JP4645004B2 - Adhesive sheet, semiconductor device and manufacturing method thereof - Google Patents

Description

（式中、Ｒ_１及びＲ_２は各々独立に水素又はメチル基を示し、ｑ及びｒは各々独立に１以上の整数である）
で表される化合物、ジオール類、一般式（２）
【化２】

（式中、ｎは０〜１の整数であり、Ｒ_３は炭素原子数が１〜３０の２価あるいは３価の有機性基である）
で表されるイソシアネート化合物、一般式（３）
【化３】

（式中、Ｒ_４は水素又はメチル基であり、Ｒ_５はエチレン基あるいはプロピレン基である）
で表される化合物からなるウレタンアクリレート又はウレタンメタクリレート、一般式（４）
【化４】

（式中、Ｒ_６は炭素原子数が２〜３０の２価の有機基を示す）
で表されるジアミン、一般式（５）
【化５】

（式中、ｎは０〜１の整数であり、Ｒ_７は炭素原子数が１〜３０の２価あるいは３価の有機性基である）
で表されるイソシアネート化合物、一般式（６）
【化６】

（式中、ｎは０〜１の整数である）
で表される化合物からなる尿素メタクリレート、または、官能基を含むビニル共重合体に少なくとも１個のエチレン性不飽和基と、オキシラン環、イソシアネート基、水酸基、カルボキシル基等の１個の官能基を有する化合物を付加反応させて得られる側鎖にエチレン性不飽和基を有する放射線重合性共重合体等などを使用することができる。これらの放射線重合性化合物は、単独で又は２種類以上を組み合わせて使用することができる。
【００４６】
また、放射線照射によって上記エポキシ樹脂の硬化を促進する塩基を発生するような化合物を放射線重合性化合物とすることもできる。
【００４７】
また、本発明の接着シートを形成する粘着剤層には、活性光の照射によって遊離ラジカルを生成する光重合開始剤を添加することもできる。このような光重合開始剤としては、例えば、ベンゾフェノン、Ｎ，Ｎ′−テトラメチル−４，４′−ジアミノベンゾフェノン（ミヒラーケトン）、Ｎ，Ｎ′−テトラエチル−４，４′−ジアミノベンゾフェノン、４−メトキシ−４′−ジメチルアミノベンゾフェノン、２−ベンジル−２−ジメチルアミノ−１−（４−モルホリノフェニル）−ブタノン−１、２，２−ジメトキシ−１，２−ジフェニルエタン−１−オン、１−ヒドロキシ−シクロヘキシル−フェニル−ケトン、２−メチル−１−（４−（メチルチオ）フェニル）−２−モルフォリノプロパノン−１、２，４−ジエチルチオキサントン、２−エチルアントラキノン、フェナントレンキノン等の芳香族ケトン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインフェニルエーテル等のベンゾインエーテル、メチルベンゾイン、エチルベンゾイン等のベンゾイン、ベンジルジメチルケタール等のベンジル誘導体、２−（ｏ−クロロフェニル）−４，５−ジフェニルイミダゾール二量体、２−（ｏ−クロロフェニル）−４，５−ジ（ｍ−メトキシフェニル）イミダゾール二量体、２−（ｏ−フルオロフェニル）−４，５−フェニルイミダゾール二量体、２−（ｏ−メトキシフェニル）−４，５−ジフェニルイミダゾール二量体、２−（ｐ−メトキシフェニル）−４，５−ジフェニルイミダゾール二量体、２，４−ジ（ｐ−メトキシフェニル）−５−フェニルイミダゾール二量体、２−（２，４−ジメトキシフェニル）−４，５−ジフェニルイミダゾール二量体等の２，４，５−トリアリールイミダゾール二量体、９−フェニルアクリジン、１，７−ビス（９，９′−アクリジニル）ヘプタン等のアクリジン誘導体などが挙げられ、これらは単独で又は二種類以上を組み合わせて使用することができる。上記光重合開始剤の使用量としては、特に制限はないが、放射線重合性共重合体１００重量部に対して通常０．０１〜３０重量部である。
【００４８】
また、本発明の接着シートを形成する粘着剤層には、接着剤層を形成する前述の各種成分が含まれていてもよい。
【００４９】
また、本発明の接着シートを形成する粘着剤層の厚みは、０．１〜５０μｍが好ましい。０．１μｍより小さいとダイシング時の粘着力が十分でなくなる傾向があり、５０μｍより厚いとダイシング時に半導体素子が傷つき易くなる傾向がある。
【００５０】
また、本発明の接着シートを形成する接着剤層もしくは粘着剤層には、異種材料間の界面結合を良くするために、各種カップリング剤を添加することができる。カップリング剤としては、例えば、シラン系、チタン系、アルミニウム系等が挙げられ、中でも効果が高い点でシラン系カップリング剤が好ましい。
【００５１】
上記シラン系カップリング剤としては、特に制限はなく、例えば、ビニルトリクロルシラン、ビニルトリス（β−メトキシエトキシ）シラン、ビニルトリエトキシシラン、ビニルトリメトキシシラン、γ−メタクリロキシプロピルトリメトキシシラン、γ−メタクリロキシプロピルメチルジメトキシシラン、β−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルメチルジメトキシシラン、γ−グリシドキシプロピルメチルジエトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルトリメトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルメチルジメトキシシラン、γ−アミノプロピルトリエトキシシラン、Ｎ‐フェニル−γ−アミノプロピルトリメトキシシラン、γ−メルカプトプロピルトリメトキシシラン、γ−メルカプトプロピルトリエトキシシラン、３−アミノプロピルメチルジエトキシシラン、３−ウレイドプロピルトリエトキシシラン、３−ウレイドプロピルトリメトキシシラン、３−アミノプロピルトリメトキシシラン、３−アミノプロピル−トリス（２−メトキシ−エトキシ−エトキシ）シラン、Ｎ−メチル−３−アミノプロピルトリメトキシシラン、トリアミノプロピルトリメトキシシラン、３−４，５−ジヒドロイミダゾール−１−イル−プロピルトリメトキシシラン、３−メタクリロキシプロピル−トリメトキシシラン、３−メルカプトプロピルメチルジメトキシシラン、３−クロロプロピルメチルジメトキシシラン、３−クロロプロピルジメトキシシラン、３−シアノプロピルトリエトキシシラン、ヘキサメチルジシラザン、Ｎ，Ｏ−ビス（トリメチルシリル）アセトアミド、メチルトリメトキシシラン、メチルトリエトキシシラン、エチルトリクロロシラン、ｎ−プロピルトリメトキシシラン、イソブチルトリメトキシシラン、アミルトリクロロシラン、オクチルトリエトキシシラン、フェニルトリメトキシシラン、フェニルトリエトキシシラン、メチルトリ（メタクリロイルオキエトキシ）シラン、メチルトリ（グリシジルオキシ）シラン、Ｎ−β（Ｎ−ビニルベンジルアミノエチル）−γ−アミノプロピルトリメトキシシラン、オクタデシルジメチル〔３−（トリメトキシシリル）プロピル〕アンモニウムクロライド、γ−クロロプロピルメチルジクロロシラン、γ−クロロプロピルメチルジメトキシシラン、γ−クロロプロピルメチルジエトキシシラン、トリメチルシリルイソシアネート、ジメチルシリルイソシアネート、メチルシリルトリイソシアネート、ビニルシリルトリイソシアネート、フェニルシリルトリイソシアネート、テトライソシアネートシラン、エトキシシランイソシアネートなどを使用することができ、単独で又は二種類以上を組み合わせて使用することができる。
【００５２】
また、チタン系カップリング剤としては、例えば、イソプロピルトリオクタノイルチタネート、イソプロピルジメタクリルイソステアロイルチタネート、イソプロピルトリドデシルベンゼンスルホニルチタネート、イソプロピルイソステアロイルジアクリルチタネート、イソプロピルトリ（ジオクチルホスフェート）チタネート、イソプロピルトリクミルフェニルチタネート、イソプロピルトリス（ジオクチルパイロホスフェート）チタネート、イソプロピルトリス（ｎ−アミノエチル）チタネート、テトライソプロピルビス（ジオクチルホスファイト）チタネート、テトラオクチルビス（ジトリデシルホスファイト）チタネート、テトラ（２，２−ジアリルオキシメチル−１−ブチル）ビス（ジトリデシル）ホスファイトチタネート、ジクミルフェニルオキシアセテートチタネート、ビス（ジオクチルパイロホスフェート）オキシアセテートチタネート、テトライソプロピルチタネート、テトラノルマルブチルチタネート、ブチルチタネートダイマー、テトラ（２−エチルヘキシル）チタネート、チタンアセチルアセトネート、ポリチタンアエチルアセトネート、チタンオクチレングリコレート、チタンラクテートアンモニウム塩、チタンラクテート、チタンラクテートエチルエステル、チタンチリエタノールアミネート、ポリヒドロキシチタンステアレート、テトラメチルオルソチタネート、テトラエチルオルソチタネート、テタラプロピルオルソチタネート、テトライソブチルオルソチタネート、ステアリルチタネート、クレシルチタネートモノマー、クレシルチタネートポリマー、ジイソプロポキシ−ビス（２，４−ペンタジオネート）チタニウム（ＩＶ）、ジイソプロピル−ビス−トリエタノールアミノチタネート、オクチレングリコールチタネート、テトラ−ｎ−ブトキシチタンポリマー、トリ−ｎ−ブトキシチタンモノステアレートポリマー、トリ−ｎ−ブトキシチタンモノステアレートなどを使用することができ、単独で又は二種類以上を組み合わせて使用することができる。
【００５３】
アルミニウム系カップリング剤としては、例えば、エチルアセトアセテートアルミニウムジイソプロピレート、アルミニウムトイス（エチルアセトアセテート）、アルキルアセトアセテートアルミニウムジイソプロピレート、アルミニウムモノアセチルアセテートビス（エチルアセトアセテート）、アルミニウムトリス（アセチルアセトネート）、アルミニウム＝モノイソプロポキシモノオレオキシエチルアセトアセテート、アルミニウム−ジ−ｎ−ブトキシドモノエチルアセトアセテート、アルミニウム−ジ−ｉｓｏ−プロポキシド−モノエチルアセトアセテート等のアルミニウムキレート化合物、アルミニウムイソプロピレート、モノ−ｓｅｃ−ブトキシアルミニウムジイソプロピレート、アルミニウム−ｓｅｃ−ブチレート、アルミニウムエチレート等のアルミニウムアルコレートなどを使用することができ、単独で又は二種類以上を組み合わせて使用することができる。
【００５４】
上記カップリング剤の使用量は、その効果や耐熱性及びコストの面から、接着剤層に混合する場合は、（Ａ）エポキシ樹脂およびエポキシ樹脂硬化剤１００重量部に対して、０．０１〜１０重量部とすることが好ましく、粘着剤層に混合する場合には、放射線重合性化合物１００重量部に対して、０．０１〜１００重量部とすることが好ましい。
【００５５】
本発明の接着シートを形成する接着剤層または粘着剤層には、イオン性不純物を吸着して、吸湿時の絶縁信頼性をよくするために、さらにイオン捕捉剤を添加することもできる。このようなイオン捕捉剤としては、特に制限はなく、例えば、トリアジンチオール化合物、ビスフェノール系還元剤等の、銅がイオン化して溶け出すのを防止するため銅害防止剤として知られる化合物、ジルコニウム系、アンチモンビスマス系マグネシウムアルミニウム化合物等の無機イオン吸着剤などが挙げられる。上記イオン捕捉剤の使用量は、添加による効果や耐熱性、コスト等の点から、接着剤層に混合する場合は、（Ａ）エポキシ樹脂およびエポキシ樹脂硬化剤１００重量部に対して、０．１〜１０重量部とすることが好ましく、粘着剤層に混合する場合には、放射線重合性化合物１００重量部に対して、０．０１〜１００重量部とすることが好ましい。
【００５６】
本発明の接着剤層または粘着剤層を構成する組成物には、熱重合性化合物を併用することもできる。熱重合性化合物としては、特に制限はなく、例えば、アクリル酸メチル、メタクリル酸メチル、アクリル酸エチル、メタクリル酸エチル、アクリル酸ブチル、メタクリル酸ブチル、アクリル酸２−エチルヘキシル、メタクリル酸２−エチルヘキシル、ペンテニルアクリレート、テトラヒドロフルフリルアクリレート、テトラヒドロフルフリルメタクリレート、ジエチレングリコールジアクリレート、トリエチレングリコールジアクリレート、テトラエチレングリコールジアクリレート、ジエチレングリコールジメタクリレート、トリエチレングリコールジメタクリレート、テトラエチレングリコールジメタクリレート、トリメチロールプロパンジアクリレート、トリメチロールプロパントリアクリレート、トリメチロールプロパンジメタクリレート、トリメチロールプロパントリメタクリレート、１，４−ブタンジオールジアクリレート、１，６−ヘキサンジオールジアクリレート、１，４−ブタンジオールジメタクリレート、１，６−ヘキサンジオールジメタクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、ペンタエリスリトールトリメタクリレート、ペンタエリスリトールテトラメタクリレート、スチレン、ジビニルベンゼン、４−ビニルトルエン、４−ビニルピリジン、Ｎ−ビニルピロリドン、２−ヒドロキシエチルアクリレート、２−ヒドロキシエチルメタクリレート、１，３−アクリロイルオキシ−２−ヒドロキシプロパン、１，２−メタクリロイルオキシ−２−ヒドロキシプロパン、メチレンビスアクリルアミド、Ｎ，Ｎ−ジメチルアクリルアミド、Ｎ−メチロールアクリルアミド、トリス（β−ヒドロキシエチル）イソシアヌレートのトリアクリレート、下記一般式（７）
【化７】

（式中、Ｒ_７は水素又はメチル基を示し、ｑ及びｒは各々独立に１以上の整数である）
で表される化合物、トリレンジイソシアネートと２−ヒドロキシエチルアクリレート又は２−ヒドロキシエチルメタクリレートとの反応物やトリメチルヘキサメチレンジイソシアネートトシクロヘキサンジメタノールと２−ヒドロキシエチルアクリレート又は２−ヒドロキシエチルメタクリレートとの反応物等のウレタンアクリレート又はウレタンメタクリレート等が挙げられる。これらは単独又は２種類以上を組み合わせて使用することができる。
【００５７】
これら熱重合性化合物の使用量は、接着剤層に混合する場合は、（Ａ）エポキシ樹脂およびエポキシ樹脂硬化剤の１００重量％以下であることが好ましく、粘着剤層に混合する場合には、放射線重合性化合物の１００重量％以下であることが好ましく、９０重量％以下であることがより好ましく、８０重量％以下であることが特に好ましい。この使用量が１００重量％を超えると、得られる接着シートの保存安定性が劣る傾向がある。
【００５８】
また、本発明の接着剤層または粘着剤層を構成する組成物には、その取り扱い性向上、熱伝導性向上、溶融粘度の調整およびチキソトロピック性付与などを目的として、無機フィラーを添加することもできる。無機フィラーとしては、特に制限はなく、例えば、水酸化アルミニウム、水酸化マグネシウム、炭酸カルシウム、炭酸マグネシウム、ケイ酸カルシウム、ケイ酸マグネシウム、酸化カルシウム、酸化マグネシウム、酸化アルミニウム、窒化アルミニウム、ほう酸アルミウイスカ、窒化ほう素、結晶性シリカ、非晶性シリカ等が挙げられ、フィラーの形状は特に制限されるものではない。これらのフィラーは単独で又は二種類以上を組み合わせて使用することができる。中でも、熱伝導性向上のためには、酸化アルミニウム、窒化アルミニウム、窒化ほう素、結晶性シリカ、非晶性シリカが好ましい。また、溶融粘度の調整やチキソトロピック性の付与の目的には、水酸化アルミニウム、水酸化マグネシウム、炭酸カルシウム、炭酸マグネシウム、ケイ酸カルシウム、ケイ酸マグネシウム、酸化カルシウム、酸化マグネシウム、酸化アルミニウム、結晶性シリカ、非晶性シリカなどが好ましい。
【００５９】
無機フィラーの使用量は、接着剤層または粘着剤層１００重量部に対して１〜２０重量部が好ましい。１重量部未満だと添加効果が得られない傾向があり、２０重量部を超えると、接着剤層の貯蔵弾性率の上昇、接着性の低下、ボイド残存による電気特性の低下等の問題を起こす傾向がある。
【００６０】
本発明の接着シートを形成する上記基材層としては、例えば、ポリエチレンテレフタレート、ポリイミド、ポリテトラフルオロエチレン、ポイエチレン、ポリプロピレン、ポリメチルペンテン、ポリ酢酸ビニル等のポリオレフィン系樹脂などのフィルムを用いることができる。
【００６１】
また、基材層の厚みは、特に制限はないが、３０〜３００μｍが好ましく、４０〜２５０μｍがより好ましく、５０〜２００μｍが特に好ましい。３０μｍより薄いと、ダイシング時に基材層まで切断され易くなり、チップが飛散し易くなる傾向があり、３００μｍより厚いと経済的でなくなる。
【００６２】
本発明の接着シートは、例えば、上記のような接着剤層および粘着剤層の組成物をそれぞれ溶剤に溶解あるいは分散してワニスとし、それぞれのワニスを異なる基材層上に塗布、加熱し溶剤を除去し、最後に異なる基材層上に形成された接着剤層と粘着剤層とを貼り合わせることにより、また、粘着剤層の組成物を溶剤に溶解あるいは分散してワニスとし、これを基材フィルム上に塗布、加熱し溶剤を除去して粘着剤層を形成した後、その粘着剤層上に、接着剤層を形成する組成物を溶剤に溶解あるいは分散してワニスとしたものを塗布、加熱して溶剤を除去することにより得ることができる。
【００６３】
上記のワニス化に用いることのできる溶剤としては、特に限定されないが、フィルム作製時の揮発性などを考慮すると、例えば、メタノール、エタノール、２−メトキシエタノール、２−エトキシエタノール、２−ブトキシエタノール、メチルエチルケトン、アセトン、メチルイソブチルケトン、トルエン、キシレンなどの比較的低沸点の溶媒を使用するのが好ましい。また、塗膜性を向上させるなどの目的で、たとえば、ジメチルアセトアミド、ジメチルホルムアミド、Ｎ−メチルピロリドン、シクロヘキサノンなどの比較的高沸点の溶媒を使用することもできる。これらの溶媒は、単独でまたは２種類以上を組み合わせて使用することができる。
【００６４】
また、無機フィラーを添加した接着剤層もしくは粘着剤層の組成物をワニス化する場合、無機フィラーの分散性を考慮して、らいかい機、３本ロール、ボールミル及びビーズミルなどを使用するのが好ましく、また、これらを組み合わせて使用することもできる。また、無機フィラーと低分子量の原料をあらかじめ混合した後、高分子量の原料を配合することによって、混合する時間を短縮することもできる。また、ワニスとした後、真空脱気等によってワニス中の気泡を除去することもできる。
【００６５】
基材層上へのワニスの塗布方法としては、公知の方法を用いることができ、例えば、ナイフコート法、ロールコート法、スプレーコート法、グラビアコート法、バーコート法、カーテンコート法等が挙げられる。
【００６６】
上記のようにして得た本発明の接着シートの粘着剤層に放射線照射すると、放射線照射後に該粘着剤層が硬化し、接着剤層と粘着剤層界面の接着強度が大きく低下するため、容易に半導体素子に接着剤層を保持したまま該接着シートの粘着剤層からピックアップすることができる。
【００６７】
また、本発明の接着シートの粘着剤層は、放射線照射のみで粘着力を低下させる方法以外に放射線照射と同時あるいは放射線照射後に硬化反応を促進する目的で加熱を併用しても良い。放射線照射と加熱を併用することにより、より低温短時間で粘着剤層と接着剤層界面の接着強度を低下させることが可能となる。加熱温度は、粘着剤層および接着剤層の分解点以下であれば特に制限は受けないが、５０〜１７０℃の温度が好ましい。
【００６８】
また、本発明の接着シートは、所望のシート厚を得るために、さらに１又は２以上の粘着剤層あるいは接着剤層を半導体ウェハと接着剤層あるいは粘着剤層と接着剤層との間に挟むように設けてもよい。間に挟む粘着剤層や接着剤層としては、本発明の方法によって調製されたものの他に、従来公知の方法によって調製されたものや商業的に入手可能な接着シートを用いることができ、例えば、ポリイミド系、シリコンオリゴマー系、ゴム−エポキシ系、エポキシ系の接着剤を用いることができる。但し、剥離する予定のない界面において、粘着剤層あるいは接着剤層同士、または粘着剤層と接着剤層の剥離が発生しないような貼り合わせ条件を従来公知の技術に基づいて考慮する必要がある。
【００６９】
また、本発明の接着シートにおいて、接着剤層と粘着剤層界面における放射線照射前後の９０°ピール剥離力による接着強度の比（照射後接着強度／照射前接着強度）は０．５以下であることが好ましく、０．４以下であることがより好ましく、０．３以下であることがさらに好ましい。この値が０．５を超えると、ピックアップ時に各素子を傷つけ易くなる傾向がある。
【００７０】
また、本発明の接着シートにおいて、接着剤層と粘着剤層界面における放射線照射前後の接着強度の差（照射前接着強度−照射後接着強度）は１００ｍＮ／ｃｍ以上であることが好ましく、２００ｍＮ／ｃｍ以上であることがより好ましく、３００ｍＮ／ｃｍ以上であることがさらに好ましい。この値が１００ｍＮ／ｃｍ未満であると、ダイシング時のチップ飛びが発生し易くなったり、ピックアップ性が低下する傾向がある。
【００７１】
次に、本発明の接着シートの製造方法および半導体装置の製造方法の一例について図を参照して具体的に説明する。
【００７２】
まず、図１および図２に示すように、基材層１および４上にそれぞれ別個に粘着剤層および接着剤層となる組成物のワニスを塗布し、基材層を備えた粘着剤層（図１）および基材層を備えた接着剤層（図２）を作製した後、これらを、接着剤層と粘着剤層が向かい合うように積層して接着シートを得る（図３）。また、基材層を備えた粘着剤層（図１）上に接着剤層となる組成物のワニスを塗布する方法や基材層を備えた接着剤層（図２）上に粘着剤層となる組成物のワニスを塗布する方法により接着シートを得ることもできる。上記基材層を備えた粘着剤層（図１）および基材層を備えた接着剤層（図２）を作製した後、これらを積層して接着シート（図３）を得る方法を選択した場合、その後半導体ウエハを貼着する工程の前に、基材層４を剥離するので、基材層１／粘着剤層２界面、粘着剤層２／接着剤層３界面に比べ、接着剤層３／基材層４界面の接着強度が最も小さくなるよに基材層を選択することが重要になる。
【００７３】
次に、上記のようにして得た接着シートの接着剤層上面に、図４に示すようにして、ダイシング加工すべき半導体ウエハＡを貼着した後、図５のように半導体ウエハＡをダイシングし、洗浄、乾燥する。この際、粘着剤層２および接着剤層３により半導体ウエハＡは接着シートに充分に保持されているので、上記各工程の間に半導体ウエハＡが脱落することはない。
【００７４】
次に、図６に示すように、放射線Ｂを接着シートの粘着剤層２に照射し、放射線重合性を有する粘着剤層の一部又は大部分を重合硬化せしめる。この際、放射線照射と同時あるいは放射線照射後に硬化反応を促進する目的で加熱を併用しても良い。接着シートへの放射線照射は、基材層１の粘着剤層２が設けられていない面から行う。したがって、前述のように、放射線としてＵＶを用いる場合には基材層１は光透過性である必要があるが、放射線としてＥＢを用いる場合には基材層１は必ずしも光透過性である必要はない。
【００７５】
放射線照射後、ピックアップすべき半導体素子Ａ１、Ａ２、Ａ３を、例えば、吸引コレット５により順次ピックアップする。この際、ピックアップすべき半導体素子Ａ１、Ａ２、Ａ３を基材層１の下面から、例えば針扞等により突き上げることもできる。半導体素子Ａ１と接着剤層３との間の接着強度は、粘着剤層２と基材層１との間、および粘着剤層２と接着剤層３との間の接着強度よりも大きいため、半導体素子Ａ１のピックアップを行うと、接着剤層３が半導体素子Ａ１の下面に付着した状態で剥離する（図８）。
【００７６】
次いで、各半導体素子Ａ１、Ａ２、Ａ３を接着剤層３を介して半導体素子搭載用支持部材６に載置し加熱する。加熱により接着剤層３は接着強度が発現し、半導体素子と半導体素子搭載用支持部材との接着が完了する（図９）。
【００７７】
以下、本発明を実施例を用いてより詳細に説明するが、本発明はこれに限定されるものではない。
【００７８】
【実施例】
（放射線重合性化合物の合成例１）
攪拌機、温度計、乾燥空気導入管、滴下ロート及び冷却管を備えたフラスコに、ＶＥＳＴＡＮＡＴ ＩＰＤＩ（ダイセル・ヒュルス（株）製商品名、イソフォロンジイソシアネート）８８８重量部及び酢酸エチル ７８９重量部を仕込み７０℃に昇温後、７０〜７５℃に保温し、２−ヒドロキシエチルアクリレート ２３２重量部、ＰＴＧ６５０ＳＮ（保土ヶ谷化学（株）製商品名、ポリオキシテトラメチレングリコール、数平均分子量約６５０）１９５０重量部、ヒドロキノンモノメチルエーテル １．５３重量部、Ｌ１０１（東京ファインケミカル（株）製商品名、ジブチル錫ラウレート）１．５３重量部及び酢酸エチル ５２６重量部の混合液体を３時間で均一滴下し反応を行った。滴下完了後約５時間反応させ、ＩＲ測定によってイソシアネート基が消失したことを確認し反応を終了し、放射線重合性化合物（Ａ−１）を得た。
【００７９】
（放射線重合性化合物の合成例２）
攪拌機、温度計、乾燥空気導入管、滴下ロート及び冷却管を備えた１ｌフラスコに、２，２−ビス〔４−（４−アミノフェノキシ）フェニル〕プロパン １９７．０６ｇ（０．４８モル）及びγ−ブチロラクトン ３１８．１４ｇを仕込んだ後、３０℃に昇温し、３０〜４０℃に保ちながら、２，２，４−トリメチルヘキサメチレンジイソシアネート ５０．４ｇ（０．２４モル）を少量ずつ滴下した。滴下後、３０℃で１時間反応を続けた後、カレンズＭＯＩ（昭和電工（株）製商品名、イソシアネートエチルメタクリレート）７０．６８ｇ（０．４５６モル）及びヒドロキノンモノメチルエーテル ０．３１８ｇを、３０℃に保ちながら、少量ずつ滴下した。滴下後、３０℃以下で２時間反応を続け、放射線重合性化合物（Ａ−２）を得た。
【００８０】
（接着剤層の製造例１）
エピコート８２８（ジャパンエポキシレジン（株）製商品名、ビスフェノールＡ型エポキシ樹脂、エポキシ当量１９０）４５．０重量部、ＥＳＣＮ１９５（住友化学工業（株）商品名、ｏ−クレゾールノボラック型エポキシ樹脂、エポキシ当量１９５）１５．０重量部、プライオーフェンＬＦ２８８２（大日本インキ化学工業（株）製商品名、ビスフェノールＡノボラック樹脂）４０．０重量部、ＨＴＲ−８６０Ｐ−３（ナガセケムテックス（株）製商品名、エポキシ基含有アクリルゴム、分子量１００万、Ｔｇ−７℃）６６．７重量部、キュアゾール２ＰＺ−ＣＮ（四国化成工業（株）製商品名、１−シアノエチル−２−フェニルイミダゾール）０．５重量部、ＮＵＣ Ａ−１８７（日本ユニカー（株）製商品名、γ−グリシドキシプロピルトリメトキシシラン）０．７重量部からなる組成物に、メチルエチルケトンを加えて攪拌混合し、真空脱気した。この接着剤ワニスを、基材層となる厚さ５０μｍのポリエチレンテレフタレート（帝人デュポンフィルム（株）製、テイジンテトロンフィルム：Ｇ２−５０、表面張力５０ｄｙｎｅ／ｃｍ）上に塗布し、１４０℃で５分間加熱乾燥して、基材層を備えた膜厚が５０μｍのＢステージ状態の接着剤層（Ｆ−１）を得た。
【００８１】
この接着剤層（Ｆ−１）を１７０℃１時間硬化させた場合の貯蔵弾性率を動的粘弾性測定装置（レオロジ社製、ＤＶＥ−Ｖ４）を用いて測定（サンプルサイズ：長さ２０ｍｍ、幅４ｍｍ、膜厚８０μｍ、昇温速度５℃／ｍｉｎ、引張りモード、１０Ｈｚ、自動静荷重）した結果、２５℃で３６０ＭＰａ、２６０℃で１４ＭＰａであった。
【００８２】
また、ＲＨＥＳＣＡ社製タッキング試験機を用いて、ＪＩＳＺ０２３７−１９９１に記載の方法により、プローブ径：５．１ｍｍΦ、引き剥がし速度：１０ｍｍ／ｓ、接触荷重：１００ｇｆ／ｃｍ^２、接触時間：１ｓの測定条件で、２５℃におけるタック強度を測定したところ、１．０Ｎであった。
【００８３】
（接着剤層の製造例２）
ＹＤＣＮ−７０３（東都化成（株）製商品名、ｏ−クレゾールノボラック型エポキシ樹脂、エポキシ当量２１０）４２．３重量部、フェノライトＬＦ２８８２（大日本インキ化学工業（株）製商品名、ビスフェノールＡノボラック樹脂）２３．９重量部、ＨＴＲ−８６０Ｐ−３（ナガセケムテックス（株）製商品名、エポキシ基含有アクリルゴム、分子量１００万、Ｔｇ−７℃）４４．１重量部、キュアゾール２ＰＺ−ＣＮ（四国化成工業（株）製商品名、１−シアノエチル−２−フェニルイミダゾール）０．４重量部、ＮＵＣ Ａ−１８７（日本ユニカー（株）製商品名、γ−グリシドキシプロピルトリメトキシシラン）０．７重量部からなる組成物に、メチルエチルケトンを加えて攪拌混合し、真空脱気した。この接着剤ワニスを、基材層となる厚さ５０μｍのポリエチレンテレフタレート（帝人デュポンフィルム（株）製、テイジンテトロンフィルム：Ｇ２−５０、表面張力５０ｄｙｎｅ／ｃｍ）上に塗布し、１４０℃で５分間加熱乾燥して、基材層を備えた膜厚が５０μｍのＢステージ状態の接着剤層（Ｆ−２）を得た。
【００８４】
この接着剤層（Ｆ−２）を１７０℃１時間硬化させた場合の貯蔵弾性率を動的粘弾性測定装置（レオロジ社製、ＤＶＥ−Ｖ４）を用いて測定（サンプルサイズ：長さ２０ｍｍ、幅４ｍｍ、膜厚８０μｍ、昇温速度５℃／ｍｉｎ、引張りモード、１０Ｈｚ、自動静荷重）した結果、２５℃で３６０ＭＰａ、２６０℃で３０ＭＰａであった。
【００８５】
また、ＲＨＥＳＣＡ社製タッキング試験機を用いて、ＪＩＳＺ０２３７−１９９１に記載の方法により、プローブ径：５．１ｍｍΦ、引き剥がし速度：１０ｍｍ／ｓ、接触荷重：１００ｇｆ／ｃｍ^２、接触時間：１ｓの測定条件で、２５℃におけるタック強度を測定したところ、１．２Ｎであった。
【００８６】
（接着剤層の製造例３）
ＹＤＣＮ−７０３（東都化成（株）製商品名、ｏ−クレゾールノボラック型エポキシ樹脂、エポキシ当量２１０）６１重量部、プライオーフェンＬＦ２８８２（大日本インキ化学工業（株）製商品名、ビスフェノールＡノボラック樹脂）３９重量部、ＨＴＲ−８６０Ｐ−３）帝国化学産業（株）製商品名、エポキシ基含有アクリルゴム、分子量１００万、Ｔｇ−７℃）１５０重量部、キュアゾール２ＰＺ−ＣＮ（四国化成工業（株）製商品名、１−シアノエチル−２−フェニルイミダゾール）０．５重量部及びＮＵＣ Ａ−１８７（日本ユニカー（株）製商品名、γ−グリシドキシプロピルトリメトキシシラン）０．７重量部からなる組成物に、メチルエチルケトンを加えて攪拌混合し、真空脱気した。この接着剤ワニスを、基材層となる厚さ５０μｍのポリエチレンテレフタレート（帝人デュポンフィルム（株）製、テイジンテトロンフィルム：Ｇ２−５０、表面張力５０ｄｙｎｅ／ｃｍ）上に塗布し、１４０℃で５分間加熱乾燥して、基材層を備えた膜厚が５０μｍのＢステージ状態の接着剤層（Ｆ−３）を得た。
【００８７】
この接着剤層（Ｆ−３）を１７０℃１時間硬化させた場合の貯蔵弾性率を動的粘弾性測定装置（レオロジ社製、ＤＶＥ−Ｖ４）を用いて測定（サンプルサイズ：長さ２０ｍｍ、幅４ｍｍ、膜厚８０μｍ、昇温速度５℃／ｍｉｎ、引張りモード、１０Ｈｚ、自動静荷重）した結果、２５℃で３８０ＭＰａ、２６０℃で５０ＭＰａであった。
【００８８】
また、ＲＨＥＳＣＡ社製タッキング試験機を用いて、ＪＩＳＺ０２３７−１９９１に記載の方法により、プローブ径：５．１ｍｍΦ、引き剥がし速度：１０ｍｍ／ｓ、接触荷重：１００ｇｆ／ｃｍ^２、接触時間：１ｓの測定条件で、２５℃におけるタック強度を測定したところ、０．４Ｎであった。
【００８９】
（粘着剤層の製造例１）
エピコート８２８（油化シェルエポキシ（株）製商品名、ビスフェノールＡ型エポキシ樹脂、エポキシ当量１９０）２３．４重量部、ＥＳＣＮ１９５（住友化学工業（株）商品名、クレゾールノボラック型エポキシ樹脂、エポキシ当量１９５）１５重量部、プライオーフェンＬＦ２８８２（大日本インキ化学工業（株）製商品名、ビスフェノールＡノボラック樹脂）２３．９重量部、ＨＴＲ−８６０Ｐ−３）帝国化学産業（株）製商品名、エポキシ基含有アクリルゴム、分子量１００万、Ｔｇ−７℃）４４．１重量部、キュアゾール２ＰＺ−ＣＮ（四国化成工業（株）製商品名、１−シアノエチル−２−フェニルイミダゾール）０．４重量部、ＮＵＣ Ａ−１８７（日本ユニカー（株）製商品名、γ−グリシドキシプロピルトリメトキシシラン）０．７重量部、上記放射線重合性化合物の合成例１で得られた放射線重合性化合物（Ａ−１）２２．０５重量部及び１−ヒドロキシシクロヘキシルフェニルケトン０．５重量部からなる組成物に、メチルエチルケトンを加えて攪拌混合し、真空脱気した。この接着剤ワニスを、基材層となる厚さ５０μｍのポリエチレンテレフタレートフィルム上に塗布し、１００℃で５分間加熱乾燥して、基材層を備えた膜厚が１０μｍのＢステージ状態の粘着剤層（Ｐ−１）を作製した
（粘着剤層の製造例２）
放射線重合性化合物（Ａ−１）の代わりに放射線重合性化合物の合成例２で得た放射線重合性化合物（Ａ−２）を用いた以外は粘着剤層の製造例１と全く同様の操作を行い、基材層を備えた膜厚が１０μｍのＢステージ状態の粘着剤層（Ｐ−２）を作製した
（粘着剤層の製造例３）
放射線重合性化合物（Ａ−１）の代わりにＮＫ−ＥＳＴＥＲ Ａ−２００（新中村化学工業（株）商品名、テトラエチレングリコールジアクリレート）を用いた以外は粘着剤層の製造例１と全く同様の操作を行い、基材層を備えた膜厚が１０μｍのＢステージ状態の粘着剤層（Ｐ−３）を作製した
（実施例１）
上記得られた基材層を備えた接着剤層（Ｆ−１）と基材層を備えた粘着剤層（Ｐ−１）を、ホットロールラミネーターを使用して、温度：３０℃、線圧：１．０〜１．５ＭＰａ、速度：０．５ｍ／ｍｉｎの条件で接着剤層と粘着剤層とが合わさるようにラミネートし、接着シート１を得た。
【００９０】
得られた接着シート１に厚さ１５０μｍの半導体ウェハを貼付け、これをダイシング装置上に載置した。次いで、半導体ウェハをダイシング装置上に固定して、１００ｍｍ／ｓｅｃの速度で５ｍｍ×５ｍｍにダイシングした後、（株）オーク製作所製ＵＶ−３３０ ＨＱＰ−２型露光機を使用して、５００ｍＪ／ｃｍ^２の露光量で接着シート１の基材層側から露光した。ついで、ピックアップ装置にて接着剤層付き半導体素子をピックアップした。ここまでの過程で、ダイシング時のチップ飛び、および接着剤付き半導体素子のピックアップ性を評価した。ダイシング時にチップ（半導体素子）が飛んだ確率（％／１００チップ）でダイシング時のチップ飛びを、ピックアップダイボンダ−により、接着剤層付き半導体素子をピックアップしたときの成功率（％／１００チップ）で接着剤層付き半導体素子のピックアップ性を示した。
【００９１】
その後、厚み２５μｍのポリイミドフィルムを半導体素子搭載用支持部材とし、上記ピックアップした接着剤層付き半導体素子をこれに貼り合せた半導体装置サンプル（片面にはんだボールを形成）を作製し、その耐熱性及び耐湿性を調べた。耐熱性の評価方法には、耐リフロークラック性と温度サイクル試験を適用した。耐リフロークラック性の評価は、サンプル表面の温度を２４０℃で２０秒間保持するように温度設定したＩＲリフロー炉に半導体装置サンプルを通し、その後、室温で放置することにより冷却する処理を２回繰り返し、サンプル中のクラックを目視と超音波顕微鏡で視察し、クラックの発生していない確率（％／１００チップ）を示した。耐温度サイクル性は、半導体装置サンプルを−５５℃雰囲気に３０分間放置し、その後１２５℃の雰囲気に３０分間放置する工程を１サイクルとして、１０００サイクル後において超音波顕微鏡を用いて剥離やクラック等の破壊が発生していない確率（％／１００チップ）で示した。また、耐湿性評価は、温度１２１℃、湿度１００％、２．０３×１０^５Ｐａの雰囲気（プレッシャークッカ−テスト：ＰＣＴ処理）で７２時間処理後に剥離を観察することにより行った。剥離の発生していない確率（％／１００チップ）で示した。
【００９２】
また、上記接着シートを露光する前と、５００ｍＪ／ｃｍ^２の露光量で基材層側から露光した後のそれぞれの接着剤層／粘着剤層界面の接着強度を、９０°ピール強度で測定した（引張り速度 ５０ｍｍ／ｍｉｎ）。
【００９３】
これらの評価結果をまとめて表３に示す。
【００９４】
（実施例２〜６）
接着剤層の製造例１および２で得られた基材層を備えた接着剤層（Ｆ−１〜２）と粘着剤層の製造例１〜３で得られた基材層を備えた粘着剤層（Ｐ−１〜３）を、表１に示す組合せで実施例１と同様にラミネートし、接着シート２〜６を得た。得られた接着シート２〜６について実施例１と同様の評価を行った。
【００９５】
結果を表３に示す。
【００９６】
【表１】

【００９７】
（比較例１〜３）
接着剤層の製造例３で得られた基材層を備えた接着剤層（Ｆ−３）と粘着剤層の製造例１〜３で得られた基材層を備えた粘着剤層（Ｐ−１〜３）を、表２に示す組合せで実施例１と同様にラミネートし、接着シート７〜９を得た。得られた接着シート７〜９について実施例１と同様の評価を行った。
【００９８】
結果を表３に示す。
【００９９】
【表２】

【０１００】
【表３】

【０１０１】
表３から、本発明の接着シートは、放射線照射前の接着剤層と粘着剤層界面の接着性に優れているため、ダイシング工程においてチップが飛散することがなく、また、ピックアップ性にも優れていることが分かった。一方、比較例の接着シートでは、ダイシング時にチップが全て飛散してしまい、後の評価を行うことができなかった。また、本発明の接着剤層付き半導体素子をダイボンドした半導体装置サンプルは、耐熱性および耐湿性が共に優れていることが分かった。
【０１０２】
【発明の効果】
本発明の接着シートは、ダイシング工程ではダイシングテープとして作用し、半導体素子と支持部材との接合工程では接続信頼性に優れる接着剤として使用でき、また、この接着シートは、半導体素子搭載用支持部材に熱膨張係数の差が大きい半導体素子を実装する場合に要求される耐熱性および耐湿性を有し、かつ作業性に優れる接着シートである。本発明は、さらに、半導体装置の製造工程を簡略化できる製造方法を提供することが可能である。
【図面の簡単な説明】
【図１】本発明に係る接着シートの基材層を備えた粘着剤層の一例の断面図である。
【図２】本発明に係る接着シートの基材層を備えた接着剤層の一例の断面図である。
【図３】本発明に係る接着シートの一例の断面図である。
【図４】本発明に係る接着シートに半導体ウェハを貼着した状態を示す断面図である。
【図５】本発明に係る接着シートを半導体ウェハのダイシング工程に用いた場合の図である。
【図６】図５に示す工程の後、接着シートに基材層側から放射線を照射した状態を示す図である。
【図７】図６に示す工程の後、半導体素子をピックアップしようとする状態を示す図である。
【図８】接着剤層付きの半導体素子をピックアップした状態を示す図である。
【図９】接着剤層付きの半導体素子を半導体素子搭載用支持部材に熱圧着した状態を示す図である。
【符号の説明】
１ 基材層
２ 粘着層
３ 接着剤層
４ 基材層
５ 吸引コレット
６ 半導体素子搭載用支持部材
Ａ 半導体ウェハ
Ａ１、Ａ２、Ａ３ 半導体素子
Ｂ 放射線[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an adhesive sheet, a semiconductor device using the same, and a method for manufacturing the same.
[0002]
[Prior art]
Conventionally, a silver paste has been mainly used for joining a semiconductor element and a semiconductor element mounting support member. However, with the recent miniaturization and high performance of semiconductor devices, the supporting members used are also required to be small and fine. In response to these requirements, silver paste has various problems such as occurrence of defects during wire bonding due to protrusion and inclination of semiconductor elements, difficulty in controlling the thickness of the adhesive layer, and generation of voids in the adhesive layer. there were.
[0003]
In order to solve these problems, a film-like adhesive has been used in recent years. As the film-like adhesive, an individual sticking method or a wafer back surface sticking method is widely used.
[0004]
In the piece pasting method, a reel-like adhesive film is cut into pieces by cutting or punching, and then adhered to a support member. The semiconductor element separated by the dicing process is joined to the support member with the adhesive film to produce the support element with the semiconductor element, and then the semiconductor element is completed through the wire bonding process, the sealing process, and the like. However, the individual sticking method requires a dedicated assembling apparatus that cuts out an adhesive film and adheres it to the support member, and there is a problem that the assembling cost is higher than the method using silver paste.
[0005]
In the wafer back surface pasting method, an adhesive film is pasted on a semiconductor wafer and pasted on a dicing tape, and then separated into individual pieces by a dicing process. The separated semiconductor element with an adhesive is bonded to a support member, and the semiconductor device is completed through subsequent processes such as heating, curing, and wire bonding. The wafer back surface pasting method joins a semiconductor element with an adhesive to a support member, so it does not require an apparatus for separating an adhesive film, and an existing assembly apparatus for silver paste is used as it is or a heating plate is added. Since it can be used by improving a part of the apparatus such as the above, it has been attracting attention as a method that can keep the assembly cost relatively low in the assembling method using a film adhesive.
[0006]
On the other hand, the dicing tape used in the dicing process has a sufficient adhesive strength so that each element does not scatter due to rotation by dicing saw at the time of cutting, and adhesive does not adhere to each element at the time of picking up. The adhesive strength is required to be low enough not to be damaged. Such dicing tape is roughly classified into a pressure-sensitive type and a UV type.
[0007]
The pressure-sensitive type is usually made by applying an adhesive to a polyvinyl chloride or polyolefin base film, so it has various adhesive strengths according to the size and processing conditions of the device with reduced tolerance of adhesive strength. Many kinds of adhesive sheets need to be prepared and switched for each process. Therefore, it is necessary to stock many kinds of products, and the management is complicated. Furthermore, the operation | work which switches an adhesive sheet for every process was required. Furthermore, with the recent increase in capacity of semiconductor elements, particularly CPUs and memories, the semiconductor elements tend to increase in size. Furthermore, in products such as IC cards and memory cards, the memory used is becoming thinner. With the increase in size and thickness of these semiconductor elements, the pressure sensitive type is no longer able to meet the conflicting requirements of fixing force during dicing (high adhesive force) and peeling force during pickup (low adhesive force). .
[0008]
Therefore, recently, a dicing tape called UV type, which has a high adhesive force during dicing and can be irradiated with ultraviolet (UV) before picking up to achieve a low adhesive force, has been adopted. However, when the UV type is used as the dicing tape and the semiconductor element is mounted on the support member by the wafer back surface attaching method, the attaching process of attaching the dicing tape and attaching the adhesive tape is performed twice. There is a problem that work must be performed and the work becomes complicated.
[0009]
[Patent Document 1]
JP-A-2-32181
[Patent Document 2]
JP-A-3-268345
[Patent Document 3]
Japanese Patent Publication No. 3-34853
[0010]
[Problems to be solved by the invention]
The present invention has been made in view of the above-described problems of the prior art, and an object thereof is to provide an adhesive sheet that acts as a dicing tape in a dicing process and acts as an adhesive tape having excellent connection reliability in a joining process between a semiconductor element and a support member. And
[0011]
The present invention also provides an adhesive sheet that has heat resistance and moisture resistance required when a semiconductor element having a large difference in thermal expansion coefficient is mounted on a semiconductor element mounting support member, and is excellent in workability. For the purpose.
[0012]
Furthermore, an object of this invention is to provide the manufacturing method which can simplify the semiconductor device manufactured using said adhesive sheet, and its manufacturing process.
[0013]
[Means for Solving the Problems]
That is, the present invention relates to the following items (1) to (10).
[0014]
(1) (A) an epoxy resin and an epoxy resin curing agent, and (B) an adhesive layer containing a high molecular weight component having a weight average molecular weight of 100,000 or more, and a pressure-sensitive adhesive layer containing a radiation polymerizable compound. And a base material layer, the adhesive strength between the adhesive layer and the pressure-sensitive adhesive layer before irradiation is 200 mN / cm or more, and the adhesive layer in an uncured or semi-cured state is measured by 5.1 mmΦ probe measurement. An adhesive sheet having a tack strength at 0 ° C. of 0.5 N or more.
[0015]
(2) The adhesive sheet according to (1), wherein a ratio of adhesive strength before and after radiation irradiation (adhesive strength after irradiation / adhesive strength before irradiation) at the interface between the adhesive layer and the pressure-sensitive adhesive layer is 0.5 or less.
[0016]
(3) The adhesive sheet according to (1) or (2), wherein the difference in adhesive strength before and after radiation irradiation (adhesive strength before irradiation-adhesive strength after irradiation) at the interface between the adhesive layer and the pressure-sensitive adhesive layer is 100 mN / cm or more. .
[0017]
(4) The high molecular weight component containing a functional monomer and having a weight average molecular weight of 100,000 or more is a glycidyl group-containing (meth) acrylic copolymer, and the amount of the epoxy resin-containing repeating unit is 0.5 to 6 The adhesive sheet according to any one of (1) to (3), wherein the adhesive sheet is wt%.
[0018]
(5) The adhesive layer contains (A) 100 parts by weight of an epoxy resin and an epoxy resin curing agent, and (B) 10 to 400 parts by weight of a high molecular weight component having a weight average molecular weight including a functional monomer of 100,000 or more. The adhesive sheet according to any one of (1) to (4) above.
[0019]
(6) The adhesive sheet according to any one of the above (1) to (5), wherein the adhesive layer has a storage elastic modulus after heat curing of 10 to 2000 MPa at 25 ° C. and 3 to 50 MPa at 260 ° C.
[0020]
(7) The adhesive sheet according to any one of (1) to (6), wherein the adhesive layer, the pressure-sensitive adhesive layer, and the base material layer are laminated in the order of the base material layer / the pressure-sensitive adhesive layer / the adhesive layer. .
[0021]
(8) The adhesive sheet according to any one of (1) to (7), wherein the adhesive strength between the adhesive layer and the pressure-sensitive adhesive layer can be controlled by irradiating the pressure-sensitive adhesive layer with radiation.
[0022]
(9) A semiconductor device in which a semiconductor element and a semiconductor element mounting support member are bonded using the adhesive sheet according to any one of (1) to (8).
[0023]
(10) A step of adhering a semiconductor wafer to the adhesive layer of the adhesive sheet according to any one of (1) to (8) above, dicing the semiconductor wafer together with at least the adhesive layer to obtain a semiconductor element with an adhesive layer A step of forming, a step of irradiating the pressure-sensitive adhesive layer of the adhesive sheet to cure it, a step of peeling the semiconductor element with the adhesive layer from the adhesive sheet at the interface between the adhesive layer and the pressure-sensitive adhesive layer, and bonding The manufacturing method of a semiconductor device including the process of adhere | attaching the semiconductor element with an agent layer, and the supporting member for semiconductor element mounting.
[0024]
Hereinafter, the present invention will be described in detail by embodiments.
[0025]
DETAILED DESCRIPTION OF THE INVENTION
In the dicing process, the adhesive sheet of the present invention has sufficient adhesive strength so that the semiconductor element does not scatter, and by controlling the adhesive strength between the adhesive layer and the adhesive layer interface by radiation irradiation when picking up the semiconductor element, It acts as a dicing tape that satisfies the conflicting requirements of not damaging each element and having a low adhesive strength, and in the die bonding process for joining the semiconductor element and the support member, the connection reliability thereof is excellent. The adhesive sheet acts as an adhesive tape, and each process of dicing and die bonding can be completed with one adhesive sheet.
[0026]
In the adhesive sheet of the present invention, the adhesive strength at the interface between the adhesive layer and the pressure-sensitive adhesive layer before irradiation is required to be 200 mN / cm or more under the conditions of a pulling angle: 90 ° and a pulling speed: 50 mm / min. Preferably it is 250 mN / cm or more, More preferably, it is 300 mN / cm or more. If this value is less than 200 mN / cm, the semiconductor element may be scattered during dicing.
[0027]
Further, in the adhesive sheet of the present invention, the tack strength at 25 ° C. measured by the 5.1 mmΦ probe of the adhesive layer in an uncured or semi-cured state needs to be 0.5 N or more. Preferably it is 0.6N or more, More preferably, it is 0.7N or more, Most preferably, it is 0.8N or more. Although the adhesive layer in the uncured or semi-cured state has a tack strength at 25 ° C. measured by a 5.1 mmΦ probe of 0.5 N or more, the adhesive sheet can be bonded to a semiconductor wafer to be diced at a low temperature. In addition, it is possible to satisfy the conflicting characteristics that a sufficient adhesive strength that does not scatter the semiconductor elements is exhibited during dicing, and a low adhesive strength that does not damage each element is exhibited during pickup.
[0028]
The adhesive sheet of the present invention comprises (A) an epoxy resin, an epoxy resin curing agent, and (B) an adhesive layer containing a high molecular weight component having a weight average molecular weight of 100,000 or more, and a radiation polymerizable compound. At least an adhesive layer and a base material layer are provided.
[0029]
The epoxy resin used in the adhesive layer of the adhesive sheet of the present invention is not particularly limited as long as it is cured and has an adhesive action. For example, bifunctional epoxy resins such as bisphenol A type epoxy, phenol novolac type Commonly known materials such as epoxy resins and cresol novolac epoxy resins, novolak epoxy resins, polyfunctional epoxy resins, glycidylamine epoxy resins, heterocyclic ring-containing epoxy resins, and alicyclic epoxy resins can be applied. it can.
[0030]
Examples of the bisphenol A epoxy resin include Epicoat 807, 815, 825, 827, 828, 834, 1001, 1004, 1007, 1009 manufactured by Yuka Shell Epoxy, DER-330, 301, 361 manufactured by Dow Chemical Co., Ltd. Examples include YD8125 and YDF8170 manufactured by Toto Kasei Co., Ltd. The phenol novolac type epoxy resin includes Epicoat 152,154 manufactured by Yuka Shell Epoxy Co., Ltd., EPPN-201 manufactured by Nippon Kayaku Co., Ltd., DEN-438 manufactured by Dow Chemical Co., Ltd., Dainippon Ink and Chemicals, Inc. Epiclon N-730-S, N-740, N-770, N-775 and the like, and as the cresol novolac type epoxy resin, EOCN-102S, 103S, 104S, 1012 manufactured by Nippon Kayaku Co., Ltd. , 1025, 1027, YDCN701, 702, 703, 704 manufactured by Toto Kasei Co., Ltd., Epicron N-600 series manufactured by Dainippon Ink & Chemicals, Inc., and the like. Furthermore, as the polyfunctional epoxy resin, Epon 1031S manufactured by Yuka Shell Epoxy Co., Ltd., Araldite 0163 manufactured by Ciba Specialty Chemicals, Denacol EX-611, 614, 614B, 622, 512, 521 manufactured by Nagase Kasei Co., Ltd. , 421, 411, 321 and Epiklon EXA-4700 manufactured by Dainippon Ink & Chemicals, Inc., as an amine type epoxy resin, Epicoat 604 manufactured by Yuka Shell Epoxy Co., Ltd., YH-434 manufactured by Tohto Kasei Co., Ltd. , Mitsubishi Gas Chemical Co., Ltd., TETRAD-X, TETRAD-C, Sumitomo Chemical Co., Ltd., ELM-120, and the like. The heterocycle-containing epoxy resins include Araldite PT810 manufactured by Ciba Specialty Chemicals, and ERL4234 manufactured by UCC. , 4299, 4221, 4206 Etc., but also, as a special epoxy resin, manufactured by Dainippon Ink & EPICLON HP-4032, etc. EXA-7120, EXA-7015 and the like. These epoxy resins can be used alone or in combination of two or more.
[0031]
As said epoxy resin hardening | curing agent used for the adhesive bond layer of the adhesive sheet of this invention, the well-known hardening | curing agent normally used can be used. For example, bisphenols having two or more phenolic hydroxyl groups in one molecule such as amines, polyamides, acid anhydrides, polysulfides, boron trifluoride, bisphenol A, bisphenol F, and bisphenol S, phenol novolac resins, bisphenol A Examples thereof include phenolic resins such as novolak resin or cresol novolak resin. Phenol resins such as phenol novolak resin, bisphenol A novolak resin or cresol novolak resin are preferred in terms of particularly excellent electric corrosion resistance at the time of moisture absorption. Specifically, for example, trade name: manufactured by Dainippon Ink & Chemicals, Inc. Phenolite LF2882, Phenolite LF2822, Phenolite TD-2090, Phenolite TD-2149, Phenolite VH-4150, Phenolite VH4170, etc. are mentioned.
[0032]
Examples of the functional group in the high molecular weight component having a weight average molecular weight of 100,000 or more containing the functional monomer (B) used in the adhesive layer of the adhesive sheet of the present invention include glycidyl group, acryloyl group, methacryloyl group, hydroxyl group. , Carboxyl group, isocyanurate group, amino group, amide group and the like, among which glycidyl group is preferable. As the functional monomer having a glycidyl group, for example, a (meth) acrylic ester copolymer, an acrylic rubber, a glycidyl group-containing (meth) acrylic copolymer such as glycidyl acrylate, glycidyl methacrylate can be preferably used. It is particularly preferred that this is incompatible with a thermosetting resin such as an epoxy resin. As what is marketed, Nagase ChemteX Co., Ltd. product HTR-860P-3 etc. are mentioned, for example.
[0033]
In the present invention, “functional monomer” means a monomer having a functional group. The acrylic rubber is a rubber mainly composed of an acrylate ester and mainly composed of a copolymer such as butyl acrylate and acrylonitrile, a copolymer such as ethyl acrylate and acrylonitrile, or the like.
[0034]
The amount of the epoxy resin-containing repeating unit of the glycidyl group-containing (meth) acrylic copolymer is preferably 0.5 to 6.0% by weight, and preferably 0.5 to 5.0% by weight. Is more preferable, and 0.8 to 5.0% by weight is particularly preferable. When the amount of the epoxy resin-containing repeating unit is within this range, the adhesive strength can be secured and gelation can be prevented.
[0035]
Examples of the functional monomer other than the glycidyl group-containing (meth) acrylic copolymer include ethyl (meth) acrylate and butyl (meth) acrylate. In the present invention, ethyl (meth) acrylate refers to both ethyl acrylate and ethyl methacrylate.
[0036]
These functional monomers can be used alone or in combination of two or more. As a functional monomer, when the glycidyl group-containing (meth) acrylic copolymer and other functional monomers are used in combination, the mixing ratio is the glass transition temperature of the glycidyl group-containing (meth) acrylic copolymer (hereinafter referred to as Tg). It is desirable to decide in consideration of
[0037]
Moreover, it is preferable that Tg of the said functional monomer is -10 degreeC or more. When a material having a Tg of −10 ° C. or higher is used, the tackiness of the adhesive layer in the B stage state is appropriate, and there is no problem in handling properties.
[0038]
In the case of producing a high molecular weight component having a weight average molecular weight of 100,000 or more containing the functional monomer by polymerizing the monomer, the polymerization method is not particularly limited. For example, a method such as pearl polymerization or solution polymerization is used. Can be used.
[0039]
Moreover, in this invention, although the weight average molecular weight of the high molecular weight component containing a functional monomer is 100,000 or more, it is preferable that it is 300,000-3 million, and it is more preferable that it is 500,000-2 million. When the weight average molecular weight is 100,000 or more, the strength, flexibility, and tackiness of sheet-like or film-like materials are appropriate, and the flowability is appropriate, so the circuit fillability of wiring is ensured. it can. In the present invention, the weight average molecular weight is a value measured by gel permeation chromatography and converted using a standard polystyrene calibration curve as will be described later in the column of the evaluation method.
[0040]
Further, the adhesive layer forming the adhesive sheet of the present invention mainly comprises a high molecular weight component having a weight average molecular weight of 100,000 or more, including the above (A) epoxy resin and epoxy resin curing agent, and (B) a functional monomer. Although it contains as a component, As each content, Preferably the said (A) epoxy resin and an epoxy resin hardening | curing agent are 100 weight part, (B) The weight average molecular weight containing a functional monomer is 100,000 or more high The molecular weight component is 10 to 400 parts by weight.
[0041]
Moreover, a hardening accelerator can also be added to the adhesive layer forming the adhesive sheet of the present invention. There is no restriction | limiting in particular as a hardening accelerator, For example, imidazole etc. are mentioned. Specific examples include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, and the like. Or in combination of two or more.
[0042]
The addition amount of the curing accelerator is preferably 5 parts by weight or less, and more preferably 3 parts by weight or less with respect to 100 parts by weight of the (A) epoxy resin and the epoxy curing agent. When the addition amount exceeds 5 parts by weight, the storage stability tends to decrease.
[0043]
The thickness of the adhesive layer forming the adhesive sheet of the present invention is not particularly limited, but is preferably 5 to 250 μm. If the thickness is less than 5 μm, the stress relaxation effect tends to be poor.
[0044]
The adhesive layer forming the adhesive sheet of the present invention preferably has a storage elastic modulus of 10 to 2000 MPa at 25 ° C. and 3 to 50 MPa at 260 ° C. at the stage of heat curing. Further, the storage elastic modulus at 25 ° C. is more preferably 20 to 1900 MPa, and particularly preferably 50 to 1800 MPa. Further, the storage elastic modulus at 260 ° C. is more preferably 5 to 50 MPa, and particularly preferably 7 to 50 MPa. When the storage elastic modulus is in the above range, the effect of relaxing the thermal stress generated by the difference in thermal expansion coefficient between the semiconductor element and the support member is maintained, and the occurrence of peeling and cracking can be suppressed, and the handling of the adhesive It is excellent in properties and can suppress the occurrence of reflow cracks. Although the conditions of the said heat-hardening differ also with compositions of an adhesive agent layer, they are the range of 120-240 degreeC and 5-600 minutes normally. This storage elastic modulus is, for example, using a dynamic viscoelasticity measuring device (DVE-V4, manufactured by Rheology), applying a tensile load to the cured adhesive, and having a frequency of 10 Hz and a heating rate of 5 to 10 ° C./min. It can be measured by a temperature dependence measurement mode in which measurement is performed from −50 ° C. to 300 ° C. under the following conditions.
[0045]
The pressure-sensitive adhesive layer forming the adhesive sheet of the present invention contains a radiation polymerizable compound as an essential component. The radiation-polymerizable compound is not particularly limited as long as it is a compound that polymerizes and cures when irradiated with radiation such as ultraviolet rays (hereinafter referred to as UV) or an electron beam (hereinafter referred to as EB). Methyl methacrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, pentenyl acrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, diethylene glycol di Acrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate , Trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butane Diol dimethacrylate, 1,6-hexanediol dimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone, 2 Hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 1,3-acryloyloxy-2-hydroxypropane, 1,2-methacryloyloxy-2-hydroxypropane, methylenebisacrylamide, N, N-dimethylacrylamide, N-methylolacrylamide, Triacrylate of tris (β-hydroxyethyl) isocyanurate, the following general formula (1)
[Chemical 1]

(Wherein R ₁ And R ₂ Each independently represents hydrogen or a methyl group, and q and r each independently represents an integer of 1 or more)
A compound represented by the formula: diols, general formula (2)
[Chemical 2]

(In the formula, n is an integer of 0 to 1, R ₃ Is a divalent or trivalent organic group having 1 to 30 carbon atoms)
Isocyanate compound represented by general formula (3)
[Chemical 3]

(Wherein R ₄ Is hydrogen or a methyl group, R ₅ Is ethylene group or propylene group)
Urethane acrylate or urethane methacrylate composed of a compound represented by the general formula (4)
[Formula 4]

(Wherein R ₆ Represents a divalent organic group having 2 to 30 carbon atoms)
Diamine represented by general formula (5)
[Chemical formula 5]

(In the formula, n is an integer of 0 to 1, R ₇ Is a divalent or trivalent organic group having 1 to 30 carbon atoms)
Isocyanate compound represented by general formula (6)
[Chemical 6]

(Where n is an integer from 0 to 1)
Urea methacrylate made of a compound represented by formula (1) or a vinyl copolymer containing a functional group having at least one ethylenically unsaturated group and one functional group such as an oxirane ring, an isocyanate group, a hydroxyl group, and a carboxyl group. The radiation-polymerizable copolymer etc. which have an ethylenically unsaturated group in the side chain obtained by carrying out addition reaction of the compound which has can be used. These radiation polymerizable compounds can be used alone or in combination of two or more.
[0046]
In addition, a compound that generates a base that promotes curing of the epoxy resin by irradiation with radiation can be used as a radiation polymerizable compound.
[0047]
Moreover, the photoinitiator which produces | generates a free radical by irradiation of actinic light can also be added to the adhesive layer which forms the adhesive sheet of this invention. Examples of such a photopolymerization initiator include benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N′-tetraethyl-4,4′-diaminobenzophenone, 4- Methoxy-4′-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2,2-dimethoxy-1,2-diphenylethane-1-one, 1- Aromatic ketones such as hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropanone-1, 2,4-diethylthioxanthone, 2-ethylanthraquinone, phenanthrenequinone , Benzoin methyl ether, benzoin ethyl ether, benzoin Benzoin ether such as nyl ether, benzoin such as methyl benzoin and ethyl benzoin, benzyl derivatives such as benzyl dimethyl ketal, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4 , 5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-phenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer 2-mer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) -5-phenylimidazole dimer, 2- (2,4-dimethoxy) 2,4,5-triarylimidazole dimer such as phenyl) -4,5-diphenylimidazole dimer , 9-phenyl acridine, 1,7-bis (9,9'-acridinyl) including acridine derivatives heptane, and the like. These may be used alone or in combinations of two or more. Although there is no restriction | limiting in particular as the usage-amount of the said photoinitiator, Usually, it is 0.01-30 weight part with respect to 100 weight part of radiation polymerizable copolymers.
[0048]
Moreover, the above-mentioned various components which form an adhesive bond layer may be contained in the adhesive layer which forms the adhesive sheet of this invention.
[0049]
Moreover, as for the thickness of the adhesive layer which forms the adhesive sheet of this invention, 0.1-50 micrometers is preferable. If the thickness is smaller than 0.1 μm, the adhesive force at the time of dicing tends to be insufficient, and if it is thicker than 50 μm, the semiconductor element tends to be easily damaged at the time of dicing.
[0050]
In addition, various coupling agents can be added to the adhesive layer or pressure-sensitive adhesive layer forming the adhesive sheet of the present invention in order to improve the interfacial bond between different materials. Examples of the coupling agent include silane-based, titanium-based, and aluminum-based, and among them, a silane-based coupling agent is preferable because it is highly effective.
[0051]
The silane coupling agent is not particularly limited, and examples thereof include vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ- Methacryloxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldi Ethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyl Limethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-ureidopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-aminopropyltri Methoxysilane, 3-aminopropyl-tris (2-methoxy-ethoxy-ethoxy) silane, N-methyl-3-aminopropyltrimethoxysilane, triaminopropyltrimethoxysilane, 3-4,5-dihydroimidazole-1- Yl-propyltrimethoxysilane, 3-methacryloxypropyl-trimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyldimethoxysilane, 3 Cyanopropyltriethoxysilane, hexamethyldisilazane, N, O-bis (trimethylsilyl) acetamide, methyltrimethoxysilane, methyltriethoxysilane, ethyltrichlorosilane, n-propyltrimethoxysilane, isobutyltrimethoxysilane, amyltrichlorosilane , Octyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, methyltri (methacryloyloxyethoxy) silane, methyltri (glycidyloxy) silane, N-β (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane , Octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride, γ-chloropropylmethyldichlorosilane, γ-chloropropylmethyldimeth Sisilane, γ-chloropropylmethyldiethoxysilane, trimethylsilyl isocyanate, dimethylsilyl isocyanate, methylsilyl triisocyanate, vinylsilyl triisocyanate, phenylsilyl triisocyanate, tetraisocyanate silane, ethoxysilane isocyanate, etc. can be used alone. Alternatively, two or more types can be used in combination.
[0052]
Examples of the titanium-based coupling agent include isopropyl trioctanoyl titanate, isopropyl dimethacrylisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumyl Phenyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tris (n-aminoethyl) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2,2-diallyl) Oxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, dic Ruphenyloxyacetate titanate, bis (dioctylpyrophosphate) oxyacetate titanate, tetraisopropyl titanate, tetranormal butyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate, titanium acetylacetonate, polytitanium acetylacetonate, titanium Octylene glycolate, Titanium lactate ammonium salt, Titanium lactate, Titanium lactate ethyl ester, Titanium chili ethanolamate, Polyhydroxy titanium stearate, Tetramethyl orthotitanate, Tetraethyl orthotitanate, Tetarapropyl orthotitanate, Tetraisobutyl orthotitanate, Stearyl Titanate, cresyl titanate monomer, cresyl titanate , Diisopropoxy-bis (2,4-pentadionate) titanium (IV), diisopropyl-bis-triethanolamino titanate, octylene glycol titanate, tetra-n-butoxytitanium polymer, tri-n-butoxytitanium mono A stearate polymer, tri-n-butoxy titanium monostearate, etc. can be used, and it can be used individually or in combination of 2 or more types.
[0053]
Examples of the aluminum coupling agent include ethyl acetoacetate aluminum diisopropylate, aluminum toys (ethyl acetoacetate), alkyl acetoacetate aluminum diisopropylate, aluminum monoacetyl acetate bis (ethyl acetoacetate), aluminum tris (acetylacetate). Nate), aluminum = monoisopropoxy monooroxyethyl acetoacetate, aluminum-di-n-butoxide monoethyl acetoacetate, aluminum chelate compounds such as aluminum-di-iso-propoxide-monoethyl acetoacetate, aluminum isopropylate, Mono-sec-butoxyaluminum diisopropylate, aluminum-sec-butyrate, aluminum It can be used such as aluminum alcoholate such Muechireto, alone or in combination of two or more kinds may be used.
[0054]
The amount of the coupling agent used is 0.01 to 100 parts by weight with respect to 100 parts by weight of the epoxy resin and the epoxy resin curing agent in the case of mixing with the adhesive layer from the viewpoint of its effect, heat resistance and cost. The amount is preferably 10 parts by weight, and when mixed in the pressure-sensitive adhesive layer, it is preferably 0.01 to 100 parts by weight with respect to 100 parts by weight of the radiation polymerizable compound.
[0055]
An ion scavenger can be further added to the adhesive layer or pressure-sensitive adhesive layer forming the adhesive sheet of the present invention in order to adsorb ionic impurities and improve insulation reliability during moisture absorption. Such an ion scavenger is not particularly limited, for example, triazine thiol compound, bisphenol-based reducing agent, etc., a compound known as a copper damage preventing agent for preventing copper ionization and dissolution, zirconium-based And inorganic ion adsorbents such as antimony bismuth-based magnesium aluminum compounds. The amount of the ion scavenger used is, in terms of the effect of addition, heat resistance, cost, etc., when mixed in the adhesive layer, 0.1% with respect to 100 parts by weight of the (A) epoxy resin and epoxy resin curing agent. It is preferable to set it as 1-10 weight part, and when mixing with an adhesive layer, it is preferable to set it as 0.01-100 weight part with respect to 100 weight part of radiation polymerizable compounds.
[0056]
A thermopolymerizable compound can be used in combination with the composition constituting the adhesive layer or the pressure-sensitive adhesive layer of the present invention. The thermopolymerizable compound is not particularly limited, and examples thereof include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, Pentenyl acrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate , Trimethylolpropane triacrylate, trimethylolpropane dimethacrylate , Trimethylolpropane trimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, pentaerythritol triacrylate, Pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 1,3 -Acryloyloxy-2-hydroxypropane, 1,2-methacryloyloxy-2-hydroxypropane, methylenebisacrylamide, N N- dimethylacrylamide, N- methylol acrylamide, tris (beta-hydroxyethyl) triacrylate isocyanurate represented by the following general formula (7)
[Chemical 7]

(Wherein R ₇ Represents hydrogen or a methyl group, and q and r are each independently an integer of 1 or more)
Or a reaction product of tolylene diisocyanate and 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate, or a reaction product of trimethylhexamethylene diisocyanate cyclohexane dimethanol and 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate. Such as urethane acrylate or urethane methacrylate. These can be used alone or in combination of two or more.
[0057]
The amount of these thermally polymerizable compounds used is preferably 100% by weight or less of the (A) epoxy resin and epoxy resin curing agent when mixed in the adhesive layer, and when mixed in the adhesive layer, It is preferably 100% by weight or less of the radiation polymerizable compound, more preferably 90% by weight or less, and particularly preferably 80% by weight or less. If the amount used exceeds 100% by weight, the storage stability of the resulting adhesive sheet tends to be poor.
[0058]
In addition, an inorganic filler may be added to the composition constituting the adhesive layer or the pressure-sensitive adhesive layer of the present invention for the purpose of improving the handleability, improving the thermal conductivity, adjusting the melt viscosity and imparting thixotropic properties. You can also. The inorganic filler is not particularly limited. For example, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, aluminum borate whisker, Examples thereof include boron nitride, crystalline silica, amorphous silica, and the like, and the shape of the filler is not particularly limited. These fillers can be used alone or in combination of two or more. Among these, aluminum oxide, aluminum nitride, boron nitride, crystalline silica, and amorphous silica are preferable for improving thermal conductivity. For the purpose of adjusting melt viscosity and imparting thixotropic properties, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, crystallinity Silica, amorphous silica and the like are preferable.
[0059]
As for the usage-amount of an inorganic filler, 1-20 weight part is preferable with respect to 100 weight part of an adhesive bond layer or an adhesive layer. If the amount is less than 1 part by weight, the addition effect tends not to be obtained. If the amount exceeds 20 parts by weight, problems such as an increase in storage elastic modulus of the adhesive layer, a decrease in adhesiveness, and a decrease in electrical characteristics due to residual voids are caused. Tend.
[0060]
As the base material layer forming the adhesive sheet of the present invention, for example, a film of a polyolefin resin such as polyethylene terephthalate, polyimide, polytetrafluoroethylene, polyethylene, polypropylene, polymethylpentene, polyvinyl acetate or the like is used. it can.
[0061]
The thickness of the base material layer is not particularly limited, but is preferably 30 to 300 μm, more preferably 40 to 250 μm, and particularly preferably 50 to 200 μm. If it is thinner than 30 μm, it tends to be cut to the base material layer at the time of dicing, and the chip tends to be scattered, and if it is thicker than 300 μm, it is not economical.
[0062]
The adhesive sheet of the present invention is prepared by, for example, dissolving or dispersing the composition of the adhesive layer and the pressure-sensitive adhesive layer as described above in a solvent to form a varnish, and applying and heating each varnish on different base material layers. Finally, the adhesive layer and the pressure-sensitive adhesive layer formed on different base material layers are bonded together, and the composition of the pressure-sensitive adhesive layer is dissolved or dispersed in a solvent to obtain a varnish. After applying on the base film and heating to remove the solvent to form an adhesive layer, the composition forming the adhesive layer is dissolved or dispersed in the solvent to form a varnish on the adhesive layer. It can be obtained by applying and heating to remove the solvent.
[0063]
Although it does not specifically limit as a solvent which can be used for said varnishing, Considering the volatility at the time of film preparation, for example, methanol, ethanol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, It is preferable to use a solvent having a relatively low boiling point such as methyl ethyl ketone, acetone, methyl isobutyl ketone, toluene, and xylene. In addition, for the purpose of improving the coating properties, for example, a solvent having a relatively high boiling point such as dimethylacetamide, dimethylformamide, N-methylpyrrolidone, cyclohexanone can be used. These solvents can be used alone or in combination of two or more.
[0064]
In addition, when the composition of the adhesive layer or the pressure-sensitive adhesive layer to which the inorganic filler is added is varnished, in consideration of the dispersibility of the inorganic filler, a raking machine, a three roll, a ball mill, a bead mill, or the like is used. Preferably, these can be used in combination. Moreover, after mixing an inorganic filler and a low molecular weight raw material beforehand, the mixing time can also be shortened by mix | blending a high molecular weight raw material. Further, after the varnish is formed, the bubbles in the varnish can be removed by vacuum degassing or the like.
[0065]
As a coating method of the varnish on the base material layer, a known method can be used, for example, knife coating method, roll coating method, spray coating method, gravure coating method, bar coating method, curtain coating method and the like. It is done.
[0066]
When the pressure-sensitive adhesive layer of the adhesive sheet of the present invention obtained as described above is irradiated with radiation, the pressure-sensitive adhesive layer is cured after irradiation, and the adhesive strength between the adhesive layer and the pressure-sensitive adhesive layer is greatly reduced. Further, it is possible to pick up from the adhesive layer of the adhesive sheet while holding the adhesive layer on the semiconductor element.
[0067]
In addition, the pressure-sensitive adhesive layer of the adhesive sheet of the present invention may be used in combination with heating for the purpose of accelerating the curing reaction simultaneously with radiation irradiation or after radiation irradiation, in addition to the method of reducing the adhesive strength only by radiation irradiation. By using radiation irradiation and heating in combination, it is possible to reduce the adhesive strength at the interface between the pressure-sensitive adhesive layer and the adhesive layer in a shorter time at a lower temperature. The heating temperature is not particularly limited as long as it is below the decomposition point of the pressure-sensitive adhesive layer and the adhesive layer, but a temperature of 50 to 170 ° C. is preferable.
[0068]
Moreover, in order to obtain a desired sheet thickness, the adhesive sheet of the present invention further includes one or two or more pressure-sensitive adhesive layers or adhesive layers between the semiconductor wafer and the adhesive layer or the pressure-sensitive adhesive layer and the adhesive layer. You may provide so that it may pinch | interpose. As the pressure-sensitive adhesive layer or adhesive layer sandwiched between them, in addition to those prepared by the method of the present invention, those prepared by a conventionally known method and commercially available adhesive sheets can be used, for example Polyimide, silicon oligomer, rubber-epoxy, and epoxy adhesives can be used. However, it is necessary to consider a bonding condition based on a conventionally known technique that does not cause peeling between the pressure-sensitive adhesive layers or the adhesive layers or between the pressure-sensitive adhesive layer and the adhesive layer at the interface where no peeling is planned. .
[0069]
In the adhesive sheet of the present invention, the ratio of the adhesive strength due to the 90 ° peel peel strength before and after irradiation at the interface between the adhesive layer and the pressure-sensitive adhesive layer (adhesive strength after irradiation / adhesive strength before irradiation) is 0.5 or less. Is preferably 0.4 or less, and more preferably 0.3 or less. If this value exceeds 0.5, each element tends to be easily damaged during pick-up.
[0070]
In the adhesive sheet of the present invention, the difference in adhesive strength before and after radiation irradiation (adhesive strength before irradiation-adhesive strength after irradiation) at the interface between the adhesive layer and the pressure-sensitive adhesive layer is preferably 100 mN / cm or more, and 200 mN / cm It is more preferable that it is cm or more, and it is more preferable that it is 300 mN / cm or more. When this value is less than 100 mN / cm, there is a tendency that chip skipping at the time of dicing is likely to occur or pick-up properties are lowered.
[0071]
Next, an example of a method for manufacturing an adhesive sheet and a method for manufacturing a semiconductor device according to the present invention will be specifically described with reference to the drawings.
[0072]
First, as shown in FIG. 1 and FIG. 2, a varnish of a composition that becomes a pressure-sensitive adhesive layer and an adhesive layer is separately applied on the base material layers 1 and 4, respectively, and a pressure-sensitive adhesive layer ( After producing the adhesive layer (FIG. 1) provided with FIG. 1) and a base material layer, these are laminated | stacked so that an adhesive layer and an adhesive layer may face each other, and an adhesive sheet is obtained (FIG. 3). In addition, a method of applying a varnish of a composition to be an adhesive layer on an adhesive layer (FIG. 1) provided with a base material layer and an adhesive layer on an adhesive layer (FIG. 2) provided with a base material layer An adhesive sheet can also be obtained by a method of applying a varnish of the composition. After producing the adhesive layer (FIG. 1) provided with the said base material layer and the adhesive bond layer (FIG. 2) provided with the base material layer, these were laminated | stacked and the method of obtaining an adhesive sheet (FIG. 3) was selected. In this case, since the base material layer 4 is peeled before the step of attaching the semiconductor wafer, the adhesive layer is compared with the base material layer 1 / adhesive layer 2 interface and the adhesive layer 2 / adhesive layer 3 interface. 3 / Base material layer 4 It is important to select the base material layer so that the adhesive strength at the interface is minimized.
[0073]
Next, after adhering the semiconductor wafer A to be diced as shown in FIG. 4 on the upper surface of the adhesive layer of the adhesive sheet obtained as described above, the semiconductor wafer A is diced as shown in FIG. Then wash and dry. At this time, since the semiconductor wafer A is sufficiently held by the adhesive sheet by the pressure-sensitive adhesive layer 2 and the adhesive layer 3, the semiconductor wafer A does not fall off during each of the above steps.
[0074]
Next, as shown in FIG. 6, the radiation B is irradiated to the adhesive layer 2 of an adhesive sheet, and a part or most of the adhesive layer having radiation polymerization property is polymerized and cured. In this case, heating may be used in combination with the purpose of accelerating the curing reaction simultaneously with irradiation or after irradiation. The adhesive sheet is irradiated with radiation from the surface of the base material layer 1 on which the pressure-sensitive adhesive layer 2 is not provided. Therefore, as described above, when UV is used as the radiation, the base material layer 1 needs to be light transmissive, but when EB is used as the radiation, the base material layer 1 is not necessarily light transmissive. There is no.
[0075]
After the radiation irradiation, the semiconductor elements A1, A2, A3 to be picked up are sequentially picked up by the suction collet 5, for example. At this time, the semiconductor elements A1, A2, and A3 to be picked up can be pushed up from the lower surface of the base material layer 1 by, for example, a needle bar. Since the adhesive strength between the semiconductor element A1 and the adhesive layer 3 is larger than the adhesive strength between the pressure-sensitive adhesive layer 2 and the base material layer 1 and between the pressure-sensitive adhesive layer 2 and the adhesive layer 3, When the semiconductor element A1 is picked up, the adhesive layer 3 is peeled off while being attached to the lower surface of the semiconductor element A1 (FIG. 8).
[0076]
Subsequently, each semiconductor element A1, A2, A3 is mounted on the semiconductor element mounting support member 6 through the adhesive layer 3 and heated. The adhesive layer 3 exhibits adhesive strength by heating, and the bonding between the semiconductor element and the semiconductor element mounting support member is completed (FIG. 9).
[0077]
EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example, this invention is not limited to this.
[0078]
【Example】
(Synthesis Example 1 of radiation polymerizable compound)
A flask equipped with a stirrer, a thermometer, a dry air introduction tube, a dropping funnel, and a cooling tube was charged with 888 parts by weight of VESTANAT IPDI (trade name, isophorone diisocyanate manufactured by Daicel Huls Co., Ltd.) and 789 parts by weight of ethyl acetate. After raising the temperature to 70 ° C., the temperature is kept at 70 to 75 ° C., 232 parts by weight of 2-hydroxyethyl acrylate, PTG650SN (trade name, polyoxytetramethylene glycol, number average molecular weight of about 650 by Hodogaya Chemical Co., Ltd.) 1950 parts by weight A liquid mixture of 1.53 parts by weight of hydroquinone monomethyl ether, 1.53 parts by weight of L101 (trade name, manufactured by Tokyo Fine Chemical Co., Ltd., dibutyltin laurate) and 526 parts by weight of ethyl acetate was uniformly added dropwise over 3 hours to carry out the reaction. It was made to react for about 5 hours after completion | finish of dripping, it confirmed that the isocyanate group had lose | disappeared by IR measurement, reaction was complete | finished, and the radiation polymerizable compound (A-1) was obtained.
[0079]
(Synthesis Example 2 of radiation polymerizable compound)
In a 1 liter flask equipped with a stirrer, thermometer, dry air introduction tube, dropping funnel and condenser tube was added 2,2-bis [4- (4-aminophenoxy) phenyl] propane 197.06 g (0.48 mol) and γ -After charging 318.14 g of butyrolactone, the temperature was raised to 30 ° C, and while maintaining the temperature at 30 to 40 ° C, 50.4 g (0.24 mol) of 2,2,4-trimethylhexamethylene diisocyanate was added dropwise little by little. After the dropwise addition, the reaction was continued at 30 ° C. for 1 hour, and then 70.68 g (0.456 mol) of Karenz MOI (trade name, isocyanate ethyl methacrylate, manufactured by Showa Denko KK) and 0.318 g of hydroquinone monomethyl ether were added at 30 ° C. The solution was added dropwise little by little. After the dropping, the reaction was continued at 30 ° C. or lower for 2 hours to obtain a radiation polymerizable compound (A-2).
[0080]
(Production Example 1 of Adhesive Layer)
Epicoat 828 (trade name, manufactured by Japan Epoxy Resin Co., Ltd., bisphenol A type epoxy resin, epoxy equivalent 190) 45.0 parts by weight, ESCN195 (trade name, Sumitomo Chemical Co., Ltd., o-cresol novolac type epoxy resin, epoxy equivalent) 195) 15.0 parts by weight, Priofen LF2882 (trade name, manufactured by Dainippon Ink and Chemicals, bisphenol A novolak resin), 40.0 parts by weight, HTR-860P-3 (trade name, manufactured by Nagase ChemteX Corporation) , Epoxy group-containing acrylic rubber, molecular weight 1 million, Tg-7 ° C.) 66.7 parts by weight, Curesol 2PZ-CN (trade name, 1-cyanoethyl-2-phenylimidazole, manufactured by Shikoku Kasei Co., Ltd.) 0.5 weight Part, NUC A-187 (Nippon Unicar Co., Ltd. trade name, γ-glycidoxypropyl) The trimethoxysilane) composition comprising 0.7 parts by weight, followed by stirring and mixing by adding methyl ethyl ketone and vacuum degassed. This adhesive varnish was applied onto a 50 μm thick polyethylene terephthalate (made by Teijin DuPont Films, Teijin Tetron film: G2-50, surface tension 50 dyne / cm) as a base material layer, and 140 ° C. for 5 minutes. It heat-dried and obtained the adhesive layer (F-1) of the B stage state whose film thickness provided with the base material layer is 50 micrometers.
[0081]
The storage elastic modulus when this adhesive layer (F-1) was cured at 170 ° C. for 1 hour was measured using a dynamic viscoelasticity measuring device (DVE-V4, manufactured by Rheology) (sample size: length 20 mm, As a result of a width of 4 mm, a film thickness of 80 μm, a heating rate of 5 ° C./min, a tensile mode, 10 Hz, and an automatic static load), it was 360 MPa at 25 ° C. and 14 MPa at 260 ° C.
[0082]
Further, using a tacking tester manufactured by RHESCA, according to the method described in JISZ0237-1991, probe diameter: 5.1 mmΦ, peeling speed: 10 mm / s, contact load: 100 gf / cm ² When the tack strength at 25 ° C. was measured under the measurement condition of contact time: 1 s, it was 1.0 N.
[0083]
(Manufacture example 2 of an adhesive bond layer)
YDCN-703 (trade name, manufactured by Toto Kasei Co., Ltd., o-cresol novolac type epoxy resin, epoxy equivalent 210) 42.3 parts by weight, Phenolite LF2882 (trade name, manufactured by Dainippon Ink & Chemicals, Inc., bisphenol A novolak) Resin) 23.9 parts by weight, HTR-860P-3 (trade name, manufactured by Nagase ChemteX Corporation, epoxy group-containing acrylic rubber, molecular weight 1 million, Tg-7 ° C.) 44.1 parts by weight, Curazole 2PZ-CN ( Shikoku Kasei Kogyo Co., Ltd. trade name, 1-cyanoethyl-2-phenylimidazole) 0.4 parts by weight, NUC A-187 (Nihon Unicar Co., Ltd. trade name, γ-glycidoxypropyltrimethoxysilane) 0 Methyl ethyl ketone was added to the composition consisting of 0.7 parts by weight, mixed with stirring, and vacuum degassed. This adhesive varnish was applied onto a 50 μm thick polyethylene terephthalate (made by Teijin DuPont Films, Teijin Tetron film: G2-50, surface tension 50 dyne / cm) as a base material layer, and 140 ° C. for 5 minutes. It heat-dried and obtained the adhesive layer (F-2) of the B-stage state whose film thickness provided with the base material layer is 50 micrometers.
[0084]
The storage elastic modulus when this adhesive layer (F-2) was cured at 170 ° C. for 1 hour was measured using a dynamic viscoelasticity measuring device (DVE-V4, manufactured by Rheology) (sample size: length 20 mm, As a result of a width of 4 mm, a film thickness of 80 μm, a heating rate of 5 ° C./min, a tensile mode, 10 Hz, and an automatic static load), it was 360 MPa at 25 ° C. and 30 MPa at 260 ° C.
[0085]
Further, using a tacking tester manufactured by RHESCA, according to the method described in JISZ0237-1991, probe diameter: 5.1 mmΦ, peeling speed: 10 mm / s, contact load: 100 gf / cm ² When the tack strength at 25 ° C. was measured under the measurement condition of contact time: 1 s, it was 1.2 N.
[0086]
(Production Example 3 of Adhesive Layer)
YDCN-703 (trade name, manufactured by Toto Kasei Co., Ltd., o-cresol novolac type epoxy resin, epoxy equivalent 210) 61 parts by weight, priofen LF2882 (trade name, manufactured by Dainippon Ink and Chemicals, bisphenol A novolak resin) 39 parts by weight, HTR-860P-3) Teikoku Chemical Industry Co., Ltd. trade name, epoxy group-containing acrylic rubber, molecular weight 1 million, Tg-7 ° C.) 150 parts by weight, Curesol 2PZ-CN (Shikoku Kasei Kogyo Co., Ltd.) Product name, 1-cyanoethyl-2-phenylimidazole) 0.5 part by weight and NUC A-187 (Nihon Unicar Co., Ltd. product name, γ-glycidoxypropyltrimethoxysilane) 0.7 part by weight Methyl ethyl ketone was added to the composition, mixed with stirring, and vacuum degassed. This adhesive varnish was applied onto a 50 μm thick polyethylene terephthalate (made by Teijin DuPont Films, Teijin Tetron film: G2-50, surface tension 50 dyne / cm) as a base material layer, and 140 ° C. for 5 minutes. It heat-dried and obtained the adhesive layer (F-3) of the B stage state whose film thickness provided with the base material layer was 50 micrometers.
[0087]
The storage elastic modulus when this adhesive layer (F-3) was cured at 170 ° C. for 1 hour was measured using a dynamic viscoelasticity measuring device (DVE-V4, manufactured by Rheology) (sample size: length 20 mm, As a result of a width of 4 mm, a film thickness of 80 μm, a heating rate of 5 ° C./min, a tensile mode, 10 Hz, and an automatic static load), it was 380 MPa at 25 ° C. and 50 MPa at 260 ° C.
[0088]
Further, using a tacking tester manufactured by RHESCA, according to the method described in JISZ0237-1991, probe diameter: 5.1 mmΦ, peeling speed: 10 mm / s, contact load: 100 gf / cm ² When the tack strength at 25 ° C. was measured under the measurement condition of contact time: 1 s, it was 0.4 N.
[0089]
(Manufacture example 1 of an adhesive layer)
Epicoat 828 (trade name, manufactured by Yuka Shell Epoxy Co., Ltd., bisphenol A type epoxy resin, epoxy equivalent 190), 23.4 parts by weight, ESCN195 (trade name, Sumitomo Chemical Co., Ltd., cresol novolac type epoxy resin, epoxy equivalent 195) ) 15 parts by weight, Priofen LF2882 (trade name, manufactured by Dainippon Ink & Chemicals, Inc., bisphenol A novolac resin) 23.9 parts by weight, HTR-860P-3) product name, manufactured by Teikoku Chemicals, Inc., epoxy group Containing acrylic rubber, molecular weight 1 million, Tg-7 ° C. 44.1 parts by weight, Curesol 2PZ-CN (trade name, 1-cyanoethyl-2-phenylimidazole manufactured by Shikoku Chemicals Co., Ltd.) 0.4 part by weight, NUC A-187 (Nippon Unicar Co., Ltd. trade name, γ-glycidoxypropyltrimethoxysilane) A composition comprising 0.7 part by weight, 22.05 parts by weight of the radiation polymerizable compound (A-1) obtained in Synthesis Example 1 of the above radiation polymerizable compound and 0.5 part by weight of 1-hydroxycyclohexyl phenyl ketone. Then, methyl ethyl ketone was added and mixed with stirring, followed by vacuum degassing. This adhesive varnish is applied on a polyethylene terephthalate film with a thickness of 50 μm to be a base material layer, dried by heating at 100 ° C. for 5 minutes, and a B-stage pressure-sensitive adhesive having a base material layer and a film thickness of 10 μm. A layer (P-1) was produced.
(Manufacture example 2 of an adhesive layer)
Except for using the radiation polymerizable compound (A-2) obtained in Synthesis Example 2 of the radiation polymerizable compound instead of the radiation polymerizable compound (A-1), the same operation as in Production Example 1 of the pressure-sensitive adhesive layer was performed. A B-stage pressure-sensitive adhesive layer (P-2) having a base layer and a film thickness of 10 μm was produced.
(Manufacture example 3 of an adhesive layer)
Except for using NK-ESTER A-200 (trade name of Shin-Nakamura Chemical Co., Ltd., tetraethylene glycol diacrylate) instead of the radiation-polymerizable compound (A-1), exactly the same as Production Example 1 of the pressure-sensitive adhesive layer The B-stage pressure-sensitive adhesive layer (P-3) having a thickness of 10 μm and having a base material layer was prepared.
Example 1
Using the hot roll laminator, the adhesive layer (F-1) provided with the base material layer and the pressure-sensitive adhesive layer (P-1) provided with the base material layer were heated at a temperature of 30 ° C. and a linear pressure. Was laminated so that the adhesive layer and the pressure-sensitive adhesive layer were combined under the conditions of: 1.0 to 1.5 MPa, and speed: 0.5 m / min. Thus, an adhesive sheet 1 was obtained.
[0090]
A 150 μm-thick semiconductor wafer was attached to the obtained adhesive sheet 1 and placed on a dicing apparatus. Next, after fixing the semiconductor wafer on a dicing apparatus and dicing to 5 mm × 5 mm at a speed of 100 mm / sec, using a UV-330 HQP-2 type exposure machine manufactured by Oak Manufacturing Co., Ltd., 500 mJ / cm ² It exposed from the base material layer side of the adhesive sheet 1 by the exposure amount of. Subsequently, the semiconductor element with an adhesive layer was picked up with a pickup device. In the process so far, the chip skipping at the time of dicing and the pickup property of the semiconductor element with adhesive were evaluated. The probability of chip (semiconductor element) flying at the time of dicing (% / 100 chips) is the success rate (% / 100 chips) of picking up the semiconductor element with an adhesive layer by pick-up die bonder. The pick-up property of the semiconductor element with the adhesive layer was shown.
[0091]
Thereafter, a polyimide film having a thickness of 25 μm was used as a semiconductor element mounting support member, and a semiconductor device sample (formed with a solder ball on one side) was prepared by bonding the picked-up semiconductor element with an adhesive layer to the semiconductor film. The moisture resistance was examined. As a heat resistance evaluation method, reflow crack resistance and a temperature cycle test were applied. The evaluation of reflow crack resistance was repeated twice by passing the semiconductor device sample through an IR reflow oven set at a temperature of 240 ° C. for 20 seconds and then allowing it to cool at room temperature. The cracks in the sample were observed visually and with an ultrasonic microscope, and the probability of occurrence of cracks (% / 100 chips) was shown. Temperature cycle resistance refers to a process in which a semiconductor device sample is allowed to stand in an atmosphere of −55 ° C. for 30 minutes and then left in an atmosphere of 125 ° C. for 30 minutes. After 1000 cycles, peeling or cracking is performed using an ultrasonic microscope. The probability that no destruction occurred (% / 100 chips). In addition, the humidity resistance evaluation is as follows: temperature 121 ° C., humidity 100%, 2.03 × 10 ⁵ This was carried out by observing peeling after treatment for 72 hours in an atmosphere of Pa (pressure cooker test: PCT treatment). It was shown by the probability (% / 100 chip) that peeling did not occur.
[0092]
Moreover, before exposing the said adhesive sheet, 500 mJ / cm ² The adhesive strength at each adhesive layer / pressure-sensitive adhesive layer interface after exposure from the base material layer side with the exposure amount was measured at 90 ° peel strength (tensile speed: 50 mm / min).
[0093]
These evaluation results are summarized in Table 3.
[0094]
(Examples 2 to 6)
Adhesive layer (F-1 to 2) provided with the base material layer obtained in Production Examples 1 and 2 of the adhesive layer and adhesive material provided with the base material layer obtained in Production Examples 1 to 3 of the pressure sensitive adhesive layer The agent layers (P-1 to P-3) were laminated in the same manner as in Example 1 with the combinations shown in Table 1 to obtain adhesive sheets 2 to 6. The obtained adhesive sheets 2 to 6 were evaluated in the same manner as in Example 1.
[0095]
The results are shown in Table 3.
[0096]
[Table 1]

[0097]
(Comparative Examples 1-3)
Adhesive layer (F-3) provided with the base material layer obtained in Production Example 3 of the adhesive layer and pressure-sensitive adhesive layer (P-3) provided with the base material layer obtained in Production Examples 1 to 3 of the pressure-sensitive adhesive layer -1 to 3) were laminated in the same manner as in Example 1 with combinations shown in Table 2 to obtain adhesive sheets 7 to 9. The obtained adhesive sheets 7 to 9 were evaluated in the same manner as in Example 1.
[0098]
The results are shown in Table 3.
[0099]
[Table 2]

[0100]
[Table 3]

[0101]
From Table 3, since the adhesive sheet of the present invention is excellent in the adhesiveness at the interface between the adhesive layer and the pressure-sensitive adhesive layer before radiation irradiation, the chip does not scatter in the dicing process, and the pickup property is also excellent. I found out. On the other hand, in the adhesive sheet of the comparative example, all chips were scattered during dicing, and subsequent evaluation could not be performed. Moreover, it turned out that the semiconductor device sample which die-bonded the semiconductor element with an adhesive layer of this invention is excellent in both heat resistance and moisture resistance.
[0102]
【The invention's effect】
The adhesive sheet of the present invention acts as a dicing tape in the dicing process, and can be used as an adhesive having excellent connection reliability in the bonding process of the semiconductor element and the support member. It is an adhesive sheet having heat resistance and moisture resistance required for mounting a semiconductor element having a large difference in thermal expansion coefficient and excellent workability. The present invention can further provide a manufacturing method capable of simplifying the manufacturing process of the semiconductor device.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view of an example of a pressure-sensitive adhesive layer provided with a base material layer of an adhesive sheet according to the present invention.
FIG. 2 is a cross-sectional view of an example of an adhesive layer provided with a base material layer of an adhesive sheet according to the present invention.
FIG. 3 is a cross-sectional view of an example of an adhesive sheet according to the present invention.
FIG. 4 is a cross-sectional view showing a state where a semiconductor wafer is bonded to the adhesive sheet according to the present invention.
FIG. 5 is a view when the adhesive sheet according to the present invention is used in a dicing process of a semiconductor wafer.
6 is a view showing a state in which the adhesive sheet is irradiated with radiation from the base layer side after the step shown in FIG. 5. FIG.
7 is a view showing a state where a semiconductor element is to be picked up after the step shown in FIG. 6;
FIG. 8 is a view showing a state where a semiconductor element with an adhesive layer is picked up.
FIG. 9 is a view showing a state in which a semiconductor element with an adhesive layer is thermocompression bonded to a semiconductor element mounting support member.
[Explanation of symbols]
1 Base material layer
2 Adhesive layer
3 Adhesive layer
4 Base material layer
5 Suction collet
6 Support elements for mounting semiconductor elements
A Semiconductor wafer
A1, A2, A3 Semiconductor element
B Radiation

Claims (9)

(A) an epoxy resin and an epoxy resin curing agent , and (B) a glycidyl group-containing (meth) acrylic copolymer having a weight average molecular weight of 100,000 or more, and the amount of the epoxy resin-containing repeating unit is 0.5 to An adhesive layer containing a resin component consisting of 6% by weight of a high molecular weight component, a pressure-sensitive adhesive layer containing a radiation polymerizable compound, and a base material layer,
The adhesive strength between the adhesive layer and the pressure-sensitive adhesive layer before irradiation is 200 mN / cm or more,
Tack strength of 25 ° C. by 5.1mmΦ probe measurement of the adhesive layer in an uncured or semi-cured state is Ri der least 0.8 N, and
The adhesive sheet in which the adhesive layer has a storage elastic modulus after heat curing at 260 ° C of 7 to 50 MPa .   The adhesive sheet according to claim 1, wherein a ratio of adhesive strength before and after radiation irradiation (adhesive strength after irradiation / adhesive strength before irradiation) at the interface between the adhesive layer and the pressure-sensitive adhesive layer is 0.5 or less.   The adhesive sheet according to claim 1 or 2, wherein a difference in adhesive strength before and after radiation irradiation (adhesive strength before irradiation-adhesive strength after irradiation) at the interface between the adhesive layer and the pressure-sensitive adhesive layer is 100 mN / cm or more.   The adhesive layer contains 100 parts by weight of the (A) epoxy resin and epoxy resin curing agent, and 10 to 400 parts by weight of a high molecular weight component having a weight average molecular weight of 100,000 or more including the functional monomer (B). The adhesive sheet according to any one of claims 1 to 3. Adhesive sheet of the adhesive layer, having a storage elastic modulus after heat curing of 10～2000MP a at 25 ° C., according to any one of claims 1 to 4.   The adhesive sheet according to any one of claims 1 to 5, wherein the adhesive layer, the pressure-sensitive adhesive layer, and the base material layer are laminated in the order of base material layer / pressure-sensitive adhesive layer / adhesive layer.   The adhesive sheet according to any one of claims 1 to 6, wherein an adhesive strength between the adhesive layer and the pressure-sensitive adhesive layer interface can be controlled by irradiating the pressure-sensitive adhesive layer with radiation.   The semiconductor device which adhere | attached the semiconductor element and the supporting member for semiconductor element mounting using the adhesive sheet of any one of Claims 1-7. A step of attaching a semiconductor wafer to the adhesive layer of the adhesive sheet according to claim 1,
Dicing the semiconductor wafer together with at least the adhesive layer to form a semiconductor element with an adhesive layer;
Irradiating the pressure-sensitive adhesive layer of the adhesive sheet with radiation to cure it,
A step of peeling the semiconductor element with an adhesive layer from the adhesive sheet at an interface between the adhesive layer and the pressure-sensitive adhesive layer; and the semiconductor element with an adhesive layer and a semiconductor element mounting support member at a predetermined position. Bonding process,
A method of manufacturing a semiconductor device including:

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