Novel Mechanism-Based Descriptors for Extreme Ultraviolet-Induced Photoacid Generation: Key Factors Affecting Extreme Ultraviolet Sensitivity
Predicting photolithography performance in silico for a given materials combination is essential for developing better patterning processes. However, it is still an extremely daunting task because of the entangled chemistry with multiple reactions among many material components. Herein, we investiga...
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| Format: | Article |
| Language: | English |
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MDPI AG
2023-08-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/28/17/6244 |
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| author | Ji Young Park Hyun-Ji Song Thanh Cuong Nguyen Won-Joon Son Daekeon Kim Giyoung Song Suk-Koo Hong Heeyoung Go Changmin Park Inkook Jang Dae Sin Kim |
| author_facet | Ji Young Park Hyun-Ji Song Thanh Cuong Nguyen Won-Joon Son Daekeon Kim Giyoung Song Suk-Koo Hong Heeyoung Go Changmin Park Inkook Jang Dae Sin Kim |
| author_sort | Ji Young Park |
| collection | DOAJ |
| description | Predicting photolithography performance in silico for a given materials combination is essential for developing better patterning processes. However, it is still an extremely daunting task because of the entangled chemistry with multiple reactions among many material components. Herein, we investigated the EUV-induced photochemical reaction mechanism of a model photoacid generator (PAG), triphenylsulfonium cation, using atomiC–Scale materials modeling to elucidate that the acid generation yield strongly depends on two main factors: the lowest unoccupied molecular orbital (LUMO) of PAG cation associated with the electron-trap efficiency ‘before C–S bond dissociation’ and the overall oxidation energy change of rearranged PAG associated with the proton-generation efficiency ‘after C–S bond dissociation’. Furthermore, by considering stepwise reactions accordingly, we developed a two-parameter-based prediction model predicting the exposure dose of the resist, which outperformed the traditional LUMO-based prediction model. Our model suggests that one should not focus only on the LUMO energies but also on the energy change during the rearrangement process of the activated triphenylsulfonium (TPS) species. We also believe that the model is well suited for computational materials screening and/or inverse design of novel PAG materials with high lithographic performances. |
| first_indexed | 2024-03-10T23:16:57Z |
| format | Article |
| id | doaj.art-012c9efdd14c4b02a0ffc4e64d12605e |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-10T23:16:57Z |
| publishDate | 2023-08-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-012c9efdd14c4b02a0ffc4e64d12605e2023-11-19T08:33:18ZengMDPI AGMolecules1420-30492023-08-012817624410.3390/molecules28176244Novel Mechanism-Based Descriptors for Extreme Ultraviolet-Induced Photoacid Generation: Key Factors Affecting Extreme Ultraviolet SensitivityJi Young Park0Hyun-Ji Song1Thanh Cuong Nguyen2Won-Joon Son3Daekeon Kim4Giyoung Song5Suk-Koo Hong6Heeyoung Go7Changmin Park8Inkook Jang9Dae Sin Kim10Innovation Center, Samsung Electronics, Samsungjeonja-ro 1, Hwaseong-si 18448, Republic of KoreaSemiconductor R&D Center, Samsung Electronics, Samsungjeonja-ro 1, Hwaseong-si 18448, Republic of KoreaInnovation Center, Samsung Electronics, Samsungjeonja-ro 1, Hwaseong-si 18448, Republic of KoreaInnovation Center, Samsung Electronics, Samsungjeonja-ro 1, Hwaseong-si 18448, Republic of KoreaInnovation Center, Samsung Electronics, Samsungjeonja-ro 1, Hwaseong-si 18448, Republic of KoreaSemiconductor R&D Center, Samsung Electronics, Samsungjeonja-ro 1, Hwaseong-si 18448, Republic of KoreaSemiconductor R&D Center, Samsung Electronics, Samsungjeonja-ro 1, Hwaseong-si 18448, Republic of KoreaSemiconductor R&D Center, Samsung Electronics, Samsungjeonja-ro 1, Hwaseong-si 18448, Republic of KoreaSemiconductor R&D Center, Samsung Electronics, Samsungjeonja-ro 1, Hwaseong-si 18448, Republic of KoreaInnovation Center, Samsung Electronics, Samsungjeonja-ro 1, Hwaseong-si 18448, Republic of KoreaInnovation Center, Samsung Electronics, Samsungjeonja-ro 1, Hwaseong-si 18448, Republic of KoreaPredicting photolithography performance in silico for a given materials combination is essential for developing better patterning processes. However, it is still an extremely daunting task because of the entangled chemistry with multiple reactions among many material components. Herein, we investigated the EUV-induced photochemical reaction mechanism of a model photoacid generator (PAG), triphenylsulfonium cation, using atomiC–Scale materials modeling to elucidate that the acid generation yield strongly depends on two main factors: the lowest unoccupied molecular orbital (LUMO) of PAG cation associated with the electron-trap efficiency ‘before C–S bond dissociation’ and the overall oxidation energy change of rearranged PAG associated with the proton-generation efficiency ‘after C–S bond dissociation’. Furthermore, by considering stepwise reactions accordingly, we developed a two-parameter-based prediction model predicting the exposure dose of the resist, which outperformed the traditional LUMO-based prediction model. Our model suggests that one should not focus only on the LUMO energies but also on the energy change during the rearrangement process of the activated triphenylsulfonium (TPS) species. We also believe that the model is well suited for computational materials screening and/or inverse design of novel PAG materials with high lithographic performances.https://www.mdpi.com/1420-3049/28/17/6244photoacid generator (PAG)acid-generation mechanismchemical amplified resist (CAR)triphenylsulfonium (TPS)extreme ultraviolet (EUV) photoresist |
| spellingShingle | Ji Young Park Hyun-Ji Song Thanh Cuong Nguyen Won-Joon Son Daekeon Kim Giyoung Song Suk-Koo Hong Heeyoung Go Changmin Park Inkook Jang Dae Sin Kim Novel Mechanism-Based Descriptors for Extreme Ultraviolet-Induced Photoacid Generation: Key Factors Affecting Extreme Ultraviolet Sensitivity Molecules photoacid generator (PAG) acid-generation mechanism chemical amplified resist (CAR) triphenylsulfonium (TPS) extreme ultraviolet (EUV) photoresist |
| title | Novel Mechanism-Based Descriptors for Extreme Ultraviolet-Induced Photoacid Generation: Key Factors Affecting Extreme Ultraviolet Sensitivity |
| title_full | Novel Mechanism-Based Descriptors for Extreme Ultraviolet-Induced Photoacid Generation: Key Factors Affecting Extreme Ultraviolet Sensitivity |
| title_fullStr | Novel Mechanism-Based Descriptors for Extreme Ultraviolet-Induced Photoacid Generation: Key Factors Affecting Extreme Ultraviolet Sensitivity |
| title_full_unstemmed | Novel Mechanism-Based Descriptors for Extreme Ultraviolet-Induced Photoacid Generation: Key Factors Affecting Extreme Ultraviolet Sensitivity |
| title_short | Novel Mechanism-Based Descriptors for Extreme Ultraviolet-Induced Photoacid Generation: Key Factors Affecting Extreme Ultraviolet Sensitivity |
| title_sort | novel mechanism based descriptors for extreme ultraviolet induced photoacid generation key factors affecting extreme ultraviolet sensitivity |
| topic | photoacid generator (PAG) acid-generation mechanism chemical amplified resist (CAR) triphenylsulfonium (TPS) extreme ultraviolet (EUV) photoresist |
| url | https://www.mdpi.com/1420-3049/28/17/6244 |
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