Elucidation of deprotonation induced mechanism in nano-and microfabrication process using ionizing radiations and its applications

• Project/Area Number: 19K05330
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Review Section: Basic Section 31010:Nuclear engineering-related
• Research Institution: Osaka University
• Principal Investigator: Okamoto Kazumasa 大阪大学, 産業科学研究所, 助教 (10437353)
• Project Period (FY): 2019-04-01 – 2022-03-31
• Project Status: Completed (Fiscal Year 2021)
• Budget Amount: ¥4,030,000 (Direct Cost: ¥3,100,000、Indirect Cost: ¥930,000); Fiscal Year 2021: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000); Fiscal Year 2020: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000); Fiscal Year 2019: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
• Keywords: レジスト / 放射線化学 / リソグラフィ / 電子線 / 極端紫外線(EUV) / 化学増幅型レジスト / 半導体微細化 / 酸生成促進剤 / ジフェニルスルホン / 極端紫外線（EUV） / 脱プロトン反応 / レジスト材料 / EUVリソグラフィ / 極端紫外線 / パルスラジオリシス / 極端紫外線（ＥＵＶ） / 極端紫外線（EUV）・Ｘ線

Outline of Research at the Start

半導体微細加工材料であるレジストの高感度化（増感）、高解像度化や解像誤差（ラフネス）の低減を同時に達成することが最も重要な課題であるが、その解決策はいまだ明らかにされていない。本研究では、電離放射線によりイオン化したレジストの脱プロトン反応を促進する酸生成促進剤 (Acid-generating promoter)のメカニズムを明らかにし、新たな電離放射線露光用レジストの解像性能向上を実現する手法の開拓を行う。

Outline of Final Research Achievements

Ionizing radiation such as extreme ultraviolet (EUV) light and electron beam has been used in lithography process used in semiconductor manufacturing. Therefore development of the resist materials with higher performance has been desired. Acid-generating promoters (AGPs) can improve the sensitivity of the chemically amplified resist upon irradiation of ionizing radiation. Research on the effectiveness and mechanism of AGPs for enhancement of the deprotonation efficiency were carried out. The details of the radiation-induced reaction of resist constituent molecules were also clarified.

Academic Significance and Societal Importance of the Research Achievements

現在半導体製造で使われているレジスト材料の性能の向上のために、現行のレジストに添加するだけで脱プロトン反応性等の向上効果のある酸生成促進剤の有効性を示すとともに、その機能の解明を行った。酸生成促進剤の化学構造が、電子または正電荷を受容した後も室温下でも安定に存在でき、酸生成の促進に寄与できることが明らかになった。また、本成果により今後の半導体製造の生産性の向上に繋がることが期待される。

Research Products

• [Journal Article] Study on deprotonation from radiation-induced ionized acrylate polymers including acidgeneration promoters for improving chemically amplified resists (2022)
  • Author(s): Kazumasa Okamoto, Akihiro Konda, Yuki Ishimaru, Takahiro Kozawa, Yasunobu Nakagawa, Masamichi Nishimura
  • Journal Title: Japanese Journal of Applied Physics Volume: － Issue: 6 Pages: 066505-066505
  • DOI: 10.35848/1347-4065/ac67ba
  • Peer Reviewed
• [Journal Article] Dependence of dose rate on the sensitivity of the resist under ultra-high flux extreme ultraviolet (EUV) pulse irradiation (2021)
  • Author(s): Okamoto Kazumasa, Kawai Shunpei, Ikari Yuta, Hori Shigeo, Konda Akihiro, Ueno Koki, Arai Yohei, Ishino Masahiko, Thanhhung Dinh, Nishikino Masaharu, Kon Akira, Owada Shigeki, Inubushi Yuichi, Kinoshita Hiroo, Kozawa Takahiro
  • Journal Title: Applied Physics Express Volume: 14 Issue: 6 Pages: 066502-066502
  • DOI: 10.35848/1882-0786/abfca3
  • Peer Reviewed / Open Access
• [Journal Article] Estimation of electron affinity of photoacid generators: density functional theory calculations using static and dynamic models (2021)
  • Author(s): Kazumasa Okamoto, Takahiro Kozawa
  • Journal Title: Japanese Journal of Applied Physics Volume: 60 Issue: SC Pages: SCCC03-SCCC03
  • DOI: 10.35848/1347-4065/abf469
  • Peer Reviewed
• [Journal Article] Formation of intramolecular dimer radical ions of diphenyl sulfones (2020)
  • Author(s): Kazumasa Okamoto, Shunpei Kawai, Takahiro Kozawa
  • Journal Title: Scientific Reports Volume: 10 Issue: 1 Pages: 19823-19823
  • DOI: 10.1038/s41598-020-76907-4
  • Peer Reviewed / Open Access
• [Journal Article] Sensitivity enhancement of chemically amplified EUV resist by adding diphenyl sulfone derivatives (2020)
  • Author(s): Okamoto Kazumasa、Kawai Shunpei、Kozawa Takahiro
  • Journal Title: Proc. SPIE, Advances in Patterning Materials and Processes XXXVII Volume: 11326 Pages: 12-12
  • DOI: 10.1117/12.2551865
  • Peer Reviewed
• [Presentation] ポリスチレンの正電荷非局在性への パルスラジオリシスおよびシミュレーション によるアプローチ (2022)
  • Author(s): 岡本一将、山本洋揮、古澤孝弘
  • Organizer: 原子力学会２０２２年春の年会
• [Presentation] Estimation of electron affinity of photoacid generators: density functional theory calculations using static and dynamic models (2020)
  • Author(s): Kazumasa Okamoto, Takahiro Kozawa
  • Organizer: MNC 2020, 33rd International Microprocesses and Nanotechnology Conference
  • Int'l Joint Research
• [Presentation] Sensitivity enhancement of chemically amplified EUV resist by adding dipheyl sulfone derivatives (2020)
  • Author(s): Kazumasa Okamoto, Shunpei Kawai, Takahiro Kozawa
  • Organizer: SPIE Advanced Lithography 2020
  • Int'l Joint Research
• [Presentation] ジフェニルスルホン酸生成促進剤による化学増幅型レジストの感度向上 (2019)
  • Author(s): 河合俊平、大沼正人、岡本一将、古澤孝弘
  • Organizer: 第80回応用物理学会秋季学術講演会
• [Remarks] 大阪大学産業科学研究所古澤研究室
  • URL: https://www.sanken.osaka-u.ac.jp/labs/bms/index.html
• [Remarks] 大阪大学産業科学研究所 量子ビーム物質科学研究分野 ホームページ
  • URL: https://www.sanken.osaka-u.ac.jp/labs/bms/