The optimized N2O fluence is demonstrated for plasma enhanced chemical vapor deposition (PECVD) of Si-rich substoichiometric silicon oxide (SiOx) films with buried Si nanocrystals. Strong room-temperature photoluminescence (PL) at 550-870 nm has been observed in SiOx films grown by PECVD under a constant SiH4 fluence of 20 sccm with an N2O fluence varying from 105 sccm to 130 sccm. A 22-nm-redshift in the central PL wavelength has been detected after annealing from 15 min to 180 min. The maximum PL irradiance is observed from the SiOx film grown at the optimal N2O fluence of 120 sccm after annealing for 30 minutes. Larger N2O fluence or longer annealing time leads to a PL band that is blue-shifted by 65 nm and 20 nm, respectively. Such a blue shift is attributed to shrinkage in the size of the Si nanocrystals with the participation of oxygen atoms from N2O incorporated within the SiOx matrix. The (220)-oriented Si nanocrystals exhibit radii ranging from 4.4 nm to 5.0 nm as determined by transmission electron microscopy (TEM). The luminescent lifetime lengthens to 52 μs as the nc-Si size increase to > 4 nm. Optimal annealing times for SiOx films prepared at different N2O fluences are also reported. A longer annealing process results in a stronger oxidation effect in SiOx films prepared at higher N2O fluences, yielding a lower PL irradiance at shorter wavelengths. In contrast, larger Si nanocrystals can be precipitated when the N2O fluence becomes lower; however, such a SiOx film usually exhibits weaker PL at longer wavelength due to a lower nc-Si density. These results indicate that a N2O/SiH4 fluence ratio of 6:1 is the optimized PECVD growth condition for the Si-rich SiO2 wherein dense Si nanocrystals are obtained after annealing.