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In this study, we integrated spectroscopy and computational techniques to meticulously investigate the pivotal factors of three prototypical PAG anions, p-toluenesulfonate (pTS\u2212), 2-(trifluoromethyl)benzene-1-sulfonate (TFMBS\u2212), and triflate (TF\u2212), in the lithography process. Our findings reveal a significant redshift in the absorption spectra caused by specific PAG anions, attributed to their involvement in electronic transition processes, thereby enhancing the transparency of the standard PAG cation, triphenylsulfonium (TPS+), particularly at \u223c193\u00a0nm. Furthermore, the electronic stability of PAG anions can be enhanced by solvent effects with varying degrees of strength. We observed the lowest vertical detachment energy of 6.6\u00a0eV of pTS\u2212 in PGMEA solution based on the polarizable continuum model, which prevents anion loss at 193\u00a0nm lithography. In addition, our findings indicate gas-phase proton affinity values of 316.4 kcal\/mol for pTS\u2212, 308.1 kcal\/mol for TFMBS\u2212, and 303.2 kcal\/mol for TF\u2212, which suggest the increasing acidity strength, yet even the weakest acid pTS\u2212 is still stronger than strong acid HBr. The photolysis of TPS+-based PAG, TPS+\u00b7pTS\u2212, generated an excited state leading to homolysis bond cleavage with the lowest reaction energy of 83 kcal\/mol. Overall, the PAG anion pTS\u2212 displayed moderate acidity, possessed the lowest photolysis reaction energy, and demonstrated an appropriate redshift. These properties collectively render it a promising candidate for an effective acid producer.<\/jats:p>","DOI":"10.1063\/5.0218918","type":"journal-article","created":{"date-parts":[[2024,8,6]],"date-time":"2024-08-06T11:32:48Z","timestamp":1722943968000},"update-policy":"https:\/\/doi.org\/10.1063\/aip-crossmark-policy-page","source":"Crossref","is-referenced-by-count":4,"title":["A comprehensive study on three typical photoacid generators using photoelectron spectroscopy and <i>ab\u00a0initio<\/i> calculations"],"prefix":"10.1063","volume":"161","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-1508-6770","authenticated-orcid":false,"given":"Yanrong","family":"Jiang","sequence":"first","affiliation":[{"name":"Center for Transformative Science, ShanghaiTech University 1 , Shanghai 201210, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2852-4047","authenticated-orcid":false,"given":"Wenjin","family":"Cao","sequence":"additional","affiliation":[{"name":"Physical Sciences Division, Pacific Northwest National Laboratory 2 , 902 Battelle Boulevard, P.O. 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