Despite its potential in the fields of optoelectronics and topological insulators, experimental electronic band structure studies of Bi-doped GaAs are scarce. The reason is the complexity of growth which tends to leave bulk and in particular surface properties in an undefined state. Here we present an in depth investigation of structural and electronic properties of GaAsBi epilayers grown by molecular beam epitaxy with high (001) crystalline order and well-defined surface structures evident from low-energy electron diffraction. X-ray and ultraviolet photoemission spectrocopy as well as angle-resolved photoemission data at variable photon energies allows to disentangle a Bi-rich surface layer with $(1times3)$ symmetry from the effects of Bi atoms incorporated in the GaAs bulk matrix. The influence of Bi concentrations up to $approx 1$% integrated in the GaAs bulk are visible in angle-resolved photoemission spectra after mild ion bombardment and subsequent annealing steps. Interpretation of our results is obtained via density functional theory simulations of bulk and $beta 2(2times 4)$ reconstructed slab geometries with and without Bi. Bi-induced energy shifts in the dispersion of GaAs heavy and light hole bulk bands are evident both in experiment and theory, which are relevant for modulations in the optical band gap and thus optoelectronic applications.
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