Bi possesses intriguing properties due to its large spin-orbit coupling, e.g., as a constituent of topological insulators. While its electronic structure and the dynamics of electron-phonon coupling have been studied in the past, photoinduced charge carriers have not been observed in the early phases of their respective relaxation pathways. Using two-photon photoemission (2PPE) we follow the deexcitation pathway of electrons along the unoccupied band structure and into a bulk hole pocket. Two decay channels are found, one of which involves an Auger process. In the hole pocket, the electrons undergo an energetic stabilization and recombine with the corresponding holes with an inverse rate of 2.5 ps. Our results contribute to the understanding of the charge carrier relaxation processes immediately upon photoexcitation, particularly along the ΓT line where the electron dynamics have not been probed with time-resolved 2PPE so far.
