JP6477413B2 - レジスト材料及びパターン形成方法 - Google Patents
レジスト材料及びパターン形成方法 Download PDFInfo
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- 0 *c1ccccc1 Chemical compound *c1ccccc1 0.000 description 11
- CUFSZRYKIDQIFK-UHFFFAOYSA-N CC(C(CCC1CC(CCC2)CC2C1)OCC(C)=C)(C(F)(F)F)O Chemical compound CC(C(CCC1CC(CCC2)CC2C1)OCC(C)=C)(C(F)(F)F)O CUFSZRYKIDQIFK-UHFFFAOYSA-N 0.000 description 1
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- G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
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Description
1.下記式(a)で表される繰り返し単位と、酸不安定基を含む繰り返し単位とを含み、下記式(a')で表される繰り返し単位を含まないベース樹脂を含むレジスト材料。
2.前記酸不安定基を含む繰り返し単位が、下記式(b1)又は(b2)で表されるものである1のレジスト材料。
3.前記ベース樹脂が、更に、下記式(c1)〜(c3)から選ばれる少なくとも1種の繰り返し単位を含む1又は2のレジスト材料。
4.前記ベース樹脂が、式(c2)で表される繰り返し単位を含む3のレジスト材料。
5.化学増幅ポジ型レジスト材料である1〜4のいずれかのレジスト材料。
6.更に、有機溶剤、溶解阻止剤、酸発生剤、塩基性化合物及び/又は界面活性剤を含む1〜5のいずれかのレジスト材料。
7.1〜6のいずれかのレジスト材料を基板上に塗布する工程と、加熱処理後、高エネルギー線で露光する工程と、現像液を用いて現像する工程とを含むパターン形成方法。
8.前記高エネルギー線が、波長3〜15nmの極端紫外線である7のパターン形成方法。
9.前記高エネルギー線が、加速電圧1〜150kVの電子線である7のパターン形成方法。
10.レジスト下層の基板面をプラスに荷電した状態で露光を行う8又は9のパターン形成方法。
本発明のレジスト材料は、α位がフッ素化されたスルホン酸のルビジウム塩又はセシウム塩を含む繰り返し単位と、酸不安定基を含む繰り返し単位とを含むベース樹脂を含む。
本発明のパターン形成方法は、前記レジスト材料を基板上に塗布する工程と、加熱処理後、高エネルギー線で露光する工程と、現像液を用いて現像する工程とを含む。この場合、前記高エネルギー線で露光する工程において、波長3〜15nmのEUVやEB、特には加速電圧が1〜150kVの範囲のEBを光源として用いることができる。
[合成例1]金属塩モノマーの合成
重合性二重結合を含み、α位がフッ素化されたスルホン酸のベンジルトリメチルアンモニウム塩と、セシウムヒドロキシド又はルビジウムヒドロキシドとを混合し、水洗によってベンジルトリメチルアンモニウムヒドロキシドを除去することによって以下に示す金属塩モノマーを合成した。
各々のモノマーを組み合わせてTHF中で共重合反応を行い、メタノールに晶出し、更にヘキサンで洗浄を繰り返した後に単離、乾燥して、以下に示す組成のベース樹脂(ポリマー1〜5、比較ポリマー1)を得た。得られたベース樹脂の組成は1H−NMRにより、Mw及びMw/Mnは溶剤としてTHFを用いたGPCにより確認した。
[1]レジスト材料の調製
合成したベース樹脂を用い、界面活性剤として3M社製界面活性剤のFC−4430を100ppmの濃度で溶解させた溶剤に表1に示される組成で所用成分を溶解させた溶液を、0.2μmサイズのフィルターでろ過して表1記載のポジ型レジスト材料を調製した。
下記表中の各組成は次の通りである。
CyH(シクロヘキサノン)
GBL(γ−ブチロラクトン)
得られたポジ型レジスト材料を直径6インチφのヘキサメチルジシラザン(HMDS)ベーパープライム処理したSi基板上に、クリーントラックMark 5(東京エレクトロン(株)製)を用いてスピンコートし、ホットプレート上で110℃、60秒間プリベークして70nmのレジスト膜を作製した。これに、(株)日立製作所製HL-800Dを用いて、真空チャンバー内、HV電圧50kVでEB描画を行った。
描画後、直ちにクリーントラックMark 5(東京エレクトロン(株)製)を用いてホットプレート上で表2に記載の温度で60秒間PEBを行い、2.38質量%のTMAH水溶液で30秒間パドル現像を行い、ポジ型のパターンを得た。
得られたレジストパターンを次のように評価した。
100nmのラインアンドスペースを1:1で解像する露光量における100nmLSのLWRをSEMで測定した。
レジスト組成とEB露光における感度、LWRの結果を表2に示す。
Claims (10)
- 下記式(a)で表される繰り返し単位と、酸不安定基を含む繰り返し単位とを含み、下記式(a')で表される繰り返し単位を含まないベース樹脂を含むレジスト材料。
- 前記ベース樹脂が、更に、下記式(c1)〜(c3)から選ばれる少なくとも1種の繰り返し単位を含む請求項1又は2記載のレジスト材料。
- 前記ベース樹脂が、式(c2)で表される繰り返し単位を含む請求項3記載のレジスト材料。
- 化学増幅ポジ型レジスト材料である請求項1〜4のいずれか1項記載のレジスト材料。
- 更に、有機溶剤、溶解阻止剤、酸発生剤、塩基性化合物及び/又は界面活性剤を含む請求項1〜5のいずれか1項記載のレジスト材料。
- 請求項1〜6のいずれか1項記載のレジスト材料を基板上に塗布する工程と、加熱処理後、高エネルギー線で露光する工程と、現像液を用いて現像する工程とを含むパターン形成方法。
- 前記高エネルギー線が、波長3〜15nmの極端紫外線である請求項7記載のパターン形成方法。
- 前記高エネルギー線が、加速電圧1〜150kVの電子線である請求項7記載のパターン形成方法。
- レジスト下層の基板面をプラスに荷電した状態で露光を行う請求項8又は9記載のパターン形成方法。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2015208575A JP6477413B2 (ja) | 2015-10-23 | 2015-10-23 | レジスト材料及びパターン形成方法 |
US15/292,772 US10162262B2 (en) | 2015-10-23 | 2016-10-13 | Resist composition and patterning process |
TW105133796A TWI624724B (zh) | 2015-10-23 | 2016-10-20 | 光阻材料及圖案形成方法 |
KR1020160138153A KR102155401B1 (ko) | 2015-10-23 | 2016-10-24 | 레지스트 재료 및 패턴 형성 방법 |
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