Doping of silicon nanocrystals has become an important topic due to its potential to enable the fabrication of environmentally friendly and cost-effective optoelectronic and photovoltaic devices. However, doping of silicon nanocrystals has been proven difficult and most of the structural and electronic properties are still not well understood. In this work, the intrinsic and boron-doped self-assembled silicon nanocrystals were prepared and mainly characterised by the transient current method to study the behaviour of charge carriers in these materials. Our experiments quantified the amount of electrically active boron dopants that contributed to charge transport. From this, the boron doping efficiency in the nanocrystal superlattice was estimated.