AbstractSilicon-rich silicon oxide (SRSO) films were prepared by thermal oxidation (700°C-950°C) of electrochemically etched crystalline silicon (c-Si). The annealing-oxidation conditions are responsible for the chemical and structural modification of SRSO as well as for the intrinsic light-emission in the visible and near infra-red spectral regions (2.0–1.8 eV, 1.6 eV and 1.1 eV). The extrinsic photoluminescence (PL) is produced by doping (via electroplating or ion implantation) with rare-earth (R-E) ions (Nd at 1.06 μm, Er at 1.5 μm) and chalcogens (S at ∼1.6 μm). The impurities can be localized within the Si grains (S), in the SiO matrix (Nd, Er) or at the Si-SiO interface (Er). The Er-related PL in SRSO was studied in detail: the maximum PL external quantum efficiency (EQE) of 0.01–0.1% was found in samples annealed at 900°C in diluted oxygen (∼ 10% in N2). The integrated PL temperature dependence is weak from 12K to 300K. Light emitting diodes (LEDs) with an active layer made of an intrinsic and doped SRSO are manufactured and studied: room temperature electroluminescence (EL) from the visible to 1.6 μmhas been demonstrated.