JP2017066485A - シートおよび複合シート - Google Patents

シートおよび複合シート Download PDF

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Publication number
JP2017066485A
JP2017066485A JP2015193244A JP2015193244A JP2017066485A JP 2017066485 A JP2017066485 A JP 2017066485A JP 2015193244 A JP2015193244 A JP 2015193244A JP 2015193244 A JP2015193244 A JP 2015193244A JP 2017066485 A JP2017066485 A JP 2017066485A
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Japan
Prior art keywords
sintering
sheet
layer
sintering layer
weight
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JP2015193244A
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English (en)
Inventor
菜穂 鎌倉
Nao Kamakura
菜穂 鎌倉
悠樹 菅生
Yuki Sugao
悠樹 菅生
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Nitto Denko Corp
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Nitto Denko Corp
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Publication date
Application filed by Nitto Denko Corp filed Critical Nitto Denko Corp
Priority to JP2015193244A priority Critical patent/JP2017066485A/ja
Priority to US15/762,504 priority patent/US10888929B2/en
Priority to CN201680058259.9A priority patent/CN108136503B/zh
Priority to PCT/JP2016/077833 priority patent/WO2017057127A1/ja
Priority to EP16851301.8A priority patent/EP3357607B1/en
Priority to TW105131686A priority patent/TWI686249B/zh
Publication of JP2017066485A publication Critical patent/JP2017066485A/ja
Pending legal-status Critical Current

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    • B22F7/06—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools
    • B22F7/08—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools with one or more parts not made from powder
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Abstract

【課題】ナノサイズの金属粒子を含むペーストを基板に塗布し、焼結してチップを固定する技術において、焼結後に焼結体に残存する有機物が少ないシートの提供。【解決手段】ポリカーボネートと、銀、銅、酸化銀及び酸化銅から選択された少なくとも１種の金属粒子を含む、焼結前層１１を含み、焼結前層１１のＤＴＡ曲線が１５０〜３５０℃に少なくとも一つのピークを有するシート７１。ポリカーボネートは、焼結によって、効果的に熱分解し、焼結体に残存する有機物を少なくすることができる。【選択図】図２

Description

本発明は、シートと複合シートとに関する。
熱硬化性樹脂を含む導電性の接着剤（以下、「熱硬化型接着剤」という）で基板にチップを固定することがある。しかしながら、熱硬化型接着剤で基板にチップを固定したパワーモジュールは所定の信頼性―たとえば温度サイクル試験で評価される信頼性―を確保できないことがある。
ところで、ナノサイズの金属粒子を含むペーストを基板に塗布し、焼結する技術などがある。たとえば特許文献１は、金属粒子を含むフィルムを開示している。
ＷＯ ２０１４／０６８２９９ Ａ１
特許文献１に記載されたフィルム―Ｅｘａｍｐｌｅ １７―の焼結体には多くの有機物が残存する可能性がある。特許文献１に記載されたフィルムはエポキシ樹脂を含有するからである。温度サイクル試験における信頼性の低下・電気伝導性の低下を焼結体中の有機物はもたらす。
本発明は、焼結体に残存する有機物が少ない焼結前層を有するシートを提供することを目的とする。本発明はまた、焼結体に残存する有機物が少ない焼結前層を有する複合シートを提供することを目的とする。
本発明は、焼結前層を含むシートに関する。焼結前層はポリカーボネートを含む。焼結前層の焼結体に残存する有機物の量は、エポキシ樹脂含有フィルムの焼結体に残存するそれとくらべて少ないだろう。エポキシ樹脂とくらべてポリカーボネートは焼結によって効果的に熱分解するからである。よって、エポキシ樹脂含有フィルムとくらべて本発明のシートは、焼結体の信頼性―温度サイクル試験の信頼性―に優れているだろう。
本発明はまた複合シートに関する。はく離ライナーと、はく離ライナー上に配置された焼結前層と、焼結前層上に配置されたダイシングシートとを複合シートは含むことができる。
本発明はまたパワーモジュールの製造方法に関する。本発明のパワーモジュールの製造方法は、半導体ウエハにシート―ダイシングシートとダイシングシート上に配置された焼結前層とを含む―を貼り付ける工程（ａ）を含む。本発明のパワーモジュールの製造方法は、工程（ａ）の後にダイ分割により焼結前チップ―半導体チップと半導体チップ上に配置された焼結前フィルムとを含む―を形成する工程（ｂ）をさらに含む。本発明のパワーモジュールの製造方法は、焼結前チップを被着体に圧着する工程（ｃ）と、工程（ｃ）の後に焼結前フィルムの焼結をおこなう工程（ｄ）とをさらに含む。
複合シートの概略平面図である。 複合シートの一部の概略断面図である。 パワーモジュールの製造工程の概略断面図である。 パワーモジュールの製造工程の概略断面図である。 パワーモジュールの製造工程の概略断面図である。 パワーモジュールの製造工程の概略断面図である。 変形例４における複合シートの一部の概略断面図である。 変形例５のシートの概略断面図である。 実施例１のＤＴＡ曲線である。
以下に実施形態を掲げ、本発明を詳細に説明するが、本発明はこれらの実施形態のみに限定されるものではない。
［実施形態１］
（複合シート１）
図１に示すように、複合シート１はロール状をなす。はく離ライナー１３と、はく離ライナー１３上に配置されたシート７１ａ、７１ｂ、７１ｃ、……、７１ｍ（以下、「シート７１」と総称する。）とを複合シート１は含む。シート７１ａとシート７１ｂのあいだの距離、シート７１ｂとシート７１ｃのあいだの距離、……シート７１ｌとシート７１ｍのあいだの距離は一定である。
図２に示すように、シート７１は焼結前層１１を含む。焼結前層１１上に配置されたダイシングシート１２をシート７１はさらに含む。ダイシングシート１２は、基材１２１と、基材１２１上に配置された粘着剤層１２２とを含む。粘着剤層１２２と接した第１主面と第１主面に対向した第２主面とで焼結前層１１の両面は定義される。第２主面は はく離ライナー１３と接する。
粘着剤層１２２は第１部分１２２Ａを含む。第１部分１２２Ａは硬化している。第１部分１２２Ａは焼結前層１１と接する。第１部分１２２Ａの周辺に配置された第２部分１２２Ｂを粘着剤層１２２はさらに含む。第２部分１２２Ｂはエネルギー線により硬化する性質を有する。エネルギー線として紫外線などを挙げることができる。第２部分１２２Ｂは焼結前層１１と接しない。
加熱により焼結体となる性質を焼結前層１１は有する。第１物体と第２物体とを接合するために焼結前層１１は使用されることができる。たとえばチップと基板との接合である。基板は、絶縁基板と絶縁基板上に配置された導体層とを含むことができる。絶縁基板としてセラミック基板などを挙げることができる。
焼結前層１１の厚みは好ましくは３０μｍ以上、より好ましくは４０μｍ以上である。焼結前層１１の厚みは好ましくは２００μｍ以下、より好ましくは１５０μｍ以下、さらに好ましくは１００μｍ以下である。
大気雰囲気下において昇温速度１０℃／ｍｉｎで２３℃から５００℃まで昇温するＴＧ−ＤＴＡにより描かれる焼結前層１１のＤＴＡ曲線は１５０℃〜３５０℃に少なくともひとつのピーク頂点を有し、３５０℃を越える範囲にピーク頂点を有しない。ＤＴＡ曲線が３５０℃を越える範囲にピーク頂点を有すると、焼結後に有機物が多く残ることがある。
焼結前層１１はポリカーボネートを含む。ポリカーボネートはバインダーに位置づけることができる。ポリカーボネートは、好ましくは２３℃で固形をなす。２３℃で固形をなすと、焼結前層１１の成形が容易である。
焼結で熱分解する性質をポリカーボネートは有することが好ましい。たとえば、大気雰囲気下において昇温速度１０℃／ｍｉｎで２３℃から４００℃まで昇温した後の炭素濃度が１５重量％以下を示す―という性質である。炭素濃度は、エネルギー分散型Ｘ線分析により測定できる。
ポリカーボネートにおける３００℃の重量減少率は好ましくは９５％以上である。９５％以上であると、焼結後のポリカーボネート量が少ない。１０℃／ｍｉｎで昇温するＴＧ−ＤＴＡによりポリカーボネートの重量が５％減少する温度は、好ましくは２６０℃以下である。２６０℃以下であると、焼結後のポリカーボネート量が少ない。
ポリカーボネートの重量平均分子量は、好ましくは１万以上、より好ましくは３万以上、さらに好ましくは５万以上である。ポリカーボネートの重量平均分子量は、好ましくは１００万以下、より好ましくは５０万以下、さらに好ましくは３５万以下である。重量平均分子量は、ＧＰＣ（ゲル・パーミエーション・クロマトグラフィー）により測定し、ポリスチレン換算により算出された値である。
ポリカーボネートはたとえば脂肪族ポリカーボネートである。主鎖の炭酸エステル基（−O−CO−O−）のあいだに芳香族化合物（たとえば、ベンゼン環）を脂肪族ポリカーボネートは有さないことが好ましい。主鎖の炭酸エステル基のあいだに脂肪族鎖を脂肪族ポリカーボネートは有することが好ましい。脂肪族ポリカーボネートはたとえばポリプロピレンカーボネート、ポリエチレンカーボネート、tert-ブチルエチレンカーボネートである。なかでも、ポリプロピレンカーボネートが好ましい。焼結で効果的に熱分解するからである。
１００重量％の焼結前層１１中のポリカーボネートの含有量は好ましくは０．５重量％以上、より好ましくは１重量％以上である。１００重量％の焼結前層１１中のポリカーボネートの含有量は好ましくは２０重量％以下、より好ましくは１５重量％以下、さらに好ましくは１０重量％以下、さらに好ましくは５重量％以下である。
焼結前層１１は金属粒子を含む。銀粒子、銅粒子、酸化銀粒子、酸化銅粒子などである。１種または２種以上の金属粒子を焼結前層１１は含むことができる。８０℃から３００℃まで１．５℃／秒で昇温し、３００℃を２．５分間 維持することにより焼結体になる―という性質を金属粒子は有することが好ましい。
金属粒子の平均粒子径の下限はたとえば０．０５ｎｍ、０．１ｎｍ、１ｎｍである。金属粒子の平均粒子径の上限はたとえば１０００ｎｍ、１００ｎｍである。粒度分布測定装置(日機装製のマイクロトラックＨＲＡ)を用い標準モードで測定することにより求められるＤ５０データを平均粒子径とする。
１００重量％の焼結前層１１中の金属粒子の含有量は好ましくは５０重量％以上、より好ましくは６０重量％以上、さらに好ましくは６５重量％以上である。１００重量％の焼結前層１１中の金属粒子の含有量は好ましくは９８重量％以下、より好ましくは９７重量％以下、さらに好ましくは９５重量％以下である。
１００℃〜３５０℃の沸点を有するバインダー（以下、「低沸点バインダー」という。）を焼結前層１１はさらに含む。
ポリカーボネート、金属粒子などを含有するワニスを調製し、ワニスを支持体に塗工し、ワニスを乾燥させる方法などにより焼結前層１１を得ることができる。ワニスの溶剤はたとえばメチルエチルケトンである。
粘着剤層１２２の厚みは好ましくは３μｍ以上、より好ましくは５μｍ以上である。粘着剤層１２２の厚みは好ましくは５０μｍ以下、より好ましくは３０μｍ以下である。
粘着剤層１２２は粘着剤により形成されている。粘着剤はたとえばアクリル系粘着剤、ゴム系粘着剤である。なかでもアクリル系粘着剤が好ましい。アクリル系粘着剤はたとえば、（メタ）アクリル酸アルキルエステルの１種または２種以上を単量体成分として用いたアクリル系重合体（単独重合体または共重合体）をベースポリマーとするアクリル系粘着剤である。
基材１２１の厚みは好ましくは５０μｍ〜１５０μｍである。エネルギー線を透過する性質を基材１２１は有することが好ましい。
はく離ライナー１３の厚みは好ましくは２０μｍ〜７５μｍ、より好ましくは２５μｍ〜５０μｍである。はく離ライナー１３としてポリエチレンテレフタレート（ＰＥＴ）フィルムなどを挙げることができる。
（パワーモジュールの製造方法）
図３に示すように、半導体ウエハ４にシート７１を貼り付ける。半導体ウエハ４はたとえばシリコンウエハ、シリコンカーバイドウエハ、窒化ガリウムウエハなどである。たとえば７０℃〜８０℃で貼り付ける。
図４に示すように、半導体ウエハ４をダイシングすることにより、焼結前チップ５を形成する。半導体チップ４１と半導体チップ４１上に配置された焼結前フィルム１１１とを焼結前チップ５は含む。
焼結前チップ５をピックアップする。すなわち、焼結前チップ５をニードルで突き上げ、つまみ、粘着剤層１２２から離す。
図５に示すように、焼結前チップ５を被着体６に圧着することにより焼結前複合体２を得る。たとえば８０℃〜１００℃で圧着する。被着体６はたとえば基板、リードフレーム、インターポーザ、ＴＡＢフィルム、半導体チップなどである。焼結前複合体２は、被着体６と、半導体チップ４１と、被着体６および半導体チップ４１に挟まれた焼結前フィルム１１１とを含む。
焼結前フィルム１１１の焼結をおこなう。すなわち焼結前複合体２に平板で力を加えながら、焼結前複合体２を加熱し、焼結前フィルム１１１を焼結体に変化させる。焼結温度の下限はたとえば２００℃、２５０℃である。焼結温度の上限はたとえば３２０℃、３５０℃である。焼結前複合体２に与える圧力の下限はたとえば１ＭＰａ、５ＭＰａである。焼結前複合体２に与える圧力の上限はたとえば２０ＭＰａ、３０ＭＰａである。
図６に示すように、半導体チップ４１の電極パッドと被着体６の端子部とをボンディングワイヤー７で電気的に接続する。ボンディングワイヤー７はたとえばアルミニウムワイヤー、金ワイヤー、銅ワイヤーである。
ワイヤーボンディングの後、封止樹脂８で半導体チップ４１を封止する。封止後にさらに加熱をしてもよい。これにより、硬化不足の封止樹脂８を完全に硬化できる。
以上の方法により得られたパワーモジュールは、被着体６と、半導体チップ４１と、被着体６および半導体チップ４１の間に挟まれた焼結体とを含む。パワーモジュールは、半導体チップ４１を覆う封止樹脂８をさらに含む。
以上のとおり、パワーモジュールの製造方法は、半導体ウエハ４にシート７１を貼り付ける工程（ａ）と、工程（ａ）の後にダイ分割により焼結前チップ５を形成する工程（ｂ）と、焼結前チップ５を被着体６に圧着する工程（ｃ）と、工程（ｃ）の後に焼結前フィルム１１１の焼結をおこなう工程（ｄ）とを含む。焼結前複合体２を加熱するステップを工程（ｄ）は含む。
工程（ｄ）の後に、ボンディングワイヤー７の第１端と半導体チップ４１とを接合するステップ、ボンディングワイヤー７の第２端と被着体６とを接合するステップを含む工程（ｅ）をパワーモジュールの製造方法はさらに含む。パワーモジュールの製造方法は、封止樹脂８で半導体チップ４１を封止する工程（ｆ）をさらに含む。
（変形例１）
粘着剤層１２２の第１部分１２２Ａはエネルギー線により硬化する性質を有する。粘着剤層１２２の第２部分１２２Ｂもエネルギー線により硬化する性質を有する。焼結前チップ５を形成する工程（ｂ）の後に、粘着剤層１２２にエネルギー線を照射し焼結前チップ５をピックアップする工程をパワーモジュールの製造方法はさらに含む。エネルギー線を照射すると、焼結前チップ５のピックアップが容易である。
（変形例２）
粘着剤層１２２の第１部分１２２Ａはエネルギー線により硬化されている。粘着剤層１２２の第２部分１２２Ｂもエネルギー線により硬化されている。
（変形例３）
焼結前層１１は、第１層および第１層上配置された第２層を含む複層形状をなす。
（変形例４）
図７に示すように、粘着剤層１２２の片面全体が焼結前層１１と接する。エネルギー線により硬化する性質を粘着剤層１２２は有する。焼結前チップ５を形成する工程（ｂ）の後に、粘着剤層１２２にエネルギー線を照射し焼結前チップ５をピックアップする工程をパワーモジュールの製造方法はさらに含む。
（変形例５）
図８に示すように、シート１７１は焼結前層１１を含む。第１面と第１面に対向した第２面とで焼結前層１１の両面が定義される。第１面上に配置された第１はく離ライナー１４と、第２面上に配置された第２はく離ライナー１５とをシート１７１はさらに含む
（そのほかの変形例）
変形例１〜変形例５などは、任意に組み合わせることができる。
以下、本発明に関し実施例を用いて詳細に説明するが、本発明はその要旨を超えない限り、以下の実施例に限定されるものではない。
［焼結前シートの原料など］
銀ペースト：応用ナノ粒子研究所製のＡＮＰ−１（バインダーにナノサイズの銀微粒子が分散したペースト）に含まれる粘度調整用の溶剤量を適宜調整したもの。
溶剤：メチルエチルケトン（ＭＥＫ）
ポリカーボネート：Ｅｍｐｏｗｅｒ社製のＱＰＡＣ４０（重量平均分子量５万〜３５万のポリプロピレンカーボネート）
アクリルポリマー：藤倉化成社製のＭＭ−２００２−１
［焼結前シートの作製］
表１の記載にしたがい、ハイブリッドミキサー(キーエンス製 ＨＭ−５００)の攪拌釜に各成分と溶剤とを入れ、２０００ｒｐｍで８分 攪拌することにより、ワニスを得た。離型処理フィルム（三菱樹脂社製のＭＲＡ３８）にワニスを塗工した。１１０℃ ３分で乾燥させることにより焼結前シートを得た。
［評価１ 信頼性］
厚み３５０μｍ、縦５ｍｍ、横５ｍｍのシリコンチップと、シリコンチップの裏面に設けられた厚み５０ｎｍのＴｉ膜と、Ｔｉ膜上に設けられた厚み１００ｎｍのＡｇ膜とを有するチップを準備した。７０℃、０．３ＭＰａ、１０ｍｍ／ｓｅｃの条件でチップのＡｇ膜に焼結前シートを貼り付けることにより、焼結前シート付きチップを作製した。ＡｇめっきＣｕ基板―厚み３ｍｍのＣｕ基板と、Ｃｕ基板全体を覆う厚み５μｍのＡｇ膜とを有する―上に焼結前シート付きチップを配置した。焼結装置（伯東社製のＨＴＭ−３０００）で焼結をおこない、ＡｇめっきＣｕ基板とチップとを接合した。具体的には、平板プレスで１０ＭＰａの圧力を加えながら８０℃から３００℃まで昇温速度１．５℃／秒で昇温し、１０ＭＰａの圧力を加えながら３００℃を２．５分間 保持する―ことにより接合した。
ＡｇめっきＣｕ基板とチップとの接合により得られた試料に冷熱衝撃試験機（エスペック社製のＴＳＥ−１０３ＥＳ）で１００サイクルの温度変化を与えた。ひとつのサイクルは、−４０℃を１５分保持する第１時間と、２００℃を１５分保持する第２時間とからなる。１００サイクル後の試料を超音波映像装置（日立建機ファインテック社製のＦｉｎｅＳＡＴ II）で観察した。ＰＱ−５０−１３：ＷＤ（周波数５０ＭＨｚ）―プローブ―を使用した。得られた像において接合が残っている部分の面積（以下、「残面積」という）を求めた。全面積を１００％としたときの残面積の割合を算出した。残面積の割合が５０％以上の場合は○と判定した。５０％より低い場合は×と判定した。結果を表１に示す。
［評価２ 銀微粒子の含有量］
１０℃／ｍｉｎで２３℃から５００℃まで昇温するＴＧ−ＤＴＡにより銀微粒子の含有量を求めた。結果を表１に示す。
Figure 2017066485
比較例１とくらべて実施例１〜２―ポリカーボネートを配合した例―の温度変化試験の信頼性がよかった。
［評価３ そのほか］
（ポリカーボネートの評価）
ポリカーボネートにおける３００℃の重量減少率は９５％以上だった。重量減少率はＴＧ−ＤＴＡで測定した。１０℃／ｍｉｎで昇温するＴＧ−ＤＴＡによりポリカーボネートの重量が５％減少する温度は２６０℃以下だった。
（焼結前シートの評価）
実施例１の焼結前シートから測定試料を切り出した。ＴＧ−ＤＴＡによりＤＴＡ曲線を描いた。大気雰囲気下において昇温速度１０℃／ｍｉｎで２３℃から５００℃まで昇温した。ＤＴＡ曲線を図９に示す。
１ 複合シート
１１ 焼結前層
１２ ダイシングシート
１３ はく離ライナー
７１ シート
１２１ 基材
１２２ 粘着剤層
１２２Ａ 第１部分
１２２Ｂ 第２部分
２ 焼結前複合体
４ 半導体ウエハ
５ 焼結前チップ
４１ 半導体チップ
１１１ 焼結前フィルム
６ 被着体
７ ボンディングワイヤー
８ 封止樹脂
１７１ シート
１４ 第１はく離ライナー
１５ 第２はく離ライナー

Claims (9)

  1. 焼結前層を含み、
    前記焼結前層はポリカーボネートを含むシート。
  2. 大気雰囲気下において昇温速度１０℃／ｍｉｎで２３℃から５００℃まで昇温するＴＧ−ＤＴＡにより描かれる前記焼結前層のＤＴＡ曲線は１５０℃〜３５０℃に少なくともひとつのピーク頂点を有し、３５０℃を越える範囲にピーク頂点を有しない請求項１に記載のシート。
  3. 前記焼結前層が金属粒子を含む請求項１または２に記載のシート。
  4. 前記金属粒子が、銀粒子、銅粒子、酸化銀粒子および酸化銅粒子からなる群より選ばれた少なくとも１種を含む請求項３に記載のシート。
  5. 前記焼結前層１００重量％中の前記金属粒子の含有量は５０重量％〜９８重量％である請求項３または４に記載のシート。
  6. 前記焼結前層は、第１物体と第２物体とを接合するために使用される請求項１〜５のいずれかに記載のシート。
  7. 第１面と前記第１面に対向した第２面とで前記焼結前層の両面が定義され、
    前記第１面上に配置された第１はく離ライナーと、
    前記第２面上に配置された第２はく離ライナーとをさらに含む請求項１〜６のいずれかに記載のシート。
  8. 前記焼結前層上に配置されたダイシングシートをさらに含む請求項１〜６のいずれかに記載のシート。
  9. はく離ライナーと、
    前記はく離ライナー上に配置された請求項８に記載のシートとを含む複合シート。

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