JP7259220B2 - 感光性樹脂組成物、配線層及び半導体装置 - Google Patents
感光性樹脂組成物、配線層及び半導体装置 Download PDFInfo
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- JP7259220B2 JP7259220B2 JP2018112843A JP2018112843A JP7259220B2 JP 7259220 B2 JP7259220 B2 JP 7259220B2 JP 2018112843 A JP2018112843 A JP 2018112843A JP 2018112843 A JP2018112843 A JP 2018112843A JP 7259220 B2 JP7259220 B2 JP 7259220B2
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- diamine
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- RTHVZRHBNXZKKB-UHFFFAOYSA-N pyrazine-2,3,5,6-tetracarboxylic acid Chemical compound OC(=O)C1=NC(C(O)=O)=C(C(O)=O)N=C1C(O)=O RTHVZRHBNXZKKB-UHFFFAOYSA-N 0.000 description 1
- YKWDNEXDHDSTCU-UHFFFAOYSA-N pyrrolidine-2,3,4,5-tetracarboxylic acid Chemical compound OC(=O)C1NC(C(O)=O)C(C(O)=O)C1C(O)=O YKWDNEXDHDSTCU-UHFFFAOYSA-N 0.000 description 1
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Images
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- Materials For Photolithography (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Description
[式中、Q1及びQ6は、各々独立に、炭素数1~5のアルキレン基、又は、置換基を有してもよいフェニレン基を示し、Q2、Q3、Q4及びQ5は、各々独立に、炭素数1~5のアルキル基、フェニル基又はフェノキシ基を示し、bは1~5の整数を示す。]
検出器:LV4000 UV Detector(株式会社日立製作所製、商品名)
ポンプ:L6000 Pump(株式会社日立製作所製、商品名)
カラム:Gelpack GL-S300MDT-5(計2本)(日立化成株式会社製、商品名)
溶離液:THF/DMF=1/1(容積比)+LiBr(0.03mol/L)+H3PO4(0.06mol/L)
流量:1mL/分
[式中、R1は、芳香環を含む2価の有機基、又は、直鎖、分岐若しくは環状の脂肪族炭化水素を含む2価の有機基を示す。]
[式中、R51及びR52は、それぞれ独立に、水素原子、炭素数1~7のアルキル基、又は、芳香族系炭化水素基を含む有機基を示し、R53は、炭素数1~7のアルキル基、又は、芳香族系炭化水素基を含む有機基を示し、R54及びR55は、芳香族系炭化水素基を含む有機基を示す。]
(PI-1)
温度計、攪拌機、冷却管及び窒素流入管を装着した300mLフラスコ中に1,12-ドデカメチレンジアミン(別名:1,12-ジアミノドデカン)9.0g(0.045mol)、1,3-ビス(3-アミノプロピル)テトラメチルジシロキサン(別名:1,1,3,3-テトラメチル-1,3-ビス(3-アミノプロピル)ジシロキサン)2.5g(0.010mol)、2,2-ビス(4-アミノフェノキシフェニル)プロパン16.4g(0.040mol)、及び、N-メチル-2-ピロリドン100gを加えた後に撹拌して各成分を溶解させることにより溶液を得た。その後、この溶液にデカメチレンビストリメリテート二無水物(1,10-(デカメチレン)ビス(トリメリテート無水物))52.2g(0.10mol)を少量ずつ添加した。室温で1時間反応させた後、窒素ガスを吹き込みながら180℃で2時間加熱することにより、ポリイミド(PI-1)の溶液を得た。得られたポリイミドの重量平均分子量MwをGPCで測定したところ、ポリスチレン換算で55000であった。また、得られたポリイミドのTgは120℃であった。
温度計、攪拌機、冷却管及び窒素流入管を装着した300mLフラスコ中に1,12-ドデカメチレンジアミン15.0g(0.075mol)、1,3-ビス(3-アミノプロピル)テトラメチルジシロキサン(別名:1,1,3,3-テトラメチル-1,3-ビス(3-アミノプロピル)ジシロキサン)5.0g(0.020mol)、及び、N-メチル-2-ピロリドン100gを加えた後に撹拌して各成分を溶解させて溶液を得た。その後、この溶液に4,4’-(4,4’-イソプロピリデンジフェノキシ)ビス(フタル酸二無水物)41.6g(0.080mol)と、デカメチレンビストリメリテート二無水物(1,10-(デカメチレン)ビス(トリメリテート無水物))10.4g(0.020mol)とを少量ずつ添加した。室温で1時間反応させた後、窒素ガスを吹き込みながら180℃で2時間加熱することにより、ポリイミド(PI-2)の溶液を得た。得られたポリイミドの重量平均分子量MwをGPCで測定したところ、ポリスチレン換算で45000であった。また、得られたポリイミドのTgは80℃であった。
温度計、攪拌機、冷却管及び窒素流入管を装着した300mLフラスコ中に1,12-ドデカメチレンジアミン15.0g(0.075mol)、1,3-ビス(3-アミノプロピル)テトラメチルジシロキサン(別名:1,1,3,3-テトラメチル-1,3-ビス(3-アミノプロピル)ジシロキサン)5.0g(0.020mol)、及び、N-メチル-2-ピロリドン100gを加えた後に撹拌して各成分を溶解させて溶液を得た。その後、この溶液に4,4’-(4,4’-イソプロピリデンジフェノキシ)ビス(フタル酸二無水物)52.0g(0.10mol)を少量ずつ添加した。室温で1時間反応させた後、窒素ガスを吹き込みながら180℃で2時間加熱することにより、ポリイミド(PI-3)の溶液を得た。得られたポリイミドの重量平均分子量MwをGPCで測定したところ、ポリスチレン換算で42000であった。また、得られたポリイミドのTgは100℃であった。
温度計、攪拌機、冷却管及び窒素流入管を装着した300mLフラスコ中に1,6-ヘキサメチレンジアミン5.22g(0.045mol)、1,3-ビス(3-アミノプロピル)テトラメチルジシロキサン(別名:1,1,3,3-テトラメチル-1,3-ビス(3-アミノプロピル)ジシロキサン)2.5g(0.010mol)、2,2-ビス(4-アミノフェノキシフェニル)プロパン16.4g(0.040mol)、及び、N-メチル-2-ピロリドン100gを加えた後に撹拌して各成分を溶解させて溶液を得た。その後、この溶液にデカメチレンビストリメリテート二無水物(1,10-(デカメチレン)ビス(トリメリテート無水物))52.2g(0.10mol)を少量ずつ添加した。室温で1時間反応させた後、窒素ガスを吹き込みながら180℃で2時間加熱することにより、ポリイミド(PI-4)の溶液を得た。得られたポリイミドの重量平均分子量MwをGPCで測定したところ、ポリスチレン換算で58000であった。また、得られたポリイミドのTgは150℃であった。
温度計、攪拌機、冷却管及び窒素流入管を装着した300mLフラスコ中にポリオキシプロピレンジアミン(三井化学ファイン株式会社製、商品名「D-400」)18.0g(0.045mol)、1,3-ビス(3-アミノプロピル)テトラメチルジシロキサン(別名:1,1,3,3-テトラメチル-1,3-ビス(3-アミノプロピル)ジシロキサン)2.5g(0.010mol)、2,2-ビス(4-アミノフェノキシフェニル)プロパン16.4g(0.040mol)、及び、N-メチル-2-ピロリドン100gを加えた後に撹拌して各成分を溶解させて溶液を得た。その後、この溶液に4,4’-(4,4’-イソプロピリデンジフェノキシ)ビス(フタル酸二無水物)52.0g(0.10mol)を少量ずつ添加した。室温で1時間反応させた後、窒素ガスを吹き込みながら180℃で2時間加熱することにより、ポリイミド(PI-5)の溶液を得た。得られたポリイミドの重量平均分子量MwをGPCで測定したところ、ポリスチレン換算で45000であった。また、得られたポリイミドのTgは80℃であった。
(実施例1)
ポリイミドPI-1(100質量部、固形分)に対し、トリシクロデカンジメタノールジアクリレート(20質量部)、エタノン,1-[9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル]-,1-(O-アセチルオキシム)(BASF社製、商品名「I-OXE02」、5質量部)、及び、シクロペンタノン(100質量部)を配合して感光性樹脂組成物を得た。
ポリイミドとしてPI-2を用いたこと以外は実施例1と同様にして感光性樹脂組成物を得た。
ポリイミドとしてPI-3を用いたこと以外は実施例1と同様にして感光性樹脂組成物を得た。
ポリイミドとしてPI-4を用いたこと以外は実施例1と同様にして感光性樹脂組成物を得た。
ポリイミドとしてPI-5を用いたこと以外は実施例1と同様にして感光性樹脂組成物を得た。
(電気特性(誘電正接))
上述の感光性樹脂組成物を高精度平行露光機(株式会社オーク製作所製、商品名「EXM-1172-B-∞」)で200mJ/cm2の条件で露光処理した後、ホットプレート上で100℃、2分の条件で加熱し、さらに、オーブンで220℃、1時間の条件で加熱して熱硬化させて厚さ300μmの感光性樹脂組成物の硬化物を得た。硬化物を長さ60mm、幅2mmに切断した後に30℃で6時間真空乾燥して得られた試験片を作製した。誘電正接は、10GHzにおいて得られる共振周波数と無負荷Q値とから算出した。測定は、キーサイトテクノロジー社製のベクトル型ネットワークアナライザE8364Bと、株式会社関東電子応用開発製のCP531(10GHz共振器)及びCPMA-V2(プログラム)とを用いて温度25℃で実施した。
上述の感光性樹脂組成物からなる厚さ2μmの層をシリコンウェハ上に形成した後、高精度平行露光機(株式会社オーク製作所製、商品名「EXM-1172-B-∞」)を用いて200mJ/cm2の条件で露光処理した後、100℃、2分の条件で加熱し、さらに、220℃、1時間の条件で加熱硬化して第1の絶縁層を形成した。その後、上述の感光性樹脂組成物からなる厚さ2μmの層を更に形成した後、ウシオ電機株式会社製の投影露光機「UX-74101SC」(商品名)を用いて、フォーカス±0μm、露光量1000mJ/cm2の条件で露光した。その後、現像液としてシクロペンタノンを用いて25℃で20秒間の条件でパドル現像を実施し、5μm径及び10μm径のビア(開口)を有する第2の絶縁層を第1の絶縁層上に形成した。顕微鏡によって5μm径及び10μm径のビアの解像性を評価した。ビアが良好に形成された最小の径を評価した。
絶縁信頼性の評価のため、図10に示す測定評価用試料50を以下のようにして作製した。まず、旭有機材株式会社製のクレゾールノボラック樹脂「TR-4020G」(商品名、100質量部)に対し、1,3,4,6-テトラキス(メトキシメチル)グリコールウリル(30質量部)、トリメチロールプロパントリグリシジルエーテル(40質量部)、トリアリールスルホニウム塩(サンアプロ株式会社、商品名「CPI-310B」、8質量部)、及び、メチルエチルケトン(100質量部)を配合して絶縁材料を得た。得られた絶縁材料を帝人デュポンフィルム株式会社製のポリエチレンテレフタレートフィルム「A-53」(商品名)に塗布した後、90℃のオーブンで10分間乾燥して厚さ3μmの感光性材料52を得た。
実施例1の誘電正接は0.005、解像性は10μm、絶縁信頼性は「A」であった。実施例2の誘電正接は0.008、解像性は5μm、絶縁信頼性は「A」であった。実施例3の誘電正接は0.008、解像性は10μm、絶縁信頼性は「A」であった。実施例4の誘電正接は0.01、解像性は5μm、絶縁信頼性は「A」であった。比較例1の誘電正接は0.03、解像性は5μm、絶縁信頼性は「B」であった。
Claims (8)
- 開口を有する絶縁部と、前記開口の内部に配置された配線と、を備える配線層における前記絶縁部を形成するための感光性樹脂組成物であって、
テトラカルボン酸二無水物とジアミンとの反応物であるポリイミド(A)と、2つ以上の炭素-炭素二重結合を有する化合物(B)と、を含有し、
前記ジアミンが、1,6-ヘキサメチレンジアミン、1,7-ヘプタメチレンジアミン、1,8-オクタメチレンジアミン、1,9-ノナメチレンジアミン、2-メチル-1,8-オクタメチレンジアミン、1,10-デカメチレンジアミン、1,11-ウンデカメチレンジアミン、1,12-ドデカメチレンジアミン、1,13-トリデカメチレンジアミン、1,16-ヘキサデカメチレンジアミン、1,18-オクタデカメチレンジアミン、2,2,4-トリメチルヘキサメチレンジアミン、及び、2,4,4-トリメチルヘキサメチレンジアミンからなる群より選ばれる少なくとも一種を10~80mol%含み、
前記(B)成分の含有量が、前記(A)成分100質量部に対して5~70質量部である、感光性樹脂組成物(但し、(I)脂環式テトラカルボン酸二無水物、環状の脂肪族ジアミン、及び鎖状の脂肪族ジアミンを縮合した構造を有するポリイミド100質量部に対し(II)3官能以上の多官能光重合性モノマー20~200質量部、(III)光重合開始剤0.02~40質量部を含むことを特徴とする感光性樹脂組成物を除く)。 - 前記ジアミンが1,12-ドデカメチレンジアミンを含む、請求項1に記載の感光性樹脂組成物。
- 前記ジアミンが1,6-ヘキサメチレンジアミンを含む、請求項1又は2に記載の感光性樹脂組成物。
- 前記ジアミンが5~50mol%のシロキサンジアミンを更に含む、請求項1~3のいずれか一項に記載の感光性樹脂組成物。
- 前記ポリイミドのガラス転移温度が60~220℃である、請求項1~4のいずれか一項に記載の感光性樹脂組成物。
- 光重合開始剤を更に含有する、請求項1~5のいずれか一項に記載の感光性樹脂組成物。
- 開口を有する絶縁部と、前記開口の内部に配置された配線と、を備え、
前記絶縁部が、請求項1~6のいずれか一項に記載の感光性樹脂組成物又はその硬化物を含む、配線層。 - 請求項7に記載の配線層を備える、半導体装置。
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| WO2018038002A1 (ja) | 2016-08-25 | 2018-03-01 | 富士フイルム株式会社 | 積層体の製造方法および電子デバイスの製造方法 |
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| WO2018038002A1 (ja) | 2016-08-25 | 2018-03-01 | 富士フイルム株式会社 | 積層体の製造方法および電子デバイスの製造方法 |
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