されるべきものである。
本発明は、上記課題を背景とするものであり、半導体素子等を基板へダイボンドするための導電性ペーストについて、上記のような欠陥発生を抑制することのできるものを提供する。
本発明者等は、上記課題を解決すべく、まず、従来の導電性ペーストによる接合プロセスで生じる上記欠陥の性状及びその発生原因について検討した。まずこの検討結果について、図１と共に説明する。図１は、従来の接合プロセスにおける接合直後の接合部と、これが高温加熱されたときの接合部の状態を説明するものである。導電性ペーストによる接合プロセスにおいては、接合時の加圧に伴い金属粒子に再配列に伴う緻密化と、次いで塑性変形（せん断変形）に伴う緻密化が進むことで接合部を形成する。このときの接合部は、図１（ａ）のように、比較的緻密な状態ではあるが、各金属粒子が完全に一体化するものではなく粒子間に空隙が残った状態である。
そして、この接合部が高温加熱を受けると、金属粒子間の拡散が進行し、金属粒子がより密に接合することとなるが、これが全ての金属粒子の間で均一に生じるのであれば、接合部はより緻密化され問題はないが、実際は必ずしもそうはならない。これは、金属粒子表面に酸化物や硫化物からなる皮膜が形成されていることによる。金属粒子表面に酸化物等の皮膜がある場合、金属粒子間の接合状態は不均一なものとなり、図１（ｂ）のように、局所的にボイドができる。本発明者等は、この高温環境下で発生する金属粒子間の接合状態のばらつきがボイドの要因であることを見出した。
上記の検討結果から次の点が確認される。即ち、上記のようなボイド発生は、接合部が高温に加熱されて発生するものであり、そのような環境で使用される半導体素子で顕著に生じる現象である。また、金属粒子の接合が不均一となる要因が金属粒子表面に酸化物や硫化物にあるのであれば、耐食性に優れる金属粉からなる導電性ペーストであれば不均一接合は生じ難いといえる。
もっとも、接合部の欠陥発生を理由として半導体素子の利用範囲を限定することはできない。また、導電性ペーストの金属粒子の構成材料についても、耐食性に優れる金であれば上記欠陥は生じない。この点は本発明者等も確認している。だが、例えば、銀のような金属は、酸化・硫化しやすいものの導電性に優れると共にコスト面で金より優れており、こうした金属の活用も必要である。そこで、本発明者等は、所定の金属の導電性ペーストについて、金属粒子の耐食性を改善し、接合後の高温加熱によるボイド発生が抑制されたものとして本発明に想到した。
即ち、本発明は、金属粉末と有機溶剤とからなる接合用の導電性ペーストであって、前記金属粉末は、純度９９．９質量％以上、平均粒径０．０１μｍ〜１．０μｍである銀粉、パラジウム粉、銅粉から選択される一種以上の金属粒子と、前記金属粒子の少なくとも一部を覆う金からなる被覆層と、からなる導電性ペーストである。
本発明は、銀、パラジウム、銅からなる金属粒子の表面に耐食性向上のための金からなる被覆層を形成して金属粉末を構成することで、金属粉末の酸化や硫化等を抑制し、ダイボンド後に高温加熱を受けたときの接合部における粒子間接合を均一にするものである。以下、本発明につきより詳細に説明する。
本発明における金属粉末を構成する金属粒子は、純度９９．９質量％以上、平均粒径０．０１μｍ〜１．０μｍである銀粉、パラジウム粉、銅粉から選択される一種以上の金属からなる。金属粒子の純度として９９．９質量％以上の高純度を要求するのは、純度が低いと粉末の硬度が上昇し、ダイボンドの際の接合部形成時に塑性変形が生じ難くなるからである。また、金属粉の平均粒径については、１．０μｍを超える粒径の金属粉では、ダイボンドの際の再配列が生じたときに好ましい近接状態を発現させ難くなるからである。一方、０．０１μｍを下限とするのはこの粒径未満の粒径では、ペーストとしたときに凝集しやすく、取扱いが困難となることを考慮するものである。そして、その構成金属を銀、パラジウム、銅のいずれかとするのは、これらの金属は導電性が良好でだからである。そして、これらの金属は比較的腐食し易く、本発明による被覆層の効果が発現するからである。
そして、この金属粒子を被覆する材料として金を選択したのは耐食性に優れ金属粒子の腐食抑制に有効だからである。ここで、被覆層の厚さは、０．００２μｍ〜０．３μｍとするのが好ましい。０．００２μｍ未満ではその効果がないからであり、０．３μｍを超えても効果に差はなく、金属粒子の価格を上昇させるからである。また、被覆層は金属粒子の少なくとも一部を被覆すれば効果が出現し、全ての金属粒子に対してその全面を被覆することを要求するものばかりではない。部分的な被覆であっても、金属粒子同士の拡散を可能とする接触点が増えることとなり、結果として金属粒子間の接合状態のばらつきを低減することができるからである。具体的には、金属粉末全体の体積に対して０．５〜３０ｖｏｌ％の金が存在することが好ましい。
被覆層の形成方法としては、メッキ法、スパッタリング法等の薄膜形成方法を適用することができる。上記通りの被覆層はきわめて薄い範囲で厚さ制御することが好ましく、そのためにはメッキ法等の薄膜形成方法の採用が的確である。特に好ましいのは、無電解メッキ法等のメッキ法によるものである。
本発明に係る導電性ペーストは、上記の金属粉末を有機溶剤に分散して形成される。導電性ペーストの有機溶剤としては、エステルアルコール、ターピネオール、パインオイル、ブチルカルビトールアセテート、ブチルカルビトール、カルビトールが好ましい。例えば、好ましいエステルアルコール系の有機溶剤として、２，２，４−トリメチル−３−ヒドロキシペンタイソブチレート（Ｃ１２Ｈ２４Ｏ３）を挙げることができる。本溶剤は、比較的低温で乾燥させることができるからである。
導電性ペースト中の金属粉末の含有量は、７０〜９９質量％とするのが好ましい。７０質量％未満では接合に必要な金属が不足し緻密な接合部を形成することができない。また、９９質量％を超えるとペーストの粘性が高くなりすぎ取扱い性に支障が生じるからである。
また、本発明に係る導電性ペーストは、上記有機溶剤に加えて、アクリル系樹脂、セルロース系樹脂、アルキッド樹脂から選択される一種以上を含有していても良い。これらの樹脂等を更に加えると導電性ペースト中の金属粉の凝集が防止されてより均質となり、接合部が形成できる。尚、アクリル系樹脂としては、メタクリル酸メチル重合体を、セルロース系樹脂としては、エチルセルロースを、アルキッド樹脂としては、無水フタル酸樹脂を、それぞれ挙げることができる。そして、これらの中でも特にエチルセルロースが好ましい。
次に、本発明に係る導電性ペーストによるダイボンド法について説明する。本発明に係るダイボンド法は、基本的に上記した従来の導電性ペーストを用いる方法と同様である。即ち、基板上へ接合部材である半導体素子等をダイボンドする方法において、前記基板又は前記接合部材に、本願に係る導電性ペーストを塗布する工程、基板上に接合部材を配置した後、一方向又は双方向から加圧しながら加熱して接合する工程、を含むダイボンド方法である。
導電性ペーストの塗布工程は特に限られるものはなく、例えば、スピンコート法、スクリーン印刷法、インクジェット法、ペーストを滴下後にヘラ等で広げる方法等、被接合部材のサイズに対応させて種々の方法を用いることができる。
そして、導電性ペーストを塗布後、他方の接合部材を載せて加熱及び加圧する。加熱及び加圧により、ペースト中の金属粒子同士、及び、接合部材の接合面と金属粒子との間に、互いに点接触した近接状態が形成され、接合部としての形状が安定する。この加熱温度は、８０〜３００℃とするのが好ましい。８０℃未満では点接触が生じないからである。一方、３００℃を超える温度とすると、金属粉末同士の結合が過度に進行し金属粉末間のネッキングが生じて強固に結合し、硬すぎる状態となるからである。また、３００℃を超える加熱は基板の変形や熱影響が生じる恐れがある。そして、接合時の加圧は、０．５ＭＰａ〜５０ＭＰａとするのが好ましい。０.５ＭＰａより低い領域では被接合面全体に導電性ペーストを密着させることが出来ないこと、５０ＭＰａより高い領域では接合状態の更なる改善が見られないからである。
また、このダイボンド方法においては、加熱に加えて超音波を印加しても良い。加熱又は加熱と超音波との組合せにより、金属粉末の塑性変形及び結合を促進し、より強固な接合部を形成することができる。超音波を印加する場合、その条件は、振幅０．５〜５μｍとし、印加時間を０．５〜３秒とするのが好ましい。過大な超音波印加は接合部材を損傷させるからである。ダイボンド工程における上記加熱及び超音波印加は、その目的から少なくとも接合部に対して行なえばよいが、接合部材全体に行っても良い。加熱の方法としては、接合部材を加圧する際の工具からの伝熱を利用するのが簡易である。同様に、超音波の印加は、接合部材を加圧する工具から超音波発振させるのが簡易である。
以上説明したように、本発明に係るダイボンド用の導電性ペーストによれば、高温加熱下でもボイドを発生・成長させることなく接合部の健全性を維持することができ、その耐久性を向上させることができる。本発明は、各種の接合部材を比較的低温で接合することができると共に、接合後の冷却過程における熱応力から接合部材を保護することができることから、熱応力の影響が懸念される半導体チップ等を基板へ接合する際に有用であり、そのダイボンディング、フリップチップ接合等へ適用することができる。そして、高温下でも接合部が安定していることから、パワーデバイス等についてのダイボンディングに特に有用である。
従来の導電性ペーストを使用する接合プロセスの接合部の状態を説明する模式図。 第１実施形態及び比較例の接合部のＳＡＴ観察写真。 １０００サイクル後の比較例の接合部断面のＳＥＭ写真。 ２００時間熱処理後の比較例の接合部のＳＡＴ観察写真。 ２００時間熱処理後の比較例の接合部の断面観察のＳＥＭ写真。
第１実施形態：ここでは、金属粒子に金からなる被覆層を形成した金属粉末を分散させた導電性ペーストを製造し、これを用いてＳｉチップを半導体基板へダイボンドして接合部の健全性を検討した。
導電性ペーストの製造：湿式還元法により製造された純度９９．９質量％の銀粉（平均粒径：０．３μｍ）に被覆層として金を被覆した。被覆層の形成は、無電解メッキ法にて行った。具体的には、メッキ液として、非シアン系の置換型無電解金メッキ液を使用した。金源は亜硫酸金を金濃度として、５ｇ／Ｌ含有させたメッキ液を使用した。前処理として、希釈硫酸により銀粉表面の酸化物や硫化物の除去を行い、メッキ条件として、メッキ温度７０℃に設定してメッキ液へ銀粉を投入して１時間の処理を行い、銀粉表面に金層形成を行った。被覆層平均厚さは０．０１μｍであった。この被覆層の厚さの算出は、銀板に同条件でメッキした際の金膜厚を蛍光Ｘ線膜厚法(ＸＲＦ)で測定した結果を基準とした。
そして、このようにして製造した金属粉末を、有機溶剤としてエステルアルコール（２，２，４−トリメチル−３−ヒドロキシペンタイソブチレート（Ｃ１２Ｈ２４Ｏ３））に混合して導電性ペーストを製造した（金属粉末の含有量９０質量％）。
接合試験：セラミック上に銅箔（０．１５ｍｍ）を接合した厚さ０．６ｍｍのＤＢＣ基板（Ｄｉｒｅｃｔ Ｂｏｎｄｉｎｇ Ｃｏｐｐｅｒ基板）と、接合部材としてＳｉチップを用意した。ＤＢＣ基板上銅箔及びＳｉチップには表面に、Ｔｉ（５０ｎｍ）、Ｐｔ（５０ｎｍ）、Ａｕ（２００ｎｍ）のスパッタ膜を予め形成している。
ＤＢＣ基板上に上記導電性ペーストを塗布後にＳｉチップ(２ｍｍ角)を載置し、５ＭＰａで加圧したところで１℃/分で３００℃まで昇温、１０分保持して接合した。
比較例：第１実施形態における導電性ペースト製造工程で、銀粉末に金をメッキすることなくそのまま有機溶剤と混合して導電性ペーストを製造した。そして、第１実施形態と同様の工程で、ＤＢＣ基板にＳｉチップを接合した。
接合部評価試験（加熱サイクル試験）：第１実施形態及び比較例でダイボンディングしたＳｉチップ付ＤＢＣ基板について、加熱サイクル試験を行いボイド発生・剥離の有無を調査した。この試験では、基板を−４０℃に５分保持した後に２００℃に５分保持する操作を１サイクルとして１０００サイクル繰返し、試験前後の基板面を超音波探傷観察（ＳＡＴ）を行った。また、１０００サイクル後のチップ／基板接合部の断面観察を行った。
図２は、加熱サイクル後の第１実施形態及び比較例のＳＡＴ観察の結果を示す。比較例においては、サイクル初期（ゼロ回）の段階から線状のボイド発生が認められており、１０００サイクル後にはＳｉチップの外周から剥離が生じていた。これに対し、第１実施形態では、サイクル初期の段階で線状のボイド発生が少なく、１０００サイクル後にはＳｉチップの外周から剥離もごく僅か観察されたのみであった。
図３は、１０００サイクル後の比較例の接合部断面について撮影したＳＥＭ写真である。図３のように、Ｓｉチップ外周からのクラックは接合材内部を伝播しており、これがチップの剥離に繋がっているものと思われる。また、クラック先端付近にはボイドが多数存在することから、これらボイドがクラックを誘因するものと推測された。
接合部評価試験（継続加熱試験）：次に、第１実施形態及び比較例でダイボンディングしたＳｉチップ付ＤＢＣ基板について、長時間（２００時間）加熱したときのボイドの発生有無を確認した。この試験では、各基板について３００℃で２００時間加熱し、加熱後の基板に対してＳＡＴ観察、断面観察を行った。
図４は、継続加熱試験後のＳＡＴ観察の結果を示す。比較例では、２００時間経過後にチップ下側半分に剥離が生じていた。一方、第１実施形態の基板では、剥離は見られなかった。また、図５は、加熱後の比較例の接合部断面の観察結果である。接合部中央にあるべき銀粉末同士が離れた結果、連続的なボイドが形成されていたことが判った。
以上の接合部に対する２つの加熱試験の結果から、金層を形成し銀粉末同士の密着性を向上させることでボイドの発生を抑制し、接合部の健全性を保つといえる。比較例におけるボイドの発生は、図１（ｂ）に示したモデルに類似しており、金属粒子表面に酸化物等の皮膜が形成されている場合は、金属粒子間の接合状態が不均一なものとなり、結果として高温環境下でボイドを発生せしめることが確認された。
第２実施形態：ここでは、被覆層の厚さを調整した２種の金属粉末（銀粉末、銅粉末）を用意して導電性ペーストを製造し、被覆層の割合による接合部健全性について検討した。金属粉末の製造は第１実施形態と同様とし、被覆層である金メッキの条件を変更しつつ、厚さ０．００１μｍ、０．００２μｍ、０．００５μｍ、０．０５μｍ、０．１μｍ、０．３μｍ、となるようにした。被覆層の厚さはメッキ条件を変更し、メッキ液の金濃度を２〜１０ｇ／Ｌとし、メッキ温度６０〜９０℃、メッキ時間を１〜２時間に設定して処理を行った。また、導電性ペーストの製造も第１実施形態と同様とした。また、同様にＳｉチップをＤＢＣ基板上に接合した。ＳｉチップとＤＢＣ基板との接合部の健全性評価は、３００℃で２００時間加熱前後の基板について、ボンディングテスタを用いて接合部のシェア強度を測定した（加圧力５ＭＰａ）。この測定結果を表１に示す。
Figure 2013206765
表１から、被覆層（金層）の厚さが０．００１μｍの銀粉末においては、加熱により接合部のシェア強度大きく低下する。一方、金膜厚が０．００２μｍ以上の銀粉末においてはシェア強度の低下はみられない。むしろ、０．００５μｍ以上ではシェア強度が上昇する傾向がみられる。これは、高温加熱により結合部がより緻密なものとなったためと考えられ、このような緻密化は被覆層形成により達成されるものと考えられる。以上の傾向は、銅粉末についても同じ傾向が得られており、一定膜厚以上の金膜を形成することにより、安定性の優れた接合状態を確保できたと言える。尚、金膜を厚く形成すれば金属粒子の価格の上昇になることから、コスト面を考慮すると、被覆層の厚さは０．００２μｍ〜０．３μｍであることが好ましく、より好ましくは０．００２μｍ〜０．０５μｍであると考えられる。
本発明に係るダイボンド用の導電性ペーストによれば、高温加熱を受けてもボイドを発生・成長が生じがたい接合部を形成することができる。本発明は、半導体チップ等のダイボンディング、フリップチップ接合等へ適用することができ、特に、高温環境下で使用されるパワーデバイスのボンディングに有用である。

Claims (5)

  1. 金属粉末と有機溶剤とからなるダイボンド用の導電性ペーストであって、
    前記金属粉末は、純度９９．９質量％以上、平均粒径０．０１μｍ〜１．０μｍである銀粉、パラジウム粉、銅粉から選択される一種以上の金属粒子と、前記金属粒子の少なくとも一部を覆う金からなる被覆層と、からなる導電性ペースト。
  2. 被覆層の厚さが０．００２μｍ〜０．３μｍである請求項１記載のダイボンド用の導電性ペースト。
  3. 被覆層を構成する金属粒子の含有量は、ペースト重量に対して７０〜９９質量％の割合である請求項１又は請求項２記載のダイボンド用の導電性ペースト。
  4. 基板上へ接合部材をダイボンドする方法において、
    前記基板又は前記接合部材に、請求項１〜請求項３のいずれかに記載の導電性ペーストを塗布する工程、
    基板上に接合部材を配置した後、一方向又は双方向から加圧しながら加熱して接合する工程、を含むダイボンド方法。
  5. 接合時の加熱温度は、８０〜３００℃の温度である請求項４記載のダイボンド方法。
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EP3070738A4 (en) * 2013-11-13 2017-06-21 Tanaka Kikinzoku Kogyo K.K. Through electrode and method for producing multilayer substrate using through electrode
KR20200093678A (ko) 2018-01-23 2020-08-05 다나카 기킨조쿠 고교 가부시키가이샤 도전성 접착제 조성물, 도전성 접착제 경화물 및 전자 기기
WO2020222542A1 (ko) * 2019-05-02 2020-11-05 파워팩 주식회사 습식공정에 의해 제조되는 산화 안정성이 향상된 은 나노 분말 및 이의 제조방법
JP2021153095A (ja) * 2020-03-24 2021-09-30 株式会社東芝 半導体装置
JP7293160B2 (ja) 2020-03-24 2023-06-19 株式会社東芝 半導体装置

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