  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,
photo-induced charge carriers have not been observed in the early phases of
their respective relaxation pathways. Using two-photon photoemission (2PPE) we
follow the de-excitation 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 photo-excitation,
particularly along the $\Gamma T$-line where the electron dynamics have not
been probed with time-resolved 2PPE so far.
