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Multilayers of SiGe nanocrystals embedded in an oxide matrix have been fabricated by low-pressure chemical vapor deposition of SiGe and SiO2 onto Si wafers (in a single run at 390 °C and 50 mTorr, using GeH4, Si2H6 and O2) followed by a rapid thermal annealing treatment to crystallize the SiGe nanoparticles. The main emission band is located at 400 nm in both cathodoluminescence and photoluminescence experiments at 80 K and also at room temperature. The annealing conditions (temperatures ranging from 700 to 1000 °C and for times of 30 and 60 s) have been investigated in samples with different diameter of the nanoparticles (from ≈3 to ≥5 nm) and oxide interlayer thickness (15 and 35 nm) in order to establish a correlation between the crystallization of the nanoparticles, the degradation of their composition by Ge diffusion and the intensity of the luminescence emission band. Structures with small nanoparticles (3&-4.5 nm) separated by thick oxide barriers (≈35 nm) annealed at 900 °C for 60 s yield the maximum intensity of the luminescence. An additional treatment at 450 °C in forming gas for dangling-bond passivation increases the intensity of the luminescence band by 25&-30%.