  We show that the optical and electronic properties of nanocrystalline silicon
can be efficiently tuned using impurity doping. In particular, we give
evidence, by means of ab-initio calculations, that by properly controlling the
doping with either one or two atomic species, a significant modification of
both the absorption and the emission of light can be achieved. We have
considered impurities, either boron or phosphorous (doping) or both (codoping),
located at different substitutional sites of silicon nanocrystals with size
ranging from 1.1 nm to 1.8 nm in diameter. We have found that the codoped
nanocrystals have the lowest impurity formation energies when the two
impurities occupy nearest neighbor sites near the surface. In addition, such
systems present band-edge states localized on the impurities giving rise to a
red-shift of the absorption thresholds with respect to that of undoped
nanocrystals. Our detailed theoretical analysis shows that the creation of an
electron-hole pair due to light absorption determines a geometry distortion
that in turn results in a Stokes shift between adsorption and emission spectra.
In order to give a deeper insight in this effect, in one case we have
calculated the absorption and emission spectra going beyond the single-particle
approach showing the important role played by many-body effects. The entire set
of results we have collected in this work give a strong indication that with
the doping it is possible to tune the optical properties of silicon
nanocrystals.
