JP7472954B2 - 接着剤組成物、フィルム状接着剤、接着シート、及び半導体装置の製造方法 - Google Patents
接着剤組成物、フィルム状接着剤、接着シート、及び半導体装置の製造方法 Download PDFInfo
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- JP7472954B2 JP7472954B2 JP2022179719A JP2022179719A JP7472954B2 JP 7472954 B2 JP7472954 B2 JP 7472954B2 JP 2022179719 A JP2022179719 A JP 2022179719A JP 2022179719 A JP2022179719 A JP 2022179719A JP 7472954 B2 JP7472954 B2 JP 7472954B2
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Description
本実施形態に係る接着剤組成物は、(A)熱硬化性樹脂と、(B)硬化剤と、(C)エラストマーと、を含有する。接着剤組成物は、熱硬化性であり、半硬化(Bステージ)状態を経て、硬化処理後に完全硬化物(Cステージ)状態となり得る。
熱硬化性樹脂は、接着性の観点から、エポキシ樹脂を含んでいてよい。本実施形態に係る接着剤組成物は、熱硬化性樹脂として、(A-1)脂環式環を有するエポキシ樹脂を含む。
(B)成分は、特に制限なく、熱硬化性樹脂の硬化剤として一般的に使用されているものを用いることができる。熱硬化性樹脂がエポキシ樹脂を含む場合、(B)成分としては、例えば、フェノール樹脂、エステル化合物、芳香族アミン、脂肪族アミン、酸無水物等が挙げられる。これらは、1種を単独で又は2種以上を組み合わせて用いてもよい。これらの中でも、反応性及び経時安定性の観点から、(B)成分はフェノール樹脂を含んでいてよい。
本実施形態に係る接着剤組成物は、(C)エラストマーを含有する。(C)成分は、エラストマーを構成する重合体のガラス転移温度(Tg)が50℃以下であるものが好ましい。
本実施形態に係る接着剤組成物は、(D)無機フィラーをさらに含有していてもよい。無機フィラーとしては、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、ホウ酸アルミウィスカ、窒化ホウ素、結晶性シリカ、非晶性シリカ等が挙げられる。これらは1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。得られるフィルム状接着剤の熱伝導性がより向上する観点から、無機フィラーは、酸化アルミニウム、窒化アルミニウム、窒化ホウ素、結晶性シリカ又は非晶性シリカを含んでいてよい。また、接着剤組成物の溶融粘度を調整する観点及び接着剤組成物にチキソトロピック性を付与する観点から、無機フィラーは、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、結晶性シリカ又は非晶性シリカを含んでいてよい。
本実施形態に係る接着剤組成物は、(E)硬化促進剤を含有していてよい。硬化促進剤は、特に限定されず、一般に使用されるものを用いることができる。(E)成分としては、例えば、イミダゾール類及びその誘導体、有機リン系化合物、第二級アミン類、第三級アミン類、第四級アンモニウム塩等が挙げられる。これらは、1種を単独で又は2種以上を組み合わせて用いてもよい。これらの中でも、反応性の観点から(E)成分はイミダゾール類及びその誘導体であってよい。
本実施形態に係る接着剤組成物は、その他の成分として、抗酸化剤、シランカップリング剤、レオロジーコントロール剤等をさらに含有していてもよい。これらの成分の含有量は、(A)成分、(B)成分、及び(C)成分の総量100質量部に対して、0.02~3質量部であってよい。
図1は、一実施形態に係るフィルム状接着剤を示す模式断面図である。フィルム状接着剤10は、上述の接着剤組成物をフィルム状に形成してなるものである。フィルム状接着剤10は、半硬化(Bステージ)状態であってよい。このようなフィルム状接着剤10は、接着剤組成物を支持フィルムに塗布することによって形成することができる。接着剤ワニスを用いる場合は、接着剤ワニスを支持フィルムに塗布し、溶剤を加熱乾燥して除去することによってフィルム状接着剤10を形成することができる。
図2は、一実施形態に係る接着シートを示す模式断面図である。接着シート100は、基材20と基材上に設けられた上述のフィルム状接着剤10とを備える。
図4は、一実施形態に係る半導体装置を示す模式断面図である。半導体装置200は、基板14に、第1のワイヤ88を介して1段目の第1の半導体素子Waがワイヤボンディング接続されると共に、第1の半導体素子Wa上に、第2の半導体素子Waaがフィルム状接着剤10を介して圧着されることで、第1のワイヤ88の少なくとも一部がフィルム状接着剤10に埋め込まれてなる半導体装置である。半導体装置は、第1のワイヤ88の少なくとも一部が埋め込まれてなるワイヤ埋め込み型の半導体装置であっても、第1のワイヤ88及び第1の半導体素子Waが埋め込まれてなる半導体装置であってもよい。また、半導体装置200では、基板14と第2の半導体素子Waaとがさらに第2のワイヤ98を介して電気的に接続されると共に、第2の半導体素子Waaが封止材42により封止されている。
本実施形態に係る半導体装置の製造方法は、基板上に第1のワイヤを介して第1の半導体素子を電気的に接続する第1のワイヤボンディング工程と、第2の半導体素子の片面に、上述のフィルム状接着剤を貼付するラミネート工程と、フィルム状接着剤が貼付された第2の半導体素子を、フィルム状接着剤を介して圧着することで、第1のワイヤの少なくとも一部をフィルム状接着剤に埋め込むダイボンド工程と、を備える。
<接着シートの作製>
以下に示す各成分を表1及び表2に示した配合割合(質量部)で混合し、溶媒としてシクロヘキサノンを用いて固形分40質量%の接着剤組成物のワニスを調製した。次に、得られたワニスを100メッシュのフィルターでろ過し、真空脱泡した。真空脱泡後のワニスを、基材フィルムとして、厚さ38μmの離型処理を施したポリエチレンテレフタレート(PET)フィルム上に塗布した。塗布したワニスを、90℃で5分間、続いて140℃で5分間の2段階で加熱乾燥した。このようにして、基材フィルム上に、半硬化(Bステージ)状態にある厚さ110μmのフィルム状接着剤を備える接着シートを得た。
(A-1)脂環式環を有するエポキシ樹脂
A-1-1:一般式(1a)で表されるエポキシ樹脂(ジシクロペンタジエン構造を有するエポキシ樹脂)、DIC株式会社製、商品名:HP-7200L、エポキシ当量:250~280g/eq
A-1-2:一般式(1a)で表されるエポキシ樹脂(ジシクロペンタジエン構造を有するエポキシ樹脂)、日本化薬株式会社製、商品名:XD-1000、エポキシ当量:254g/eq
A-1―3:一般式(2)で表されるエポキシ樹脂(25℃で液体)、株式会社ダイセル製、商品名:セロキサイド2021P、エポキシ当量:128~145g/eq
A-1-4:一般式(4)で表されるエポキシ樹脂、株式会社ダイセル製、商品名:EHPE3150、エポキシ当量:170~190g/eq
(A-2)脂環式環を有しない芳香族エポキシ樹脂
A-2-1:多官能芳香族エポキシ樹脂、株式会社プリンテック製、商品名:VG3101L、エポキシ当量:210g/eq
A-2-2:クレゾールノボラック型エポキシ樹脂、新日鉄住金化学株式会社製、商品名:YDCN-700-10、エポキシ当量:209g/eq
A-2-3:ビスフェノールF型エポキシ樹脂(25℃で液体)、DIC株式会社製、商品名:EXA-830CRP、エポキシ当量:159g/eq
(B)硬化剤
B-1:ビスフェノールAノボラック型フェノール樹脂、DIC株式会社製、商品名:LF-4871、水酸基当量:118g/eq
B-2:フェニルアラルキル型フェノール樹脂、三井化学株式会社製、商品名:XLC-LL、水酸基当量:175g/eq
B-3:フェニルアラルキル型フェノール樹脂、エア・ウォーター株式会社製、商品名:HE100C-30、水酸基当量:170g/eq
(C)エラストマー
C-1:エポキシ基含有アクリル樹脂(アクリルゴム)、ナガセケムテックス株式会社製、商品名:HTR-860P、重量平均分子量:80万、グリシジル官能基モノマー比率:3%、Tg:-7℃
C-2:アクリル樹脂(アクリルゴム)、ナガセケムテックス株式会社製、商品名:SG-70L、重量平均分子量:90万、酸価:5mgKOH/g、Tg:-13℃
(D)無機フィラー
D-1:シリカフィラー分散液、溶融シリカ、株式会社アドマテックス製、商品名:SC2050-HLG、平均粒径:0.50μm
(E)硬化促進剤
E-1:1-シアノエチル-2-フェニルイミダゾール、四国化成工業株式会社製、商品名:キュアゾール2PZ-CN
得られた接着シートについて、埋め込み性及びブリード量の評価を行った。
接着シートの埋め込み性を以下の評価サンプルを作製して評価した。上記で得られたフィルム状接着剤(厚さ110μm)を、基材フィルムを剥がし、ダイシングテープに貼り付け、ダイシングダイボンディング一体型接着シートを得た。次に、厚さ100μmの半導体ウェハ(8インチ)を、接着剤側に70℃に加熱して貼り付けた。その後、この半導体ウェハを7.5mm角にダイシングすることによって、半導体チップAを得た。次に、ダイシングダイボンディング一体型接着シート(日立化成株式会社製、商品名:HR9004-10)(厚さ10μm)を用意し、厚さ50μmの半導体ウェハ(8インチ)に70℃に加熱して貼り付けた。その後、この半導体ウェハを4.5mm角にダイシングすることによって、ダイボンディングフィルム付きの半導体チップBを得た。次いで、ソルダーレジスト(太陽日酸株式会社製、商品名:AUS308)を塗布した総厚さ260μmの評価用基板を用意し、ダイボンディングフィルム付きの半導体チップBのダイボンディングフィルムと評価用基板のソルダーレジストとが接するように、120℃、0.20MPa、2秒間の条件で圧着した。その後、半導体チップAのフィルム状接着剤と半導体チップBの半導体ウェハとが接するように、120℃、0.20MPa、1.5秒間の条件で圧着し、評価サンプルを得た。この際、先に圧着している半導体チップBが半導体チップAの中央となるように位置合わせを行った。このようにして得られた評価サンプルを超音波デジタル画像診断装置(インサイト株式会社製、プローブ:75MHz)にてボイドの観測の有無を観測し、ボイドが観測された場合は、単位面積あたりのボイドの面積の割合を算出し、これらの分析結果を埋め込み性として評価した。評価基準は、以下のとおりである。結果を表1及び表2に示す。
A:ボイドが観測されなかった。
B:ボイドが観測されたが、その割合が5面積%未満であった。
C:ボイドが観測され、その割合が5面積%以上であった。
上記埋め込み性評価で作製した評価サンプルと同様にして、ブリード量評価の評価サンプルを作製した。顕微鏡を用いて、評価サンプルの4辺の中心から、フィルム状接着剤のはみ出し量を測長し、その最大値をブリード量とした。結果を表1及び表2に示す。
上記埋め込み性評価で「A」又は「B」であったものについて、ブリード量評価を行った。上記埋め込み性評価で作製した評価サンプルと同様にして、ブリード量評価の評価サンプルを作製した。顕微鏡を用いて、評価サンプルの4辺の中心から、フィルム状接着剤のはみ出し量を測長し、その最大値をブリード量とした。結果を表1及び表2に示す。
Claims (9)
- 熱硬化性樹脂と、硬化剤と、エラストマーと、無機フィラーとを含有し、
前記熱硬化性樹脂がエポキシ樹脂であり、
前記硬化剤がフェノール樹脂であり、
前記エラストマーがアクリル樹脂であり、
前記無機フィラーがシリカフィラーであり、
前記熱硬化性樹脂が脂環式環を有するエポキシ樹脂を含み、
前記脂環式環を有するエポキシ樹脂が下記一般式(1a)で表されるエポキシ樹脂であり、
前記熱硬化性樹脂及び前記硬化剤の合計の含有量が、接着剤組成物全量を基準として、30~55質量%であり、
前記脂環式環を有するエポキシ樹脂の含有量が、接着剤組成物全量を基準として、5質量%以上であり、
前記無機フィラーの含有量が、前記熱硬化性樹脂、前記硬化剤、及び前記エラストマーの総量100質量部に対して、10~90質量部であり、
前記エラストマーの含有量が、前記熱硬化性樹脂及び前記硬化剤の総量100質量部に対して、20~200質量部であり、
基板上に第1のワイヤを介して第1の半導体素子がワイヤボンディング接続されると共に、前記第1の半導体素子上に、第2の半導体素子が圧着されてなる半導体装置において、前記第2の半導体素子を圧着すると共に前記第1のワイヤ及び前記第1の半導体素子を埋め込むために用いられる、接着剤組成物。
[式(1a)中、n1は1~10の整数を示す。] - 前記脂環式環を有するエポキシ樹脂の含有量が、前記熱硬化性樹脂の全量を基準として、50~100質量%である、請求項1に記載の接着剤組成物。
- 前記熱硬化性樹脂が、前記熱硬化性樹脂の全量を基準として、50~100質量%の前記脂環式環を有するエポキシ樹脂と、0~50質量%の脂環式環を有しない芳香族エポキシ樹脂とから構成される、請求項1又は2に記載の接着剤組成物。
- 硬化促進剤をさらに含有する、請求項1~3のいずれか一項に記載の接着剤組成物。
- 請求項1~4のいずれか一項に記載の接着剤組成物をフィルム状に形成してなる、フィルム状接着剤。
- 基材と、
前記基材上に設けられた、請求項5に記載のフィルム状接着剤と、
を備える、接着シート。 - 前記基材がダイシングテープである、請求項6に記載の接着シート。
- 前記フィルム状接着剤の前記基材とは反対側の面に積層された保護フィルムをさらに備える、請求項6又は7に記載の接着シート。
- 基板上に第1のワイヤを介して第1の半導体素子を電気的に接続するワイヤボンディング工程と、
第2の半導体素子の片面に、請求項5に記載のフィルム状接着剤を貼付するラミネート工程と、
前記フィルム状接着剤が貼付された第2の半導体素子を、前記フィルム状接着剤を介して圧着することで、前記第1のワイヤ及び前記第1の半導体素子を前記フィルム状接着剤に埋め込むダイボンド工程と、
を備える、半導体装置の製造方法。
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