As building blocks of novel multifunctional materials involving coupling at the nanoscale, highly doped semiconductor nanocrystals are of great interest for potential applications in nanophotonics. In this work, we investigate the plasmonic properties of highly doped Si nanocrystals embedded in a silica matrix. These materials are obtained by evaporation of heavily Phosphorus-doped SiO/SiO2 multilayers in a ultrahigh vacuum chamber followed by rapid thermal annealing. For P contents between 0.7 and 1.9 at%, structural investigations at the nanoscale give clear evidence that P atoms are mainly located in the core of Si nanocrystals with concentrations reaching up to 10 at%, i.e. well beyond the solid solubility limit of P in bulk Si. Alloyin...