JP2008277421A - ダイボンド剤及びこれを用いてなる半導体装置 - Google Patents
ダイボンド剤及びこれを用いてなる半導体装置 Download PDFInfo
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- JP2008277421A JP2008277421A JP2007117126A JP2007117126A JP2008277421A JP 2008277421 A JP2008277421 A JP 2008277421A JP 2007117126 A JP2007117126 A JP 2007117126A JP 2007117126 A JP2007117126 A JP 2007117126A JP 2008277421 A JP2008277421 A JP 2008277421A
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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Abstract
【解決手段】(A)エポキシ樹脂、(B)硬化剤及び(C)無機充填剤を含むダイボンド剤において、 該ダイボンド剤0.5mlを、ブルックフィールド型粘度計でNo.51のスピンドルを用いて、0.5rpmで攪拌した際の粘度(V1)と5rpmで攪拌した際の粘度(V2)との比V1/V2が、(i)室温〜50℃において1.5〜4であり、且つ、(ii)該ダイボンド剤が0.5〜1.5時間で硬化する温度で、ブルックフィールド型粘度計の試料台に該ダイボンド剤を置いてから10分以内に測定されたときに、0.5以上1.5未満である、ことを特徴とするダイボンド剤。
【選択図】なし
Description
(A)エポキシ樹脂、(B)硬化剤及び(C)無機充填剤を含むダイボンド剤において、
該ダイボンド剤0.5mlを、ブルックフィールド型粘度計でNo.51のスピンドルを用いて、0.5rpmで攪拌した際の粘度(V1)と5rpmで攪拌した際の粘度(V2)との比V1/V2が、
(i)室温〜50℃において1.5〜4であり、且つ、
(ii)該ダイボンド剤が0.5〜1.5時間で硬化する温度で、ブルックフィールド型粘度計の試料台に該ダイボンド剤を置いて10分以内に測定されたときに、0.5以上1.5未満である、
ことを特徴とするダイボンド剤である。
(I)B〜C間の距離がA〜B間の距離以下であり、且つ、
(II)該フィレットがAとCを結ぶ直線より外部にはみ出していない。
上記A〜Cの各点については、図1に示す。
(i)室温〜50℃において1.5〜4であり、且つ、
(ii)該ダイボンド剤が0.5〜1.5時間で硬化する温度で、ブルックフィールド型粘度計の試料台に該ダイボンド剤を置いてから10分以内に測定されたときに、0.5以上1.5未満であるダイボンド剤によって形成することができる。
上記特徴(i)は、ダイボンディング工程の際の特性であり、特徴(ii)は硬化直前の特性である。なお上記の粘度測定条件は、絶対的なものではなく、例えばレオロジーメータ等の他の測定方法を用いて、上記条件と同等の範囲を定めてもよい。
(i)室温〜50℃において測定する工程、及び
(ii)該ダイボンド剤が0.5〜1.5時間で硬化する温度で、ブルックフィールド型粘度計の試料台に該ダイボンド剤を置いて10分以内に測定する工程、
を含む方法にも関する。
工程(i)の結果が、1.5〜3.5であるもののみ、工程(ii)を行なってもよい。
本発明において、(A)エポキシ樹脂としては、公知のものを使用することができる。例えば、ノボラック型、ビスフェノール型、ビフェニル型、フェノールアラルキル型、ジシクロペンタジエン型、ナフタレン型、アミノ基含有型、後述するシリコーン変性エポキシ樹脂及びこれらの混合物等が挙げられる。なかでもビスフェノールA型、ビスフェノールF型及びシリコーン変性エポキシ樹脂が好ましい。また、25℃において液状の樹脂が好ましく、より好ましくは、25℃における粘度が100Pa・s以下、より好ましくは10Pa・s以下である。
硬化剤(B)としては公知のものを使用することができ、例えばフェノール樹脂(後述するシリコーン変性フェノール樹脂を含む)、酸無水物、及びアミン類が挙げられる。この中でも硬化性とBステージ状態の安定性のバランスを考慮すると、フェノール樹脂及びシリコーン変性フェノール樹脂が好ましい。該フェノール樹脂としては、ノボラック型、ビスフェノール型、トリスヒドロキシフェニルメタン型、ナフタレン型、シクロペンタジエン型、フェノールアラルキル型等が挙げられ、これらを単独、あるいは2種類以上を混合して用いても良い。なかでもノボラック型、ビスフェノール型が好ましく、また、25℃における粘度が100℃において10Pa・s、特に1Pa・s以下であることが望ましい。
但し、R11は、フェノール樹脂の場合には水素原子であり、エポキシ樹脂である場合には下記式で表されるオキシラン基含有基であり、
R12は水素原子又はメチル基であり、Xは水素原子又は臭素原子であり、nは0以上の整数、好ましくは0乃至50、特に好ましくは1乃至20の整数である。
但し、R11、R12、X及びnについては上で述べた通りであり、mは0以上の整数、好ましくは0乃至5の整数、特に好ましくは0或いは1である。
(R13)a(R14)bSiO(4−a−b)/2 (9)
但し、R13は水素原子、或いは、アミノ基、エポキシ基、ヒドロキシ基もしくはカルボキシ基を含有する有機基、或いはアルコキシ基。であり、R14は置換、或いは非置換の1価炭化水素基、ヒドロキシ基、アルコキシ基、或いはアルケニルオキシ基であり、a、bは0.001≦a≦1、1≦b≦3、1≦a+b≦4を満足する数である。1分子中のケイ素原子数は1乃至1000であり、1分子中のケイ素原子に直結したR13は1以上である。
エポキシ基含有有機基としては、下記のものが例示され、ここで cは1、2、又は3である。
ヒドロキシ基含有有機基としては、下記のものが例示され、ここで、dは0、1、2、又は3であり、eは1、2又は3である。
カルボキシ基含有有機基としては、下記が例示され、ここで、fは1〜10の整数である。
またアルコキシ基としては、メトキシ基、エトキシ基、n-プロポキシ基等の炭素数1〜4のものが挙げられる。
但し、R16はアミノ基、エポキシ基、ヒドロキシ基、又はカルボキシ基含有の1価炭化水素基であり、R15は置換、或いは非置換の1価炭化水素基、好ましくはメチル基或いはフェニル基であり、pは0乃至1000の整数、好ましくは3乃至400の整数であり、qは0乃至20の整数、好ましくは0乃至5の整数である。
無機充填剤としては、例えば、溶融シリカ、結晶シリカ、アルミナ、酸化チタン、シリカチタニア、窒化ホウ素、窒化アルミニウム、窒化ケイ素、マグネシア、マグネシウムシリケート、タルク、マイカ等及びこれらの組合わせを挙げることができ、特に、シリカ、アルミナ、タルク及びこれらの組合わせが好ましい。
本発明のダイボンド剤は、(D)硬化促進剤をさらに含んでよい。(D)硬化促進剤としては、公知のものを使用することができる。例えば有機リン、イミダゾール、3級アミン等の塩基性有機化合物が挙げられる。有機リンの例としては、トリフェニルホスフィン、トリブチルホスフィン、トリ(p−トルイル)ホスフィン、トリ(p−メトキシフェニル)ホスフィン、トリ(p−エトキシフェニル)ホスフィン、トリフェニルホスフィン・トリフェニルボレート誘導体、テトラフェニルホスフィン・テトラフェニルボレート等が挙げられる。イミダゾールの例としては、2−メチルイミダゾール、2−エチルイミダゾール、2−エチル−4−メチルイミダゾール、2−フェニルイミダゾール、2−フェニル−4−メチルイミダゾール、2−フェニル-4-メチル−5−ヒドロキシメチルイミダゾール、2−フェニル−4,5−ジヒドロキシメチルイミダゾール等が挙げられ、3級アミンの例としてはトリエチルアミン、ベンジルジメチルアミン、α−メチルベンジルジメチルアミン、1,8−ジアザビシクロ(5,4,0)ウンデセン−7等が挙げられる。これらのなかでも、テトラフェニルホスフィン・テトラフェニルボレート誘導体、又はメチロールイミダゾール誘導体を、硬化剤としてのフェノール樹脂と組合わせて使用することが好ましい。
但し、R1乃至R8は夫々独立に水素原子又は或いは炭素数1乃至10の炭化水素基、或いはハロゲン原子である。
但し、R9はメチル基或いはメチロール基であり、R10は炭素数1乃至10の炭化水素基である。
本発明のダイボンド剤は、希釈剤を含んでよい。該希釈剤をとしては、例えば、トルエン、キシレン、ヘキサン、ヘプタン、エタノール、イソプロピルアルコール、アセトン、メチルエチルケトン等が挙げられる。
エポキシ樹脂A(ビスフェノール型エポキシ樹脂、エポキシ当量180、日本化薬製RE310S)、
フェノール樹脂B(フェノールノボラック樹脂、当量110、明和化学製DL−92)、
シリコーン変性エポキシ樹脂C(合成例1)、
シリコーン変性フェノール樹脂D(合成例2)、
硬化促進剤E(テトラフェニルホスフィン・テトラフェニルボレート、北興化学製TPP−K)、
シリカF(球状溶融シリカ、平均粒径0.8ミクロン、最大粒径3ミクロン、アドマッテクス製SE2030)、
シリカG(球状溶融シリカ、KBM−403処理品、平均粒径0.8ミクロン、最大粒径3ミクロン、アドマッテクス製SE2030−SEE)、
接着助剤H(γ−グリシドキシプロピルトリメトキシシラン、信越化学工業製KBM−403)、
希釈剤I(カルビトールアセテート)
(合成例1)
攪拌羽、滴下漏斗、温度計、エステルアダプターと環流管を取り付けたフラスコに、式(12)のエポキシ樹脂42.0g(0.10mol)とトルエン168.0gを入れ、130℃/2時間で共沸脱水を行った。これを100℃に冷却し、触媒(信越化学製CAT−PL−50T)0.5gを滴下し、直ちに式(13)のオルガノポリシロキサン36.3g(0.05mol)とトルエン145.2gの混合物を30分程度で滴下し、更に100℃/6時間で熟成した。これからトルエンを除去し、黄色透明液体(η=5Pa・s/25℃、エポキシ当量400、オルガノポリシロキサン含有量46.4重量部)を得た。これをシリコーン変性エポキシ樹脂Cとした。
攪拌羽、滴下漏斗、温度計、エステルアダプターと環流管を取り付けたフラスコに、式(14)のフェノール樹脂30.8g(0.10mol)とトルエン123.2gを入れ、130℃/2時間で共沸脱水を行った。これを100℃に冷却し、触媒(信越化学製CAT−PL−50T)0.5gを滴下し、直ちに式(13)のオルガノポリシロキサン36.3g(0.05mol)とトルエン145.2gの混合物を30分程度で滴下し、更に100℃/6時間で熟成した。これからトルエンを除去し、褐色透明液体(η=20Pa・s/25℃、フェノール当量340、オルガノポリシロキサン含有量54.1重量部)を得た。これをシリコーン変性フェノール樹脂Dとした。
表1に示す各量(重量部)の各成分を、25℃のプラネタリーミキサーで混合した後、25℃の3本ロールを通過させ、再度25℃のプラネタリーミキサーで混合して、ダイボンド剤を得た。これらのダイボンド剤について、以下の(a)〜(g)の諸試験を行い、表1の結果を得た。
(a)室温〜50℃における粘度及び(b)室温〜50℃における粘度比
各ダイボンド剤0.5mlを採取し、ブルックフィールド型粘度計とNo.51のスピンドルを用いて、実施例1及び3、比較例1では50℃、実施例2及び4、比較例2では25℃における0.5rpmと5rpmの粘度を測定し、0.5rpmの粘度を5rpmの粘度で割り、粘度比を算出した。
各ダイボンド剤0.5mlを、150℃のオイルバスに入れた、ブルックフィールド型粘度計用の試料台上に置き、5分以内に、No.51のスピンドルを用いて、150℃における0.5rpmと5rpmの粘度を測定した。
試験片の作成
図11に示すように、表面にソルダーレジスト(20ミクロン厚)が塗布されたBT基板(200ミクロン厚、35mm×35mm)上に各ダイボンド剤を塗布した(50ミクロン厚、12mm×12mm)。得られた樹脂膜上に、窒化珪素膜を施したシリコンチップ(300ミクロン厚、12.5mm×12.5mm)を、実施例1及び3、比較例1では50℃/100g/0.1秒で、実施例2及び4、比較例2では25℃/100g/0.1秒の条件で搭載した後、150℃で、後硬化時間2.5時間を含む合計4時間で硬化して試験片を作成した。
上記試験方法(e)と試験方法(f)の両方に関して、試験結果が0/20であるものを合格、それ以外のものを不合格とした。
Claims (6)
- (A)エポキシ樹脂、(B)硬化剤及び(C)無機充填剤を含むダイボンド剤において、
該ダイボンド剤0.5mlを、ブルックフィールド型粘度計でNo.51のスピンドルを用いて、0.5rpmで攪拌した際の粘度(V1)と5rpmで攪拌した際の粘度(V2)との比V1/V2が、
(i)室温〜50℃において1.5〜4であり、且つ、
(ii)該ダイボンド剤が0.5〜1.5時間で硬化する温度で、ブルックフィールド型粘度計の試料台に該ダイボンド剤を置いてから10分以内に測定されたときに、0.5以上1.5未満であることを特徴とするダイボンド剤。 - 前記ダイボンド剤が、(D)硬化促進剤をさらに含む、請求項1記載のダイボンド剤。
- 前記粘度比V1/V2が、
(i)室温〜50℃において1.5〜3.5であり、且つ、
(ii)130〜170℃で、前記ブルックフィールド型粘度計の試料台に該ダイボンド剤を置いてから10分以内に測定されたときに、0.8〜1.4である、
ことを特徴とする請求項1または2記載のダイボンド剤。 - 少なくとも1の半導体チップがダイボンド剤により接着された半導体装置において、
半導体チップの線対称中心線に沿って切断したときに観察される該ダイボンド剤により形成されたフィレットの断面形状が、該フィレットが接している半導体チップの側面上における該フィレットの最も高い点をA、該フィレットの半導体チップから最も遠い基板上の点をC、点Aから基板上に降ろした垂線と基板との交点をBとしたときに、
(I)B〜C間の距離がA〜B間の距離以下であり、且つ、
(II)該フィレットが、AとCを結ぶ直線より外部にはみ出していない、
ことを特徴とする半導体装置。 - 前記フィレットが、エポキシ樹脂硬化物を含む、請求項4記載の半導体装置。
- 半導体製造工程において、半導体チップ用のダイボンド剤を評価又は管理する方法であって、該ダイボンド剤0.5mlを、ブルックフィールド型粘度計でNo.51のスピンドルを用いて、0.5rpmで攪拌した際の粘度(V1)と5rpmで攪拌した際の粘度(V2)との比V1/V2を
(i)室温〜50℃において測定する工程、及び
(ii)該ダイボンド剤が0.5〜1.5時間で硬化する温度で、ブルックフィールド型粘度計の試料台に該ダイボンド剤を置いて10分以内に測定する工程、
を含む方法。
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