Accurate and efficient evaluation of the ionization potentials of extreme ultraviolet photoresists using density functionals and semi-empirical methods

doi:10.1007/s44275-024-00002-3

Moore and More ›› 2025, Vol. 1 ›› Issue (2): 102-113.DOI: 10.1007/s44275-024-00002-3

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Accurate and efficient evaluation of the ionization potentials of extreme ultraviolet photoresists using density functionals and semi-empirical methods

Kun Du¹, Jiafeng Ying², Lixin Han¹, Jie Xue¹, Hanshen Xin¹, Jianhua Zhang¹, Haoyuan Li¹

1. School of Microelectronics, Shanghai University, Shanghai, 201800, China;
2. School of Materials Science and Engineering, Shanghai University, Shanghai, 201800, China

Received:2023-10-12 Revised:2024-01-04 Accepted:2024-01-22 Online:2024-05-28 Published:2024-05-28
Contact: Haoyuan Li,E-mail:lihaoyuan@shu.edu.cn
Supported by:
This work was supported by the National Natural Science Foundation of China (grant number 22090013) and the Shanghai Committee of Science and Technology (grant numbers: 21QA1402900 and YDZX20213100002672).

Accurate and efficient evaluation of the ionization potentials of extreme ultraviolet photoresists using density functionals and semi-empirical methods

Kun Du¹, Jiafeng Ying², Lixin Han¹, Jie Xue¹, Hanshen Xin¹, Jianhua Zhang¹, Haoyuan Li¹

1. School of Microelectronics, Shanghai University, Shanghai, 201800, China;
2. School of Materials Science and Engineering, Shanghai University, Shanghai, 201800, China

通讯作者: Haoyuan Li,E-mail:lihaoyuan@shu.edu.cn
作者简介:Kun Du graduated from Fuyang Normal University in 2018 with a bachelor’s degree in engineering. He obtained a master’s degree in engineering from Jiangxi Science and Technology Normal University in 2021. He is currently a Ph.D. candidate supervised by Prof. Haoyuan Li in the School of Microelectronics at Shanghai University. He uses molecular simulations to study photoresists and two-dimensional materials.
Jiafeng Ying graduated from the Zhejiang University of Science and Technology in 2021 with a Bachelor’s degree in engineering. He then obtained a master’s degree from the School of Microelectronics at Shanghai University in 2023, supervised by Prof.
Jianhua Zhang and Prof. Haoyuan Li. His research focuses on photoresists. Lixin Han graduated from Shanghai University in 2021 with a bachelor’s degree in engineering. He is currently studying as a master candidate in the School of Microelectronics at Shanghai University, supervised by Prof. Haoyuan Li. His research interest is polyimide materials.
Jie Xue received his B.S. degree in applied chemistry in 2013 from Beijing University of Chemical Technology and his Ph.D. degree in physical chemistry in 2018 from Tsinghua University. Currently, he is an associate professor in the School of Micro-electronics, Shanghai University. His research interests mainly focus on organic materials for organic light-emitting diodes and solar cells.
Hanshen Xin obtained his B.Sc. degree in chemistry from Zhengzhou University in 2013. He then joined Prof. Xike Gao’s group at Shanghai Institute of Organic Chemistry (SIOC), Chinese Academy of Sciences, and received his Ph.D. in 2018. After postdoctoral training in the lab of Prof. Timothy Swager at MIT, he joined Shanghai University as an associate professor in 2021. His research interests include materials for organic semiconductors and photoresists.
Jianhua Zhang is the executive dean of the School of Microelectronics at Shanghai University in Shanghai, China. Meanwhile, she concurrently serves as the president of the Beijing Chapter of the Society for Information Display (SID), an executive director of the Robotics Branch of the Chinese Mechanical Engineering Society, a director of the Tribology Branch of the Chinese Mechanical Engineering Society, a director of the Micro nano Manufacturing Technology Branch of the Chinese Mechanical Engineering Society, and a director of the Luminescence Branch of the Chinese Physical Society.
Haoyuan Li is currently a professor in the School of Microelectronics at Shanghai University in China. He obtained his PhD degree from Tsinghua University in 2015, under the supervision of Prof. Yong Qiu. He then joined the group of Prof. Jean-Luc Brédas as a postdoctoral fellow and became a research scientist later on. He worked at King Abdullah University of Science and Technology, Georgia Institute of Technology, and the University of Arizona from 2015 to 2020. His research interests include molecular simulations and machine learning of organic functional materials and energy storage systems.
基金资助:
This work was supported by the National Natural Science Foundation of China (grant number 22090013) and the Shanghai Committee of Science and Technology (grant numbers: 21QA1402900 and YDZX20213100002672).

Abstract

Abstract: Extreme ultraviolet (EUV) photoresists have become the core materials in lithography with nanometer-sized patterns and are actively explored on the path to realizing smaller critical dimensions. These photoresists can be small molecule-, polymer-, or organic–inorganic hybrid-based, with the full molecular working mechanism under investigation. For the rational design of EUV photoresists, theoretical guidance using tools like first-principle calculations and multi-scale simulations can be of great help. Considering the extremely high standard of accuracy in EUV lithography, it is critical to ensure the adoption of the appropriate methodologies in the theoretical evaluation of EUV photoresists. However, it is known that density functionals and semi-empirical methods differ in accuracy and efficiency, without a universal rule across materials. This poses a challenge in developing a reliable theoretical framework for calculating EUV photoresists. Here, we present a benchmark investigation of density functionals and semi-empirical methods on the three main types of EUV photoresists, focusing on the ionization potential, a key parameter in their microscopic molecular reactions. The vertical detachment energies (VDE) and adiabatic detachment energies (ADE) were calculated using 12 functionals, including pure functionals, hybrid functionals, Minnesota functionals, and the recently developed optimally tuned range-separated (OTRS) functionals. Several efficient semi-empirical methods were also chosen, including AM1, PM6, PM7, and GFN1-xTB in the extended tight-binding theoretical framework. These results guide the accurate and efficient calculation of EUV photoresists and are valuable for the development of multi-scale lithography protocols.

Key words: Extreme ultraviolet (EUV), Photoresist, Density functional theory, Semi-empirical methods, Ionization potentials

摘要： Extreme ultraviolet (EUV) photoresists have become the core materials in lithography with nanometer-sized patterns and are actively explored on the path to realizing smaller critical dimensions. These photoresists can be small molecule-, polymer-, or organic–inorganic hybrid-based, with the full molecular working mechanism under investigation. For the rational design of EUV photoresists, theoretical guidance using tools like first-principle calculations and multi-scale simulations can be of great help. Considering the extremely high standard of accuracy in EUV lithography, it is critical to ensure the adoption of the appropriate methodologies in the theoretical evaluation of EUV photoresists. However, it is known that density functionals and semi-empirical methods differ in accuracy and efficiency, without a universal rule across materials. This poses a challenge in developing a reliable theoretical framework for calculating EUV photoresists. Here, we present a benchmark investigation of density functionals and semi-empirical methods on the three main types of EUV photoresists, focusing on the ionization potential, a key parameter in their microscopic molecular reactions. The vertical detachment energies (VDE) and adiabatic detachment energies (ADE) were calculated using 12 functionals, including pure functionals, hybrid functionals, Minnesota functionals, and the recently developed optimally tuned range-separated (OTRS) functionals. Several efficient semi-empirical methods were also chosen, including AM1, PM6, PM7, and GFN1-xTB in the extended tight-binding theoretical framework. These results guide the accurate and efficient calculation of EUV photoresists and are valuable for the development of multi-scale lithography protocols.

关键词: Extreme ultraviolet (EUV), Photoresist, Density functional theory, Semi-empirical methods, Ionization potentials

Kun Du, Jiafeng Ying, Lixin Han, Jie Xue, Hanshen Xin, Jianhua Zhang, Haoyuan Li. Accurate and efficient evaluation of the ionization potentials of extreme ultraviolet photoresists using density functionals and semi-empirical methods[J]. Moore and More, 2025, 1(2): 102-113.

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Accurate and efficient evaluation of the ionization potentials of extreme ultraviolet photoresists using density functionals and semi-empirical methods

Accurate and efficient evaluation of the ionization potentials of extreme ultraviolet photoresists using density functionals and semi-empirical methods

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