Er-containing silicon compatible materials have been widely used as infrared emitters for microphotonics application. In this field, the additional introduction of a proper sensitizer permits to increase the Er excitation cross sections, thus increasing its optical efficiency. This work aims to investigate the influence of a post-transition metal, bismuth, on the optical properties of erbium-yttrium disilicate thin films synthesized by magnetron co-sputtering. After thermal treatments at 1000 °C in O2 or N2 environment, the presence of small precipitates, about 6 nm in diameter, was evidenced by transmission electron microscopy analyses. The spatially resolved chemical nature of the nanoparticles was discerned in the Si and O rich environments by means of scanning transmission electron microscopy–energy dispersive X-ray and scanning transmission electron microscopy–electron energy loss spectroscopy analyses …