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Some fundamental aspects of this process, such as the evolution of exciton binding energy, have not been resolved in time experimentally. Here, we apply a combination of sub-10-fs Pump-Push-Photocurrent, Pump-Push-Photoluminescence, and Pump-Probe spectroscopies to polyfluorene devices to track the ultrafast formation of excitons. While Pump-Probe is sensitive to the total concentration of excited states, Pump-Push-Photocurrent and Pump-Push-Photoluminescence are sensitive to bound states only, providing access to exciton binding dynamics. We find that excitons created by near-absorption-edge photons are intrinsically bound states, or become such within 10\u2009fs after excitation. Meanwhile, excitons with a modest &gt;0.3\u2009eV excess energy can dissociate spontaneously within 50\u2009fs before acquiring bound character. These conclusions are supported by excited-state molecular dynamics simulations and a global kinetic model which quantitatively reproduce experimental data.<\/jats:p>","DOI":"10.1038\/s41467-022-32478-8","type":"journal-article","created":{"date-parts":[[2022,8,23]],"date-time":"2022-08-23T16:05:43Z","timestamp":1661270743000},"update-policy":"https:\/\/doi.org\/10.1007\/springer_crossmark_policy","source":"Crossref","is-referenced-by-count":18,"title":["Sub-10-fs observation of bound exciton formation in organic optoelectronic devices"],"prefix":"10.1038","volume":"13","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-3474-9565","authenticated-orcid":false,"given":"Marios","family":"Maimaris","sequence":"first","affiliation":[]},{"given":"Allan J.","family":"Pettipher","sequence":"additional","affiliation":[]},{"given":"Mohammed","family":"Azzouzi","sequence":"additional","affiliation":[]},{"given":"Daniel J.","family":"Walke","sequence":"additional","affiliation":[]},{"given":"Xijia","family":"Zheng","sequence":"additional","affiliation":[]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5440-2185","authenticated-orcid":false,"given":"Andrei","family":"Gorodetsky","sequence":"additional","affiliation":[]},{"given":"Yifan","family":"Dong","sequence":"additional","affiliation":[]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2096-3483","authenticated-orcid":false,"given":"Pabitra Shakya","family":"Tuladhar","sequence":"additional","affiliation":[]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5716-7181","authenticated-orcid":false,"given":"Helder","family":"Crespo","sequence":"additional","affiliation":[]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1048-1330","authenticated-orcid":false,"given":"Jenny","family":"Nelson","sequence":"additional","affiliation":[]},{"given":"John W. 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