Paradoxical Enhancement of the Power Factor of Polycrystalline Silicon as a Result of the Formation of Nanovoids

Hole-containing silicon has been regarded as a viable candidate thermoelectric material because of its low thermal conductivity. However, because voids are efficient scattering centers not just for phonons but also for charge carriers, achievable power factors (PFs) are normally too low for its most common form, i.e. porous silicon, to be of practical interest. In this communication we report that high PFs can, indeed, be achieved with nanoporous structures obtained from highly doped silicon. High PFs, up to a huge 22 mW K−2 m−1 (more than six times higher than values for the bulk material), were observed for heavily boron-doped nanocrystalline silicon films in which nanovoids (NVs) were generated by He+ ion implantation. In contrast with single-crystalline silicon in which He+ implantation leads to large voids, in polycrystalline films implantation followed by annealing at 1000°C results in homogeneous distribution of NVs with final diameters of approximately 2 nm and densities of the order of 1019 cm−3 with average spacing of 10 nm. Study of its morphology revealed silicon nanograins 50 nm in diameter coated with 5-nm precipitates of SiB x . We recently reported that PFs up to 15 mW K−2 m−1 could be achieved for silicon–boron nanocomposites (without NVs) because of a simultaneous increase of electrical conductivity and Seebeck coefficient. In that case, the high Seebeck coefficient was achieved as a result of potential barriers on the grain boundaries, and high electrical conductivity was achieved as a result of extremely high levels of doping. The additional increase in the PF observed in the presence of NVs (which also include SiB x precipitates) might have several possible explanations; these are currently under investigation. Experimental results are reported which might clarify the reason for this paradoxical effect of NVs on silicon PF.