JP6466882B2 - 樹脂組成物、樹脂フィルム、樹脂フィルムの製造方法、半導体装置の製造方法及び半導体装置 - Google Patents
樹脂組成物、樹脂フィルム、樹脂フィルムの製造方法、半導体装置の製造方法及び半導体装置 Download PDFInfo
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- JP6466882B2 JP6466882B2 JP2016089533A JP2016089533A JP6466882B2 JP 6466882 B2 JP6466882 B2 JP 6466882B2 JP 2016089533 A JP2016089533 A JP 2016089533A JP 2016089533 A JP2016089533 A JP 2016089533A JP 6466882 B2 JP6466882 B2 JP 6466882B2
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Description
(B)エポキシ樹脂硬化剤、及び
(C)フィラー
を含有し、全質量に対し、前記(C)成分を50〜95質量%含有するものであることを特徴とする樹脂組成物を提供する。
本発明において、(A)成分のシリコーン樹脂はフィルム形成能を与えるものとして機能する。また、得られた樹脂フィルムをウエハモールド材として用いた場合、ウエハへの密着性、低反り性、良好なモールド性と耐熱性を与える。
本発明における(A)シリコーン樹脂は、下記一般式(4)、下記一般式(5)、下記一般式(6)及び下記一般式(7)で表される化合物から選択される化合物を用いて金属触媒存在下、付加重合することにより製造することができる。
(B)成分は、シリコーン樹脂(A)と架橋反応するための成分であり、(B)成分を加えることで、樹脂のウエハへの密着性、保護性、信頼性がより向上する。本発明においてエポキシ樹脂硬化剤は、エポキシ樹脂の硬化に通常使用されるものであればよく、特に限定されないが、耐熱性の観点から芳香族系硬化剤や脂環式硬化剤がより好ましい。該エポキシ樹脂硬化剤としては、例えば、アミン系硬化剤、フェノール系硬化剤、酸無水物系硬化剤、三フッ化ホウ素アミン錯塩等が挙げられ、特に、アミン系、フェノール系、及び酸無水物系のいずれかのエポキシ樹脂硬化剤であることが好ましい。また、エポキシ樹脂硬化剤は、1種を単独で用いても、2種以上を併用してもよい。
(C)成分は、本発明の樹脂組成物に、ウエハ保護性を与え、更に、耐熱性、耐湿性、強度等を向上させ、信頼性を上げることができる。フィラーとしては、例えばタルク、焼成クレー、未焼成クレー、マイカ、ガラス等のケイ酸塩、酸化チタン、アルミナ、溶融シリカ(溶融球状シリカ、溶融破砕シリカ)、結晶シリカ粉末等の酸化物、炭酸カルシウム、炭酸マグネシウム、ハイドロタルサイト等の炭酸塩、水酸化アルミニウム、水酸化マグネシウム、水酸化カルシウム等の水酸化物、硫酸バリウム、硫酸カルシウム、亜硫酸カルシウム等の硫酸塩又は亜硫酸塩、ホウ酸亜鉛、メタホウ酸バリウム、ホウ酸アルミニウム、ホウ酸カルシウム、ホウ酸ナトリウム等のホウ酸塩、窒化アルミニウム、窒化ホウ素、窒化ケイ素等の窒化物等を挙げることができる。これらのフィラーは1種単独で混合しても、2種以上を併せて混合してもよい。これらの中でも溶融シリカ、結晶シリカ等のシリカ粉末が好ましい。前記シリカ粉末としては、例えば、ヒュームドシリカ、沈降性シリカ等の補強性シリカ;石英等の結晶性シリカが挙げられる。具体的には、日本アエロジル(株)製のAerosil R972、R974、R976;(株)アドマテックス製のSE−2050、SC−2050、SE−1050、SO−E1、SO−C1、SO−E2、SO−C2、SO−E3、SO−C3、SO−E5、SO−C5;信越化学工業(株)製のMusil120A、Musil130A等が例示される。
本発明の樹脂組成物にウエハへの密着性、保護性を一層向上させる目的で、更に、(A)成分以外のエポキシ樹脂を添加することもできる。エポキシ樹脂は(A)シリコーン樹脂とともに(B)エポキシ樹脂硬化剤と架橋反応するため、樹脂のウエハへの密着性、保護性、信頼性がより向上する。
本発明の樹脂組成物はシランカップリング剤を含んでもよい。シランカップリング剤を含むことにより、樹脂組成物の被接着体への密着性を更に高めることができる。シランカップリング剤としては、エポキシシランカップリング剤、芳香族含有アミノシランカップリング剤等が挙げられる。これらは単独で用いても、2種以上を組み合わせて用いてもよい。シランカップリング剤の含有量は、特に限定されないが、配合させる場合には、本発明の樹脂組成物の総質量の0.01質量%以上5質量%以下とすることが好ましい。
その他の任意成分として有機溶剤を用いることができる。即ち、本発明の樹脂組成物は、無溶剤で用いてもよいが、有機溶剤に溶解又は分散し、溶液又は分散液(以下、単に「溶液」という)として調製してから使用してもよい。この有機溶剤としては、N,N−ジメチルアセトアミド、メチルエチルケトン、N,N−ジメチルホルムアミド、シクロヘキサノン、シクロペンタノン、N−メチル−2−ピロリドン、トルエン、メタノール、エタノール、イソプロパノール、アセトン、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート等が挙げられ、好ましくはメチルエチルケトン、シクロペンタノン、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテートが挙げられる。これらの有機溶剤は、1種を単独で用いても、2種以上を併用してもよい。
本発明の樹脂組成物はフィルム状に形成されることが好ましい。このような樹脂フィルムであれば、特に、大口径、薄膜ウエハに対して良好なモールド性を有するものとなり、ウエハを一括してモールドする際に、樹脂を流し込む必要がない。そのため、従来のトランスファー成形で生じうるワイヤ変形、ウエハ表面への充填不良や、圧縮成形法で生じうる成形範囲の制御の難しさ、液状封止樹脂の流動性と物性の問題は根本的に解消することができる。
予め、本発明における(A)シリコーン樹脂、(B)エポキシ樹脂硬化剤、(C)フィラー、必要に応じて、その他の任意成分(有機溶剤含む)を混合して液状に調製した樹脂組成物溶液を作製し、該樹脂組成物溶液をリバースロールコータ、コンマコータ等を用いて、保護層(剥離フィルム)に塗布する。前記樹脂組成物溶液が塗布された保護層をインラインドライヤに通し、80〜160℃で2〜20分間かけて有機溶剤を除去することにより乾燥させ、次いでロールラミネーターを用いて別の保護層(保護フィルム)と圧着し、積層することにより、本発明の樹脂フィルムを得ることができる。
樹脂フィルム(樹脂組成物層)を保護するための保護フィルムや、樹脂組成物溶液が塗布される剥離フィルムとしては、いずれも、本発明の樹脂組成物からなる樹脂フィルムの形態を損なうことなく剥離できるものであれば特に限定されないが、ウエハ用の保護フィルム及び剥離フィルムとして活用するものであり、通常、ポリエチレン(PE)フィルム、ポリプロピレン(PP)フィルム、ポリメチルペンテン(TPX)フィルム、離型処理を施したポリエステルフィルム等のプラスチックフィルム等が挙げられる。また、剥離力は50〜300mN/minが好ましく、厚さは25〜100μm、好ましくは38〜75μmである。
本発明の樹脂フィルムにより一括してモールドされるウエハとしては、特に制限されないが、表面に半導体素子(チップ)が積載されたウエハであっても、表面に半導体素子が作製された半導体ウエハであってもよい。本発明の樹脂フィルムは、モールド前にはこのようなウエハ表面に対する充填性が良好であり、また、モールド後には低反り性を有し、このようなウエハの保護性に優れる。また、本発明の樹脂フィルムは特に制限されないが、直径8インチ(200mm)以上、例えば、直径8インチ(200mm)、12インチ(300mm)といった大口径のウエハや薄膜ウエハをモールドするのに好適に用いることができる。また、薄型ウエハとしては、厚さ5〜300μmに薄型加工されたウエハが好ましい。
本発明の樹脂フィルムを用いたウエハのモールド方法については、特に限定されないが、例えば、樹脂フィルム上に貼られた一方の保護層を剥がし、図1に示すように、樹脂フィルム1を、ウエハ2の回路面をモールドするように回路面積に合わせて貼付する方法や(図1(A))、ウエハ2全体を覆うようにウエハ2上に一括貼付する方法が挙げられる(図1(B))。具体的方法としては、例えば、樹脂フィルム上に貼られた一方の保護層を剥がし、(株)タカトリ製の真空ラミネーター(製品名:TEAM−100RF)を用いて、真空チャンバー内を真空度50〜1,000Pa、好ましくは50〜500Pa、例えば100Paに設定し、80〜200℃、好ましくは80〜130℃、例えば100℃で他方の保護層が貼られた樹脂フィルムを上記ウエハに一括して密着させ、常圧に戻した後、上記ウエハを室温まで冷却して上記真空ラミネーターから取り出し、他方の保護層を剥離することで行うことができる。その後、120〜220℃で15〜180分間の条件で樹脂フィルムを加熱硬化することができる。
更に、本発明では前記樹脂フィルムを加熱硬化した加熱硬化皮膜でモールドされた半導体ウエハが個片化されたものである、加熱硬化皮膜を有する半導体装置を提供する。モールドされたウエハは、ダイシングテープなどの半導体加工用保護テープにモールド樹脂面、あるいは、ウエハ面が接するように貼られ、ダイサーの吸着テーブル上に設置され、このモールドされたウエハは、ダイシングブレードを備えるダイシングソー(例えば、DISCO製、DFD6361)を使用して切断される。ダイシング時のスピンドル回転数及び切断速度は適宜選択すればよいが、通常、スピンドル回転数25,000〜45,000rpm、切断速度10〜50mm/secである。また、個片化されるサイズは半導体パッケージの設計によるが、概ね2mm×2mm〜30mm×30mm程度である。
また、本発明では、本発明の樹脂フィルムを半導体ウエハに貼り付け、該半導体ウエハを前記樹脂フィルムでモールドする工程と、該モールドされた半導体ウエハを個片化する工程とを有することを特徴とする半導体装置の製造方法を提供する。
撹拌機、温度計、窒素置換装置及び還流冷却器を具備した3Lフラスコ内に、上記式(S−1)で示される化合物133g(0.50モル)を加えた後、トルエン2,000gを加え、70℃に加温した。その後、塩化白金酸トルエン溶液(白金濃度0.5質量%)1.0gを投入し、上記式(S−3)で示される化合物58.3g(0.30モル)及び上記式(S−4)で示される化合物(y=10)141g(0.20モル)を1時間かけて滴下した(ヒドロシリル基の合計モル数/アルケニル基の合計モル数=1/1、シリコーン含有率42.5質量%)。滴下終了後、100℃まで加温し6時間熟成した後、反応溶液からトルエンを減圧留去して得られた生成物のGPCにより測定したポリスチレン換算の重量平均分子量は42,000であった。得られた樹脂を樹脂(1)とし、実施例、比較例に供した。
撹拌機、温度計、窒素置換装置及び還流冷却器を具備した3Lフラスコ内に、上記式(S−1)で示される化合物106g(0.40モル)及び上記式(S−2)で示される化合物18.6g(0.10モル)を加えた後、トルエン2,000gを加え、70℃に加温した。その後、塩化白金酸トルエン溶液(白金濃度0.5質量%)1.0gを投入し、上記式(S−3)で示される化合物58.3g(0.30モル)及び上記式(S−4)で示される化合物(y=20)317g(0.20モル)を2時間かけて滴下した(ヒドロシリル基の合計モル数/アルケニル基の合計モル数=1/1、シリコーン含有率67.1質量%)。滴下終了後、100℃まで加温し6時間熟成した後、反応溶液からトルエンを減圧留去して得られた生成物のGPCにより測定したポリスチレン換算の重量平均分子量は44,000であった。得られた樹脂を樹脂(2)とし、実施例に供した。
撹拌機、温度計、窒素置換装置及び還流冷却器を具備した5Lフラスコ内に、上記式(S−1)で示される化合物133g(0.50モル)を加えた後、トルエン2,000gを加え、70℃に加温した。その後、塩化白金酸トルエン溶液(白金濃度0.5質量%)0.5gを投入し、上記式(S−3)で示される化合物58.3g(0.30モル)及び上記式(S−4)で示される化合物(y=40)553g(0.20モル)を1時間かけて滴下した(ヒドロシリル基の合計モル数/アルケニル基の合計モル数=1/1、シリコーン含有率74.4質量%)。滴下終了後、100℃まで加温し6時間熟成した後、反応溶液からトルエンを減圧留去して得られた生成物のGPCにより測定したポリスチレン換算の重量平均分子量は40,000であった。得られた樹脂を樹脂(3)とし、実施例に供した。
撹拌機、温度計、窒素置換装置及び還流冷却器を具備した5Lフラスコ内に、上記式(S−5)で示される化合物210g(0.50モル)を加えた後、トルエン2,000gを加え、70℃に加温した。その後、塩化白金酸トルエン溶液(白金濃度0.5質量%)1.0gを投入し、上記式(S−3)で示される化合物58.3g(0.30モル)及び上記式(S−4)で示される化合物(y=10)141g(0.20モル)を1時間かけて滴下した(ヒドロシリル基の合計モル数/アルケニル基の合計モル数=1/1、シリコーン含有率34.5質量%)。滴下終了後、100℃まで加温し6時間熟成した後、反応溶液からトルエンを減圧留去して得られた生成物のGPCにより測定したポリスチレン換算の重量平均分子量は39,000であった。得られた樹脂を樹脂(4)とし、比較例に供した。
(実施例1〜5)
下記表1に記載した組成で、(A)上記合成例1〜3で合成したシリコーン樹脂(上記樹脂(1)〜(3))、(B)エポキシ樹脂硬化剤、(C)フィラー及びエポキシ樹脂硬化促進剤、その他の任意成分を配合した。更に固形成分濃度が75質量%となる量のシクロペンタノンを添加し、ボールミルを使用して撹拌し、混合及び溶解分散して、樹脂組成物の分散液を調製した(実施例1〜5)。なお、表1中の配合量を示す数値の単位は「質量部」である。
実施例1〜5と同様の方法で、下記表1に記載した組成で樹脂組成物の分散液を調製した(比較例1〜6)。尚、比較例1は本発明におけるシリコーン樹脂(A)とは異なるシリコーン樹脂(上記樹脂(4))を含む樹脂組成物であり、本発明要件を満たしていない組成物である。更に、比較例2は本発明におけるシリコーン樹脂(A)を含む組成物であるが、エポキシ樹脂硬化剤(B)を含まず、本発明要件を満たしていない組成物である。比較例3は本発明のシリコーン樹脂(A)を含む組成物であるが、フィラー(C)を含まず、本発明要件を満たしていない組成物である。また、比較例4〜6は、本発明におけるフィラー(C)の含有量(樹脂組成物総質量に対し50〜95質量%)を満たしていない組成物である。
(B)エポキシ樹脂硬化剤
・フェノライトTD−2093(DIC(株)製、フェノールノボラック樹脂、OH当量:98〜102)
・リカジットHH(商品名)(新日本理化(株)製、ヘキサヒドロ無水フタル酸、分子量:154)
・シリカ((株)アドマテックス製、平均粒子径5.0μm)
エポキシ樹脂硬化促進剤:
・キュアゾール2P4MHZ(商品名)(四国化成工業(株)製、2−フェニル−4−メチル−5−ヒドロキシメチルイミダゾール)
・EOCN−103S(商品名)(日本化薬(株)製エポキシ樹脂、エポキシ当量:209〜219)
ここで、エポキシ当量とは各成分一分子あたりが有するエポキシ基の当量をいう。
(実施例1)
下記に示す剥離フィルム、保護フィルムを用いて、以下のようにして樹脂フィルムを形成した。
剥離フィルム(2):E7302(東洋紡績(株)製ポリエステル、厚さ75μm、剥離力90mN/50mm)
保護フィルム:ポリエチレンフィルム(100μm)
実施例1と同様の方法にて、表1の樹脂組成物を用いて膜厚が200μmの樹脂フィルムを有する複合フィルムを作製した(実施例2〜5、比較例1〜6)。なお、実施例5では、実施例4と同じ樹脂組成物で、膜厚が500μmの樹脂フィルムを作製した。
ウエハ厚み100μmの直径12インチ(300mm)シリコンウエハを用意した。実施例1〜5及び比較例1〜6の複合フィルムについて、剥離フィルム(2)を剥離し、真空ラミネーター((株)タカトリ製、製品名:TEAM−300M)を用いて、真空チャンバー内を真空度250Paに設定し、110℃で、樹脂フィルムを一括して上記シリコンウエハに貼り付けた。常圧に戻した後、上記シリコンウエハを25℃に冷却して上記真空ラミネーターから取り出し、残りの剥離フィルム(1)を剥離した。
得られた樹脂フィルム付ウエハは、イナートオーブンにて、180℃、2時間加熱することにより樹脂の硬化を行った。
樹脂フィルム硬化後のウエハ反り量をレーザー(東朋テクノロジー(株)製、FLX−3300−T)測定し、得られた値を表2に示す。なお、反り量が大きく、本装置で測定できなかった場合は、定規(JIS1級)を用いて測定した値を示した。
ウエハサポート性は、ウエハの端を支持した際のウエハのたわみ量を測定し、20mm以内を良好とし、20mmを超えた場合を不良と判断した結果を表2に示す。
各樹脂フィルム(25μm)を真空フィルムラミネーター(温度:100℃、圧力:100Pa、TEAM−100、(株)タカトリ製)を用いて、直径6インチ半導体ウエハ(厚み625μm、信越化学工業(株)製)に貼り合わせた。次いで、ダイシングブレードを備えるダイシングソー(DAD685、DISCO社製)を使用して2mm×2mm角の大きさに切断した。別途用意した、15mm×15mm角のシリコンウエハ(ベース基板)上に、樹脂フィルムを介して150℃、50mNの荷重にて2mm×2mm角のチップ貼り合わせた。その後、180℃にて2時間加熱して樹脂フィルムを硬化させ、試験片を得た。試験片は各5個ずつ製造し、以下の接着力測定試験に供した。
硬化後の樹脂フィルム付ウエハをダイシングブレードを備えるダイシングソー(DAD685、DISCO社製、スピンドル回転数は40,000rpm、切断速度は20mm/sec)を使用して10mm×10mm角の試験片を得た。得られた試験片(各10片づつ)をヒートサイクル試験(−25℃で10分間保持、125℃で10分間保持を1,000サイクル繰り返す)に供し、ヒートサイクル試験後の樹脂フィルムのウエハからの剥離状態を確認した。全く剥離を生じなかったものを良好、1つでも剥離を生じたものを不良として判定した結果を表2に示す。
評価4で作製した試験片の試験前質量を測定し、その後、試験片を200℃に加熱したオーブンに1000時間放置した後、試験片をオーブンから取り出し、試験後質量を測定した。試験前後の質量変化率が0.5質量パーセント未満だった場合を良好、試験前後の重量変化率が0.5質量パーセント以上だった場合を不良として判定した結果を表2に示す。
Claims (11)
- 下記組成式(1)で表される構成単位を有する重量平均分子量が3,000〜500,000の(A)シリコーン樹脂、
(B)エポキシ樹脂硬化剤、及び
(C)フィラー
を含有し、全質量に対し、前記(C)成分を50〜95質量%含有するものであることを特徴とする樹脂組成物。 - 前記(B)成分が、アミン系、フェノール系、酸無水物系のいずれかのエポキシ樹脂硬化剤であることを特徴とする請求項1に記載の樹脂組成物。
- 前記(B)成分の量が、前記(A)成分100質量部に対し5〜50質量部であることを特徴とする請求項1又は請求項2に記載の樹脂組成物。
- 更に、エポキシ樹脂硬化促進剤を含有するものであることを特徴とする請求項1から請求項3のいずれか1項に記載の樹脂組成物。
- 更に、前記(A)成分以外のエポキシ樹脂を含有するものであることを特徴とする請求項1から請求項4のいずれか1項に記載の樹脂組成物。
- 前記(C)成分がシリカであることを特徴とする請求項1から請求項5のいずれか1項に記載の樹脂組成物。
- 請求項1から請求項6のいずれか1項に記載の樹脂組成物がフィルム化されたものであることを特徴とする樹脂フィルム。
- 請求項1から請求項6のいずれか1項に記載の樹脂組成物を、剥離フィルム上にコートすることにより、前記剥離フィルム上に樹脂組成物層を有する樹脂形成フィルムを2つ以上作製して用意し、
該2つ以上の樹脂形成フィルム相互の前記樹脂組成物層同士を重ね合わせることを特徴とする樹脂フィルムの製造方法。 - 前記用意する樹脂形成フィルムのうち少なくとも1つを、前記剥離フィルム上に前記樹脂組成物層、及び該樹脂組成物層を保護するための保護フィルムが順に形成された樹脂形成フィルムとし、
前記樹脂形成フィルム相互の前記樹脂組成物層同士の重ね合わせを、前記樹脂形成フィルムから、互いに積層すべき前記樹脂組成物層が露呈するように前記保護フィルム又は前記剥離フィルムを取り除き、露呈した樹脂組成物層同士を重ね合わせることで行うことを特徴とする請求項8に記載の樹脂フィルムの製造方法。 - 請求項7に記載の樹脂フィルムを半導体ウエハに貼り付け、該半導体ウエハを前記樹脂フィルムでモールドする工程と、該モールドされた半導体ウエハを個片化する工程とを有することを特徴とする半導体装置の製造方法。
- 請求項7に記載の樹脂フィルムの加熱硬化皮膜でモールドされた半導体ウエハが個片化されたものであることを特徴とする半導体装置。
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