We present a combined analysis of scanning transmission electron microscopy (STEM) imaging and electron energy loss spectroscopy (EELs) of silicon-rich-silicon-oxide (SRSO) thin film on silicon, grown by plasma enhanced chemical vapour deposition (PECVD). For un-doped samples, strong room temperature luminescence at ~1.6 eV (780 nm) is observed, which we ascribe, by way of plasmon intensity mapping and dasiachemical fingerprintingpsila to phase segregated, highly crystalline, silicon-rich nano-clusters embedded in an amorphous-silicon dioxide (a-SiO2) matrix. For samples doped with increasing concentrations of Er, a quenching of the 1.6 eV line, concurrent with the emergence of a second emission with increasing intensity at ~0.8 eV (1535 nm) is observed. This is attributed to a rapid and efficient, indirect nano-crystal mediated excitation of the Er.