Absence of quantum confinement effects in the photoluminescence of Si3N4–embedded Si nanocrystals

Superlattices of Si-rich silicon nitride and Si3N4 are prepared by plasma-enhanced chemical vapor deposition and, subsequently, annealed at 1150 °C to form size-controlled Si nanocrystals (Si NCs) embedded in amorphous Si3N4. Despite well defined structural properties, photoluminescence spectroscopy (PL) reveals inconsistencies with the typically applied model of quantum confined excitons in nitride-embedded Si NCs. Time-resolved PL measurements demonstrate 105 times faster time-constants than typical for the indirect band structure of Si NCs. Furthermore, a pure Si3N4 reference sample exhibits a similar PL peak as the Si NC samples. The origin of this luminescence is discussed in detail on the basis of radiative defects and Si3N4 band tail states in combination with optical absorption measurements. The apparent absence of PL from the Si NCs is explained conclusively using electron spin resonance data from the Si/Si3N4 interface defect literature. In addition, the role of Si3N4 valence band tail states as...