In this work we aim at understanding the effect of n- and p-type substitutional doping in the case of matrix-embedded and freestanding Si nanocrystals. By means of ab initio calculations we identify the preferential positioning of the dopants and its effect on the structural properties with respect to the undoped case. Subsequently, we consider the case of B phosphorus and boron co-doped nanocrystals showing that, against the single-doping situation, the energetics strongly favors the binding of the impurities at the nanocrystal surface. Indeed we demonstrate that the polar B P bond forms a stable permanent electric dipole that radially points inward in the nanocrystal. Such a noteworthy characteristic and its physical consequences are discussed alongside new potential applications.