JP6180661B2 - 積層体の製造方法、基板の処理方法及び積層体 - Google Patents
積層体の製造方法、基板の処理方法及び積層体 Download PDFInfo
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- JP6180661B2 JP6180661B2 JP2016562353A JP2016562353A JP6180661B2 JP 6180661 B2 JP6180661 B2 JP 6180661B2 JP 2016562353 A JP2016562353 A JP 2016562353A JP 2016562353 A JP2016562353 A JP 2016562353A JP 6180661 B2 JP6180661 B2 JP 6180661B2
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Description
図1の(a)〜(e)を用いて、本発明の一実施形態に係る積層体10の製造方法について詳細に説明する。
分離層形成工程では、図1の(a)に示すサポートプレート2上に、反応性ポリシルセスキオキサンを溶剤に溶解した溶液を塗布する。その後、当該溶液を塗布したサポートプレート2を加熱することによって、反応性ポリシルセスキオキサンを重合させる。これによって、図1の(b)に示すように、サポートプレート2上に分離層4を形成する。
サポートプレート(支持体)2は、基板の薄化、搬送、実装等のプロセス時に、基板の破損又は変形を防ぐために基板1を支持するためのものである(図1の(a))。
分離層4は、反応性ポリシルセスキオキサンを加熱することで重合させることにより形成される層であり、光を照射することで変質させることができる。
本明細書中において、反応性ポリシルセスキオキサンとは、ポリシルセスキオキサン骨格の末端にシラノール基、又は、加水分解することによってシラノール基を形成することができる官能基を有するポリシルセスキオキサンであり、当該シラノール基又はシラノール基を形成することができる官能基を縮合することによって、互いに重合することができるものである。また、反応性ポリシルセスキオキサンは、シラノール基、又は、シラノール基を形成することができる官能基を備えていれば、ランダム構造、籠型構造、ラダー構造等のシルセスキオキサン骨格を備えたものを採用することができる。
溶剤は、反応性ポリシルセスキオキサンを溶解することができるものであればよく、以下に示す溶剤を用いることができる。
接着層形成工程では、図1の(c)に示す基板1上に、接着剤を塗布して接着層3を形成する(図1の(d))。
基板1は、サポートプレート2に支持された状態で、薄化、実装等のプロセスに供され得る。本実施形態に係る積層体の製造方法では、基板1として、シリコンウエハを用いる。
接着層3は、基板1とサポートプレート2とを貼り付けるために用いられる。
一実施形態に係る積層体の製造方法では、接着層3を形成すための接着剤は、ポリサルホン系樹脂を含んでいることが好ましい。接着層3をポリサルホン系樹脂によって形成することにより、高温において積層体10を処理しても、その後の工程において接着層を溶解し、基板からサポートプレートを剥離することが可能な積層体10を製造することができる。
ポリサルホン系樹脂は、式(2)で表されるポリサルホン構成単位及び式(3)で表されるポリエーテルサルホン構成単位のうちの少なくとも1つを備えていることによって、基板1とサポートプレート2とを貼り付けた後、高い温度条件において基板1を処理しても、分解及び重合等により接着層3が不溶化することを防止することができる積層体10を形成することができる。また、ポリサルホン系樹脂は、上記式(2)で表されるポリサルホン構成単位からなるポリサルホン樹脂であれば、より高い温度に加熱しても安定である。このため、洗浄後の基板に接着層に起因する残渣が発生することを防止することができる。
炭化水素樹脂は、炭化水素骨格を有し、単量体組成物を重合してなる樹脂である。炭化水素樹脂として、シクロオレフィン系ポリマー(以下、「樹脂(A)」ということがある)、並びに、テルペン樹脂、ロジン系樹脂及び石油樹脂からなる群より選ばれる少なくとも1種の樹脂(以下、「樹脂(B)」ということがある)等が挙げられるが、これに限定されない。
このようなシクロオレフィンコポリマーとしては、APL 8008T、APL 8009T、及びAPL 6013T(全て三井化学株式会社製)等を使用することができる。
アクリル−スチレン系樹脂としては、例えば、スチレン又はスチレンの誘導体と、(メタ)アクリル酸エステル等とを単量体として用いて重合した樹脂が挙げられる。
マレイミド系樹脂としては、例えば、単量体として、N−メチルマレイミド、N−エチルマレイミド、N−n−プロピルマレイミド、N−イソプロピルマレイミド、N−n−ブチルマレイミド、N−イソブチルマレイミド、N−sec−ブチルマレイミド、N−tert−ブチルマレイミド、N−n−ペンチルマレイミド、N−n−ヘキシルマレイミド、N−n−へプチルマレイミド、N−n−オクチルマレイミド、N−ラウリルマレイミド、N−ステアリルマレイミド等のアルキル基を有するマレイミド、N−シクロプロピルマレイミド、N−シクロブチルマレイミド、N−シクロペンチルマレイミド、N−シクロヘキシルマレイミド、N−シクロヘプチルマレイミド、N−シクロオクチルマレイミド等の脂肪族炭化水素基を有するマレイミド、N−フェニルマレイミド、N−m−メチルフェニルマレイミド、N−o−メチルフェニルマレイミド、N−p−メチルフェニルマレイミド等のアリール基を有する芳香族マレイミド等を重合して得られた樹脂が挙げられる。
エラストマーは、主鎖の構成単位としてスチレン単位を含んでいることが好ましく、当該「スチレン単位」は置換基を有していてもよい。置換基としては、例えば、炭素数1〜5のアルキル基、炭素数1〜5のアルコキシ基、炭素数1〜5のアルコキシアルキル基、アセトキシ基、カルボキシル基等が挙げられる。また、当該スチレン単位の含有量が14重量%以上、50重量%以下の範囲内であることがより好ましい。さらに、エラストマーは、重量平均分子量が10,000以上、200,000以下の範囲内であることが好ましい。
また、接着層3を構成する接着剤は、本質的な特性を損なわない範囲において、混和性のある他の物質をさらに含んでいてもよい。例えば、接着剤の性能を改良するための付加的樹脂、可塑剤、接着補助剤、安定剤、着色剤、熱重合禁止剤及び界面活性剤等、慣用されている各種添加剤をさらに用いることができる。
図1の(e)に示すように、積層工程は積層体10を形成するための工程である。
本実施形態に係る積層体の製造方法によって製造された積層体10も本発明の範疇である。
次に、一実施形態に係る基板の処理方法について説明する。一実施形態に係る基板の処理方法は、一実施形態に係る積層体の製造方法によって積層体10を製造する積層体製造工程(図1の(a)〜(e))と、積層体製造工程の後、分離層4に光を照射することにより、分離層4を変質させ、サポートプレート2を積層体10から分離する分離工程(図1の(f)及び(g))とを包含している。
図1の(f)に示すように、分離工程では、サポートプレート2を介して分離層4に光を照射する。これにより、積層体10の分離層4を変質させ、基板1とサポートプレート2とを分離する(図1の(g))。なお、分離工程では、例えば、所望の処理を行なった後の積層体10における基板1側の面をダイシングテープに貼り付け、サポートプレート2側から分離層4に対して光を照射するとよい。これによって、薄化処理を施された基板1が破損することを防止しつつ、以後の工程を行なうことができる。
サポートプレート2を分離した基板1には、洗浄工程、ダイシング工程等のその他の工程が行なわれる。これによって、基板1から半導体チップを製造する。
本発明に係る積層体の製造方法は、上記実施形態に限定されない。例えば、別の実施形態に係る積層体の製造方法では、基板として、セラミックス基板、薄いフィルム基板及びフレキシブル基板等の任意の基板を使用し、支持体としてシリコンからなるサポートプレートを使用する。
高温プロセスにおける積層体の評価では、実施例1〜4として、異なる反応性ポリシルセスキオキサンを用いて分離層を形成した積層体を作製し、積層体の耐熱性、反り、分離性の評価を行なった。また、比較例1として、非反応性ポリシルセスキオキサンを用いて分離層を形成した積層体を作製し、比較例2として、フルオロカーボンからなる分離層を形成した積層体を作製し、実施例1〜4の評価と同じ評価を行なった。
まず、実施例1の分離層を形成するための溶液の調製を行なった。実施例1には、反応性ポリシルセスキオキサンとしてSR−21(小西化学工業株式会社製)を用い、SR−21が20重量%になるように、溶剤であるPGMEAに溶解した。
実施例1〜4の積層体、並びに比較例1及び2の積層体を用いて耐熱性の評価を行なった。まず、積層体への処理として、DISCO社製バックグラインド装置にて厚さ50μmになるまで、各積層体のウエハ基板を薄化した。その後、各積層体を加熱炉中、380℃、3時間の条件で加熱処理した。
次に、耐熱性の評価を行なった実施例1〜4の積層体、並びに比較例1及び2の積層体を用いて積層体の反りの評価を行なった。
次に、実施例1〜4の積層体、並びに比較例1及び2の積層体を用いて基板と支持体との分離性の評価を行なった。
次に、TSVプロセスにおける積層体の評価を行なった。実施例5〜8として、異なる反応性ポリシルセスキオキサンを用いて分離層を形成した積層体を作製し、積層体の耐薬品性、耐熱性、反り、剥離性の評価を行なった。また、比較例3として、非反応性ポリシルセスキオキサンを用いて分離層を形成した積層体を作製し、比較例4として、フルオロカーボンからなる分離層を形成した積層体を作製し、実施例5〜8の評価と同じ評価を行なった。
実施例5〜8の積層体及び比較例3の積層体は、基板として半導体ウエハ基板(12インチシリコン)を用い、支持体として12インチのシリコンサポートプレートを用い、接着層を形成する接着剤としてTZNR(登録商標)−A4017(東京応化工業株式会社製)を用いた以外は、実施例1の手順と同じ手順に従って積層体を形成した。また、比較例4についても、実施例5の手順と同じ基板、接着剤を用い、12インチのガラス支持体を用いた以外は、比較例2の手順と同じ手順で積層体を作製した。実施例5〜8の積層体、並びに比較例3及び4の積層体の構成は、以下の表3に示す通りである。
実施例5〜8の積層体、並びに比較例3及び4の積層体を用いて耐熱性の評価を行なった。まず、積層体への処理として、DISCO社製バックグラインド装置にて厚さ50μmになるまで、各積層体のウエハ基板を薄化した。その後、各積層体を60℃のN−メチル−2−ピロリドン(NMP)中に10分間浸漬することによって耐薬品性の評価を行なった。
次に、耐薬品性を評価した実施例5〜8の積層体、並びに比較例3及び4の積層体を用いて耐熱性の評価を行なった。耐熱性の評価は、真空条件下、各積層体を220℃にて10分間加熱し、次いで、大気圧下、各積層体を260℃、60分間の条件で加熱することにより行なった。
次に、耐熱性の評価を行なった実施例5〜8の積層体、並びに比較例3及び4の積層体を用いて積層体の反りの評価を行なった。
次に、実施例5〜8の積層体、並びに比較例3及び4の積層体を用いて基板と支持体との分離性の評価を行なった。なお、実施例5〜8、及び比較例3の積層体には、実施例1の条件と同じ条件で分離層に光を照射し、分離性を評価した。また、比較例4の積層体には、比較例2の条件と同じ条件で、分離層に光を照射し、分離性を評価した。評価結果は、以下の表3に示す通りである。
2 サポートプレート(支持体)
3 接着層
4 分離層
10 積層体
Claims (19)
- 基板と、光を透過する支持体とを、接着層と、光を吸収することによって変質する分離層とを介して積層してなる積層体の製造方法であって、
上記支持体の上記基板に対向する側の面に、下記式(1)
に示す構造を有する反応性ポリシルセスキオキサンを塗布し、加熱することで上記反応性ポリシルセスキオキサンが有している、Si−O−R’結合を互いに縮合させることで重合させることによって上記分離層を形成する分離層形成工程を包含していることを特徴とする積層体の製造方法。 - 上記式(1)に示す、Rは、それぞれ独立してアリール基及びアルキル基からなる群から選択されることを特徴とする請求項1に記載の積層体の製造方法。
- 上記分離層形成工程では、上記式(1)に示す構造を有する反応性ポリシルセスキオキサンを100℃以上の温度で加熱することを特徴とする請求項1又は2に記載の積層体の製造方法。
- 上記支持体は、シリコンからなることを特徴とする請求項1〜3の何れか1項に記載の積層体の製造方法。
- 上記接着層は、ポリサルホン系樹脂を含んでいることを特徴とする請求項1〜4の何れか1項に記載の積層体の製造方法。
- 基板と、光を透過する支持体とを、接着層と、光を吸収することによって変質する分離層とを介して積層してなる積層体の製造方法であって、
上記支持体の上記基板に対向する側の面に、反応性ポリシルセスキオキサンを塗布し、加熱することで上記反応性ポリシルセスキオキサンを重合させることによって上記分離層を形成する分離層形成工程を包含しており、
上記接着層は、ポリサルホン系樹脂を含んでいることを特徴とする積層体の製造方法。 - 請求項1〜6の何れか1項に記載の製造方法によって積層体を製造する積層体製造工程と、
上記積層体製造工程の後、上記分離層に光を照射することにより、上記分離層を変質させ、上記支持体を上記積層体から分離する分離工程と、を包含していることを特徴とする基板の処理方法。 - 基板上又はシリコンからなる支持体上に、下記式(1)
に示す構造を有する反応性ポリシルセスキオキサンを塗布し、加熱して上記反応性ポリシルセスキオキサンが有している、Si−O−R’結合を互いに縮合させることにより重合させることで、光を吸収することによって変質する分離層を形成する分離層形成工程と、
上記基板と、上記支持体とを、接着層と上記分離層とを介して積層することによって積層体を製造する積層体製造工程と、
上記積層体製造工程の後、9μm以上、11μm以下の波長の光を照射することにより、上記分離層を変質させ、上記支持体を上記積層体から分離する分離工程と、を包含していることを特徴とする基板の処理方法。 - 上記式(1)に示す、Rは、それぞれ独立してアリール基及びアルキル基からなる群から選択されることを特徴とする請求項8に記載の基板の処理方法。
- 上記分離層形成工程では、上記式(1)に示す構造を有する反応性ポリシルセスキオキサンを100℃以上の温度で加熱することを特徴とする請求項8又は9に記載の基板の処理方法。
- 上記接着層は、ポリサルホン系樹脂を含んでいることを特徴とする請求項8〜10の何れか1項に記載の基板の処理方法。
- 上記積層体製造工程後、上記分離工程前に、上記積層体を260℃以上の温度で加熱することを特徴とする請求項7〜11の何れか1項に記載の基板の処理方法。
- 基板と、上記基板を支持する支持体とを、接着層と、光を吸収することによって変質する分離層とを介して積層してなる積層体であって、
上記分離層は、下記式(1)
(式中、Rは、それぞれ独立して有機基からなる群より選択され、R’は、それぞれ独立して水素及び炭素数1以上、10以下のアルキル基、からなる群より選択され、mは、1以上、100以下の整数である)
に示す構造を有する反応性ポリシルセスキオキサンが有している、Si−O−R’結合を互いに縮合させることで重合した重合体で形成されていることを特徴とする積層体。 - 上記式(1)に示す、Rは、それぞれ独立してアリール基及びアルキル基からなる群から選択されることを特徴とする請求項13に記載の積層体。
- 100℃以上の温度で加熱することで、上記式(1)に示す構造を有する反応性ポリシルセスキオキサンが有している、Si−O−R’結合を互いに縮合させていることを特徴とする請求項13又は14に記載の積層体。
- 上記支持体は、シリコンからなることを特徴とする請求項13〜15の何れか1項に記載の積層体。
- 上記接着層は、ポリサルホン系樹脂を含んでいることを特徴とする請求項13〜16の何れか1項に記載の積層体。
- 260℃以上の温度で加熱されることを特徴とする請求項13〜17の何れか1項に記載の積層体。
- 基板と、上記基板を支持する支持体とを、接着層と、光を吸収することによって変質する分離層とを介して積層してなる積層体であって、
上記分離層は、反応性ポリシルセスキオキサンの重合体で形成されており、
上記接着層は、ポリサルホン系樹脂を含んでいることを特徴とする積層体。
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