Interfaces between a bulk-insulating topological insulator (TI) and metallic adatoms have been studied using high-resolution, angle-resolved and core-level photoemission. Fe, Nb and Ag were evaporated onto Bi1.5Sb0.5Te1.7Se1.3 (BSTS) surfaces both at room temperature and 38K. The coverage- and temperature-dependence of the adsorption and interfacial formation process have been investigated, highlighting the effects of the overlayer growth on the occupied electronic structure of the TI. For all coverages at room temperature and for those equivalent to less than 0.1 monolayer at low temperature all three metals lead to a downward shift of the TIs bands with respect to the Fermi level. At room temperature Ag appears to intercalate efficiently into the van der Waals gap of BSTS, accompanied by low-level substitution of the Te/Se atoms of the termination layer of the crystal. This Te/Se substitution with silver increases significantly for low temperature adsorption, and can even dominate the electrostatic environment of the Bi/Sb atoms in the BSTS near-surface region. On the other hand, Fe and Nb evaporants remain close to the termination layer of the crystal. On room temperature deposition, they initially substitute isoelectronically for Bi as a function of coverage, before substituting for Te/Se atoms. For low temperature deposition, Fe and Nb are too immobile for substitution processes and show a behaviour consistent with clustering on the surface. For both Ag and Fe/Nb, these differing adsorption pathways leads to the qualitatively similar and remarkable behavior for low temperature deposition that the chemical potential first moves upward (n-type dopant behavior) and then downward (p-type behavior) on increasing coverage.
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