The synthesis of silicon nanocrystals in standard radio-frequency glow discharge systems is studied with respect to two main objectives: (i) the production of devices based on quantum size effects associated with the small dimensions of silicon nanocrystals and (ii) the synthesis of polymorphous and polycrystalline silicon films in which silicon nanocrystals are the elementary building blocks. In particular we discuss results on the mechanisms of nanocrystal formation and their transport towards the substrate. We found that silicon nanocrystals can contribute to a significant fraction of deposition (50–70%) and that they can be positively charged. This has a strong influence on their deposition because positively charged nanocrystals will be accelerated towards the substrate with energy of the order of the plasma potential. However, the important parameter with respect to the deposition of charged nanocrystals is not the accelerating voltage but the energy per atom and thus a doubling of the diameter will result in a decrease in the energy per atom by a factor of 8. To leverage this geometrical advantage we propose the use of more electronegative gases, which may have a strong effect on the size and charge distribution of the nanocrystals. This is illustrated in the case of deposition from silicon tetrafluoride plasmas in which we observe low-frequency plasma fluctuations, associated with successive generations of nanocrystals. The contribution of larger nanocrystals to deposition results in a lower energy per deposited atom and thus polycrystalline films.

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