Elucidation of local ionization in ultra-thin polymer films and its application

• Project/Area Number: 24561037
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Nuclear engineering
• Research Institution: Hokkaido University
• Principal Investigator: OKAMOTO Kazumasa 北海道大学, 工学(系)研究科(研究院), 助教 (10437353)
• Project Period (FY): 2012-04-01 – 2015-03-31
• Project Status: Completed (Fiscal Year 2014)
• Budget Amount: ¥4,940,000 (Direct Cost: ¥3,800,000、Indirect Cost: ¥1,140,000); Fiscal Year 2014: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000); Fiscal Year 2013: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000); Fiscal Year 2012: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000)
• Keywords: レジスト / 放射線化学 / 極端紫外線（ＥＵＶ） / 自由電子レーザー / パルスラジオリシス / 電子線 / ラジカルカチオン / 脱プロトン反応 / フッ素系高分子 / 放射線、X線、粒子線 / 放射線、Ｘ線、粒子線

Outline of Final Research Achievements

Dynamics of charges caused by the ionization in ultra-thin resist films and the following radiation chemistry have been investigated. Dependence of the acid yield in the resist on the local energy deposition was clarified by the irradiations of extreme-ultraviolet (EUV) free-electron laser and simulations. The reaction dynamics in the resist was also studied by using pulse radiolysis. Moreover, cause of decrease of the acid yield in fluorinated polymers with high EUV absorptivity was shown.

Research Products

• [Journal Article] Pulse Radiolysis Study of Polystyrene-based Polymers with Added Photoacid Generators: Reaction Mechanism of Extreme-ultraviolet and Electron-beam Chemically Amplified Resist (2015)
  • Author(s): Kazumasa Okamoto, Hiroki Yamamoto, Takahiro Kozawa, Ryoko Fujiyoshi, Kikuo Umegaki
  • Journal Title: Jpn. J. Appl. Phys. Volume: 54 Issue: 2 Pages: 026501-026501
  • DOI: 10.7567/jjap.54.026501
  • NAID: 210000144787
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Radiation Chemistry of Fluorinated Polymers for Extreme Ultraviolet Resist (2015)
  • Author(s): Naoya Nomura, Kazumasa Okamoto, Hiroki Yamamoto, Takahiro Kozawa, Ryoko Fujiyoshi, Kikuo Umegaki
  • Journal Title: Jpn. J. Appl. Phys. Volume: 印刷中
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Fluidity dependence of deprotonation kinetics of chemically amplified resist (2014)
  • Author(s): Kazumasa Okamoto , Takuya Ishida , Hiroki Yamamoto , Takahiro Kozawa , Ryoko Fujiyoshi, and Kikuo Umegaki
  • Journal Title: Proc. SPIE Volume: 9051 Pages: 90511T-90511T
  • DOI: 10.1117/12.2046057
  • Peer Reviewed
• [Journal Article] Deprotonation mechanism of ionized poly(4-hydroxystyrene) (2014)
  • Author(s): Toshihiko Susa, Kazumasa Okamoto , Takuya Ishida , Hiroki Yamamoto , Takahiro Kozawa , Ryoko Fujiyoshi, and Kikuo Umegaki
  • Journal Title: Proc. SPIE Volume: 9051 Pages: 90511O-90511O
  • DOI: 10.1117/12.2045881
  • Peer Reviewed
• [Journal Article] Deprotonation of poly(4-hydroxystyrene) intermediates: pulse radiolysis study of EUV and electron beam resist (2013)
  • Author(s): Kazumasa Okamoto, Tyo Matsuda, Hiroki Yamamoto, Takahiro Kozawa, Seiichi Tagawa, Ryoko Fujiyoshi, and Takashi Sumiyoshi
  • Journal Title: Jpn. J. Appl. Phys. Volume: 52 Issue: 6S Pages: 06GC04-06GC04
  • DOI: 10.7567/jjap.52.06gc04
  • Peer Reviewed
• [Journal Article] Deprotonation of poly(4-hydroxystyrene) intermediates: Pulse radiolysis study of EUV and electron beam resist (2013)
  • Author(s): Kazumasa Okamoto, Ryo Matsuda, Hiroki Yamamoto, Takahiro Kozawa, Seiichi Tagawa, Ryoko Fujiyoshi, and Takashi Sumiyoshi
  • Journal Title: Jpn. J. Appl. Phys. Volume: 52
  • Peer Reviewed
• [Journal Article] Effect of Ultrahigh-Density Ionization of Resist Films on Sensitivity Using Extreme-Ultraviolet Free-Electron Laser (2012)
  • Author(s): K. Okamoto, T. Kozawa, K. Oikawa, T. Hatsui, M. Nagasono, T. Kameshima, T. Togashi, K. Tono, M. Yabashi, H. Kimura, Y. Senba, H. Ohashi, R. Fujiyoshi, and T. Sumiyoshi
  • Journal Title: Appl. Phys. Express Volume: 5巻 Issue: 9 Pages: 96701-96701
  • DOI: 10.1143/apex.5.096701
  • NAID: 40019425422
  • Peer Reviewed
• [Presentation] EUVレジストに向けたフッ素ポリマーの放射線化学反応の解明 (2015)
  • Author(s): 野村直矢、岡本一将、藤吉亮子、梅垣菊男、山本洋揮、古澤孝弘
  • Organizer: 日本原子力学会 ２０１５年春の年会
  • Place of Presentation: 茨城大学 日立キャンパス
  • Year and Date: 2015-03-20 – 2015-03-22
• [Presentation] 光酸発生剤を添加した芳香族系レジスト樹脂のパルスラジオリシス (2015)
  • Author(s): 岡本一将、石田拓也、藤吉亮子、梅垣菊男、山本洋揮、古澤孝弘
  • Organizer: 日本原子力学会 ２０１５年春の年会
  • Place of Presentation: 茨城大学 日立キャンパス
  • Year and Date: 2015-03-20 – 2015-03-22
• [Presentation] Radiation Chemistry of Fluorinated Polymers for Extreme Ultraviolet Resist (2014)
  • Author(s): Naoya Nomura, Kazumasa Okamoto, Hiroki Yamamoto, Takahiro Kozawa, Ryoko Fujiyoshi, Kikuo Umegaki
  • Organizer: MNC2014
  • Place of Presentation: Hilton Fukuoka Sea Hawk, Fukuoka, Japan
  • Year and Date: 2014-11-04 – 2014-11-07
• [Presentation] Pulse Radiolysis Study of EUV Resist Polymers with Photoacid Generator (2014)
  • Author(s): Kazumasa Okamoto, Hiroki Yamamoto, Takahiro Kozawa, Ryoko Fujiyoshi, Kikuo Umegaki
  • Organizer: APSRC2014
  • Place of Presentation: Univ. Tokyo, Tokyo, Japan
  • Year and Date: 2014-09-08 – 2014-09-11
• [Presentation] Radiation Chemistry of Fluorinated Polymers for Extreme-ultraviolet Resist (2014)
  • Author(s): Naoya Nomura, Kazumasa Okamoto, Hiroki Yamamoto, Takahiro Kozawa, Ryoko Fujiyoshi, Kikuo Umegaki
  • Organizer: APSRC2014
  • Place of Presentation: Univ. Tokyo, Tokyo, Japan
  • Year and Date: 2014-09-08 – 2014-09-11
• [Presentation] Acid Generation Mechanism in Solid Poly(4-hydroxystyrene) upon Exposeure to Electron Beam (2013)
  • Author(s): H. Yamamoto, K. Okamoto, and T. Kozawa
  • Organizer: MNC2013
  • Place of Presentation: Royton Sapporo, Sapporo, Japan
• [Presentation] Viscosity Effect on Deprotonation Dynamics of Poly(4-hydroxystyrene) (2013)
  • Author(s): T. Ishida, K. Okamoto, H. Yamamoto, T. Kozawa, R. Fujiyoshi, and T. Sumiyoshi
  • Organizer: MNC2013
  • Place of Presentation: Royton Sapporo, Sapporo, Japan
• [Presentation] Simulation of Kinetics in High-density Ionization Extra-ultraviolet (EUV) Resist Process (2013)
  • Author(s): K. Nishono, K. Okamoto, H. Yamamoto, T. Kozawa, R. Fujiyoshi, and T. Sumiyoshi
  • Organizer: MNC2013
  • Place of Presentation: Royton Sapporo, Sapporo, Japan
• [Presentation] Pulse Radiolysis Study of Polystyrene-based Polymers with Adding Photoacid Generators (PAGs): Molecular Dynamics of Extreme-ultraviolet and Electron Beam Resist (2013)
  • Author(s): K. Okamoto, K. Tominaga, T. Hori, H. Yamamoto, T. Kozawa, R. Fujiyoshi, and T. Sumiyoshi
  • Organizer: MNC2013
  • Place of Presentation: Royton Sapporo, Sapporo, Japan
• [Presentation] ポリ(4-ヒドロキシスチレン)のラジカルカチオンの脱プロトン反応 (2013)
  • Author(s): 須佐俊彦、岡本一将、石田拓也、山本洋揮、古澤孝弘、藤吉亮子、住吉 孝
  • Organizer: 第56回放射線化学討論会
  • Place of Presentation: 広島大学（東広島市）
• [Presentation] 化学増幅レジストモデルのパルスラジオリシス (2013)
  • Author(s): 岡本一将、山本洋揮、古澤孝弘、藤吉亮子、住吉 孝
  • Organizer: 第56回放射線化学討論会
  • Place of Presentation: 広島大学（東広島市）
• [Presentation] ポリ(4-ヒドロキシスチレン)(PHS)濃厚溶液の脱プロトン反応の粘度効果 (2013)
  • Author(s): 石田拓也、岡本一将、山本洋揮、古澤孝弘、藤吉亮子、住吉 孝
  • Organizer: 第56回放射線化学討論会
  • Place of Presentation: 広島大学（東広島市）
• [Presentation] ポリ（4-ヒドロキシスチレン）（PHS）濃厚溶液の脱プロトン反応の粘度効果
  • Author(s): 石田拓也、岡本一将、山本洋揮、古澤孝弘、藤吉亮子、梅垣菊男
  • Organizer: 日本原子力学会 ２０１４年春の年会
  • Place of Presentation: 東京都市大学 世田谷キャンパス(世田谷区)
• [Presentation] パルスラジオリシスによるポリヒドロキシスチレン固体中での 脱プロトン化反応に関する研究
  • Author(s): 山本洋揮、岡本一将、古澤孝弘
  • Organizer: 第61 回応用物理学会春季学術講演会
  • Place of Presentation: 青山大学相模原キャンパス（相模原市）
• [Presentation] Fluidity dependence of deprotonation kinetics of chemically amplified resist
  • Author(s): Kazumasa Okamoto , Takuya Ishida , Hiroki Yamamoto , Takahiro Kozawa , Ryoko Fujiyoshi , Kikuo Umegaki
  • Organizer: SPIE Advanced Lithography 2014
  • Place of Presentation: San Jose Marriott and San Jose Convention Center San Jose, California, United States
• [Presentation] Deprotonation mechanism of ionized poly(4-hydroxystyrene)
  • Author(s): Toshihiko Susa, Kazumasa Okamoto , Takuya Ishida , Hiroki Yamamoto , Takahiro Kozawa , Ryoko Fujiyoshi , Kikuo Umegaki
  • Organizer: SPIE Advanced Lithography 2014
  • Place of Presentation: San Jose Marriott and San Jose Convention Center San Jose, California, United States
• [Presentation] 高密度イオン化状態におけるＥＵＶリソグラフィプロセスのシミュレーション
  • Author(s): 西野圭一郎、岡本一将、古澤孝弘、藤吉亮子、梅垣菊男
  • Organizer: 日本原子力学会北海道支部第３０回研究発表会
  • Place of Presentation: 北海道大学（札幌市）
• [Presentation] レジストモデル高分子のパルスラジオリシス
  • Author(s): 岡本一将，古澤孝弘，田川精一, 藤吉亮子, 住吉 孝
  • Organizer: 日本原子力学会「2012年秋の大会」
  • Place of Presentation: 広島大学（東広島市）
• [Presentation] Deprotonation of Poly(4-hydroxystyrene)Intermediates: Pulse Radiolysis Study of EUV and Electron Beam Resist
  • Author(s): K. Okamoto, R. Matsuda, T. Kozawa, S. Tagawa, R. Fujiyoshi, and T. Sumiyoshi
  • Organizer: ＭＮＣ2012
  • Place of Presentation: Kobe Meriken Park Oriental Hotel, Kobe (Japan)
• [Presentation] 化学増幅型レジストモデル溶液のパルスラジオリシス及びパルスラジオリシス-レーザーフラッシュフォトリシス
  • Author(s): 井上浩彰, 岡本一将, 藤吉亮子, 住吉孝
  • Organizer: 日本化学会第93春季年会(2013)
  • Place of Presentation: 立命館大学（草津市）
• [Remarks] 北大院工 量子ビーム応用医工学研究室
  • URL: http://labs.eng.hokudai.ac.jp/labo/qsre/QSciEngjp/
• [Remarks] 量子ビーム応用医工学研究室
  • URL: http://labs.eng.hokudai.ac.jp/labo/qsre/QSciEngjp/
• [Remarks] 量子放射線科学研究室
  • URL: http://www.eng.hokudai.ac.jp/labo/qsre/QSciEngjp/theme.html