ACS Publications. Most Trusted. Most Cited. Most Read
Effect of Ambient Conditions on Radiation-Induced Chemistries of a Nanocluster Organotin Photoresist for Next-Generation EUV Nanolithography
My Activity

Figure 1Loading Img
    Article

    Effect of Ambient Conditions on Radiation-Induced Chemistries of a Nanocluster Organotin Photoresist for Next-Generation EUV Nanolithography
    Click to copy article linkArticle link copied!

    • J. Trey Diulus
      J. Trey Diulus
      School of Chemical, Biological and Environmental Engineering, Oregon State University, Corvallis, Oregon 97331, United States
    • Ryan T. Frederick
      Ryan T. Frederick
      School of Chemical, Biological and Environmental Engineering, Oregon State University, Corvallis, Oregon 97331, United States
    • Danielle C. Hutchison
      Danielle C. Hutchison
      Department of Chemistry, Oregon State University, Corvallis, Oregon 97331, United States
    • Igor Lyubinetsky
      Igor Lyubinetsky
      School of Chemical, Biological and Environmental Engineering, Oregon State University, Corvallis, Oregon 97331, United States
    • Rafik Addou
      Rafik Addou
      School of Chemical, Biological and Environmental Engineering, Oregon State University, Corvallis, Oregon 97331, United States
      More by Rafik Addou
    • May Nyman
      May Nyman
      Department of Chemistry, Oregon State University, Corvallis, Oregon 97331, United States
      More by May Nyman
    • Gregory S. Herman*
      Gregory S. Herman
      School of Chemical, Biological and Environmental Engineering, Oregon State University, Corvallis, Oregon 97331, United States
      Department of Chemistry, Oregon State University, Corvallis, Oregon 97331, United States
      Department of Physics, Oregon State University, Corvallis, Oregon 97331, United States
      *Email: [email protected]
    Other Access OptionsSupporting Information (1)

    ACS Applied Nano Materials

    Cite this: ACS Appl. Nano Mater. 2020, 3, 3, 2266–2277
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acsanm.9b02387
    Published February 25, 2020
    Copyright © 2020 American Chemical Society

    Abstract

    Click to copy section linkSection link copied!
    Abstract Image

    Solution-based organometallic nanoclusters are unique nanoscale precursors due to the ability to precisely control their size, shape, structure, and assembly. The interaction of extreme ultraviolet (EUV) or X-ray photons with these organometallic nanoclusters can result in processes that can lead to a change in solubility. This makes these materials prime candidates for next-generation photoresists for EUV nanolithography. In this study, we investigate the interaction of X-ray radiation with a charge neutral, sodium templated, butyl-tin Keggin (β-NaSn13) nanocluster. This nanocluster is used as a model EUV photoresist to better understand the radiation induced solubility transition. Ambient pressure X-ray photoelectron spectroscopy (AP-XPS) was used to characterize the β-NaSn13 thin films, where Sn 3d, O 1s, and C 1s core levels were measured under a range of ambient conditions, including ultrahigh vacuum and 1 mbar of oxygen, water, methanol, or nitrogen. A photon dose array was obtained for each ambient condition to determine their effect on the photon induced chemistries which result in the solubility transition. The resulting contrast curves indicate that an oxygen ambient significantly reduces the required photon dose for the solubility transition relative to UHV, while all other ambients increase the required photon dose for the solubility transition relative to UHV. We performed in situ XPS after postexposure annealing β-NaSn13 thin films in multiple ambients to study the chemistry that occurs after a postexposure bake (PEB). The β-NaSn13 thin films retained a significant amount of aliphatic carbon following the PEB in all the ambients we studied. On the basis of our studies, we propose that the solubility transition for β-NaSn13 thin films occurs through radical hydrogen abstraction and radical–radical coupling reactions. These studies further improve the understanding of photon induced chemistries in a β-NaSn13 model resist and provide mechanistic insights for EUV lithography processing with organometallic nanomaterials.

    Copyright © 2020 American Chemical Society

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.

    Recommended

    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. Add or change your institution or let them know you’d like them to include access.

    Supporting Information

    Click to copy section linkSection link copied!

    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsanm.9b02387.

    • Low energy Zr Mζ X-rays (151.4 eV) used for XPS survey to display significant generation of secondary electrons through absorption of photons. Zr Mζ X-rays chosen due to close energy proximity to EUV photons. Additional contrast curve using Zr Mζ X-rays to emphasize ability to pattern resist material with low energy photons in addition to Al Kα photons. Sn 3d spectra reported to confirm no significant change seen in spectra before or after exposure/anneal. (PDF)

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

    Click to copy section linkSection link copied!
    Citation Statements
    Explore this article's citation statements on scite.ai

    This article is cited by 32 publications.

    1. Jingbin Li, Zhefeng Wang, Han Wang. Computational Study of Organotin Oxide Systems for Extreme Ultraviolet Photoresist. The Journal of Physical Chemistry A 2025, 129 (5) , 1420-1428. https://doi.org/10.1021/acs.jpca.4c07585
    2. Fang-Fang Liu, Guang-Yue Shi, Ni Zhen, Zuo-Hu Zhou, Tao-Li Guo, Yang Qiao, Jun Zhao, Jin-Cheng Liu, Feng Luo, Lei Zhang. Single Rare-Earth Ion Doped Tin-Oxo Nanocluster Photoresists for High-Resolution Extreme Ultraviolet Lithography. Nano Letters 2025, 25 (5) , 2067-2073. https://doi.org/10.1021/acs.nanolett.4c06140
    3. Gayoung Lim, Kangsik Lee, Chawon Koh, Tsunehiro Nishi, Hyo Jae Yoon. Multinuclear Tin-Based Macrocyclic Organometallic Resist for EUV Photolithography. ACS Materials Au 2024, 4 (5) , 468-478. https://doi.org/10.1021/acsmaterialsau.4c00010
    4. Najmeh Sadegh, Quentin Evrard, Peter M. Kraus, Albert M. Brouwer. XUV Absorption Spectroscopy and Photoconversion of a Tin-Oxo Cage Photoresist. The Journal of Physical Chemistry C 2024, 128 (9) , 3965-3974. https://doi.org/10.1021/acs.jpcc.3c07480
    5. Santu Nandi, Lalit Khillare, Sunil Kumar, Mohamad G. Moinuddin, Manvendra Chauhan, Sumit Choudhary, Satinder K. Sharma, Subrata Ghosh, Kenneth E. Gonsalves. Induced Chemical Networking of Organometallic Tin in a Cyclic Framework for Sub-10 nm Patterning and Interconnect Application. ACS Applied Nano Materials 2023, 6 (6) , 4132-4140. https://doi.org/10.1021/acsanm.2c04831
    6. Qianqian Wang, Hao Cui, Xiaolin Wang, Ziyu Hu, Peipei Tao, Mingyang Li, Jianlong Wang, Yaping Tang, Hong Xu, Xiangming He. Exceptional Light Sensitivity by Thiol–Ene Click Lithography. Journal of the American Chemical Society 2023, 145 (5) , 3064-3074. https://doi.org/10.1021/jacs.2c11887
    7. Midathala Yogesh, Mohamad. G. Moinuddin, Manvendra Chauhan, Satinder K. Sharma, Subrata Ghosh, Kenneth E. Gonsalves. Organoiodine Functionality Bearing Resists for Electron-Beam and Helium Ion Beam Lithography: Complex and Sub-16 nm Patterning. ACS Applied Electronic Materials 2021, 3 (5) , 1996-2004. https://doi.org/10.1021/acsaelm.0c01120
    8. Nizan Kenane, Douglas A. Keszler. High-Resolution Lithographic Patterning with Organotin Films: Role of CO2 in Differential Dissolution Rates. ACS Applied Materials & Interfaces 2021, 13 (16) , 18974-18983. https://doi.org/10.1021/acsami.0c21942
    9. Weizhou Chen, Liming Wang, Zi‐Rui Wang, Tao Zhu, Yuting Ye, Qiao‐Hong Li, Xiaofeng Yi, Jian Zhang. Improving the Lithography Sensitivity of Atomically Precise Tin‐Oxo Nanoclusters via Heterometal Strategy. Angewandte Chemie 2025, 137 (2) https://doi.org/10.1002/ange.202414360
    10. Cheng-Dun Li, Chun-Fu Chou, Yu-Fang Tseng, Burn-Jeng Lin, Tsai-Sheng Gau, Po-Hsiung Chen, Po-Wen Chiu, Sun-Zen Chen, Shin-Lin Tsai, Wen-Bin Jian, Jui-Hsiung Liu. A highly hydroxylated 6-tin oxide cluster serves as an efficient e-beam and EUV-photoresist to achieve high-resolution patterns. Nanoscale Advances 2025, 86 https://doi.org/10.1039/D4NA00651H
    11. Youmei Xing, Tao Hu, Weihua Fang, Yunjian Yin, Lijiang Gao, Weixin Liu, Ding Xu, Haian Jin, Guojie Wang. Nano metal-oxygen cluster EUV photoresists and their performance influencing factors. SCIENTIA SINICA Chimica 2024, 54 (12) , 2452-2462. https://doi.org/10.1360/SSC-2024-0008
    12. Weizhou Chen, Liming Wang, Zi‐Rui Wang, Tao Zhu, Yuting Ye, Qiao‐Hong Li, Xiaofeng Yi, Jian Zhang. Improving the Lithography Sensitivity of Atomically Precise Tin‐Oxo Nanoclusters via Heterometal Strategy. Angewandte Chemie International Edition 2024, 73 https://doi.org/10.1002/anie.202414360
    13. Yeo Kyung Kang, Sun Jin Lee, Sunghun Eom, Byeong Geun Kim, Chan-Cuk Hwang, Myung-Gil Kim. Recent progress of inorganic photoresists for next-generation EUV lithography. Journal of Materials Chemistry C 2024, 12 (39) , 15855-15887. https://doi.org/10.1039/D4TC02671C
    14. Jonathan Jenderny, Nils Boysen, Jens Rubner, Frederik Zysk, Florian Preischel, Teresa de los Arcos, Varun Raj Damerla, Aleksander Kostka, Jonas Franke, Rainer Dahlmann, Thomas D. Kühne, Matthias Wessling, Peter Awakowicz, Anjana Devi. Tuning the Permeation Properties of Poly(1‐trimethylsilyl‐1‐propyne) by Vapor Phase Infiltration Using Trimethylaluminum. Advanced Materials Interfaces 2024, 40 https://doi.org/10.1002/admi.202400171
    15. Yanhui Zhang, Haojie Yu, Li Wang, Xudong Wu, Jiawen He, Wenbing Huang, Chengaung Ouyang, Dingning Chen, Basem E. Keshta. Advanced lithography materials: From fundamentals to applications. Advances in Colloid and Interface Science 2024, 329 , 103197. https://doi.org/10.1016/j.cis.2024.103197
    16. Cheng-Dun Li, Ting-An Lin, Po-Hsiung Chen, Tsai-Sheng Gau, Burn-Jeng Lin, Po-Wen Chiu, Jui-Hsiung Liu. Synthesis of pentameric chlorotin carboxylate clusters for high resolution EUV photoresists under small doses. Nanoscale Advances 2024, 6 (11) , 2928-2944. https://doi.org/10.1039/D4NA00006D
    17. Tingli Du, Xiaowei Yang, Yanyan Zhao, Pingping Han, Jijun Zhao, Si Zhou. Tin-oxo nanoclusters for extreme ultraviolet photoresists: Effects of ligands, counterions, and doping. The Journal of Chemical Physics 2024, 160 (15) https://doi.org/10.1063/5.0200630
    18. Yuko Tsutsui Ito, Kyoko Watanabe, Takahiro Kozawa, Kazuo Sakamoto, Makoto Muramatsu. Dissolution dynamics of poly(4-hydroxystyrene) in potassium hydroxide (KOH) and sodium hydroxide (NaOH) aqueous solutions investigated by quartz crystal microbalance (QCM) method. Japanese Journal of Applied Physics 2024, 63 (4) , 046502. https://doi.org/10.35848/1347-4065/ad3373
    19. Jarich Haitjema, Sonia Castellanos, Olivier Lugier, Ivan Bespalov, Rebecka Lindblad, Martin Timm, Christine Bülow, Vicente Zamudio-Bayer, J. Tobias Lau, Bernd von Issendorff, Ronnie Hoekstra, Katharina Witte, Benjamin Watts, Thomas Schlathölter, Albert M. Brouwer. Soft X-ray absorption and fragmentation of tin-oxo cage photoresists. Physical Chemistry Chemical Physics 2024, 26 (7) , 5986-5998. https://doi.org/10.1039/D3CP05428D
    20. 赵慧芳 Zhao Huifang, 周作虎 Zhou Zuohu, 张磊 Zhang Lei. 极紫外光刻胶的研究进展与展望. Chinese Journal of Lasers 2024, 51 (18) , 1801002. https://doi.org/10.3788/CJL241047
    21. Yu-Fang Tseng, Pin-Chia Liao, Po-Hsiung Chen, Tsai-Sheng Gau, Burn-Jeng Lin, Po-Wen Chiu, Jui-Hsiung Liu. Highly hydroxylated hafnium clusters are accessible to high resolution EUV photoresists under small energy doses. Nanoscale Advances 2023, 6 (1) , 197-208. https://doi.org/10.1039/D3NA00508A
    22. Gayoung Lim, Kangsik Lee, Suin Choi, Hyo Jae Yoon. Organometallic and coordinative photoresist materials for EUV lithography and related photolytic mechanisms. Coordination Chemistry Reviews 2023, 493 , 215307. https://doi.org/10.1016/j.ccr.2023.215307
    23. Najmeh Sadegh, Quentin Evrard, Nicola Mahne, Angelo Giglia, Stefano Nannarone, Albert M. Brouwer. Electron Generation in Tin-oxo Cage Extreme Ultraviolet Photoresists. Journal of Photopolymer Science and Technology 2023, 36 (5) , 373-378. https://doi.org/10.2494/photopolymer.36.373
    24. Fang-Fang Liu, Di Wang, Guang-Hui Chen, Yang Qiao, Feng Luo, Jian Zhang, Lei Zhang. Alkenyl-type ligands functionalized tin-lanthanide oxo nanoclusters as molecular lithography resists. Science China Chemistry 2023, 66 (6) , 1731-1736. https://doi.org/10.1007/s11426-023-1598-3
    25. Jia-Rong Wu, Ting-An Lin, Yan-Ru Wu, Po-Hsiung Chen, Tsi-Sheng Gau, Burn-Jeng Lin, Po-Wen Chiu, Rai-Shung Liu. Novel hexameric tin carboxylate clusters as efficient negative-tone EUV photoresists: high resolution with well-defined patterns under low energy doses. Nanoscale Advances 2023, 5 (11) , 3033-3043. https://doi.org/10.1039/D3NA00131H
    26. Yutaro Iwashige, Yuko Tsutsui Ito, Takahiro Kozawa, Kazuo Sakamoto, Makoto Muramatsu. Effects of photoacid generator decomposition on dissolution kinetics of poly(4-hydroxystyrene) in tetraalkylammonium hydroxide aqueous solutions. Japanese Journal of Applied Physics 2023, 62 (3) , 036502. https://doi.org/10.35848/1347-4065/acbcb6
    27. Pin-Chia Liao, Po-Hsiung Chen, Yu-Fang Tseng, Ting-An Shih, Ting-An Lin, Tsi-Sheng Gau, Burn-Jeng Lin, Po-Wen Chiu, Jui-Hsiung Liu. Partial decarboxylation of hafnium oxide clusters for high resolution lithographic applications. Journal of Materials Chemistry C 2022, 10 (41) , 15647-15655. https://doi.org/10.1039/D2TC02912J
    28. Dario L. Goldfarb. Evolution of patterning materials towards the Moore’s Law 2.0 Era. Japanese Journal of Applied Physics 2022, 61 (SD) , SD0802. https://doi.org/10.35848/1347-4065/ac5534
    29. Di Wang, Xiaofeng Yi, Lei Zhang. Non-alkyl tin-oxo clusters as new-type patterning materials for nanolithography. Science China Chemistry 2022, 65 (1) , 114-119. https://doi.org/10.1007/s11426-021-1092-2
    30. Richard P. Oleksak, Rafik Addou, Bharat Gwalani, John P. Baltrus, Tao Liu, J. Trey Diulus, Arun Devaraj, Gregory S. Herman, Ömer N. Doğan. Molecular-scale investigation of the oxidation behavior of chromia-forming alloys in high-temperature CO2. npj Materials Degradation 2021, 5 (1) https://doi.org/10.1038/s41529-021-00194-1
    31. Xiaofeng Yi, Di Wang, Fan Li, Jian Zhang, Lei Zhang. Molecular bixbyite-like In 12 -oxo clusters with tunable functionalization sites for lithography patterning applications. Chemical Science 2021, 12 (43) , 14414-14419. https://doi.org/10.1039/D1SC04491E
    32. Peipei Tao, Li Sheng, Qianqian Wang, Hao Cui, Xiaolin Wang, Xiangming He, Hong Xu. Photoresist for Extreme Ultraviolet Lithography. 2020, 1-4. https://doi.org/10.1109/IWAPS51164.2020.9286794

    ACS Applied Nano Materials

    Cite this: ACS Appl. Nano Mater. 2020, 3, 3, 2266–2277
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acsanm.9b02387
    Published February 25, 2020
    Copyright © 2020 American Chemical Society

    Article Views

    2525

    Altmetric

    -

    Citations

    Learn about these metrics

    Article Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.

    Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.

    The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.