Thermoelectric device is a promising next-generation energy solution owing to its capability to transform waste heat into useful electric energy, which can be realized in materials with high electric conductivities and low thermal conductivities. A recently synthesized silicon allotrope of Si24 features highly anisotropic crystal structure with nanometer-sized regular pores. Here, based on first-principles study without any empirical parameter we show that the slightly doped Si24 can provide an order-of-magnitude enhanced thermoelectric figure of merit at room temperature, compared with the cubic diamond phase of silicon. We ascribe the enhancement to the intrinsic nanostructure formed by the nanopore array, which effectively hinders heat conduction while electric conductivity is maintained. This can be a viable option to enhance the thermoelectric figure of merit without further forming an extrinsic nanostructure. In addition, we propose a practical strategy to further diminish the thermal conductivity without affecting electric conductivity by confining rattling guest atoms in the pores.
Keywords: First-principles calculations; electron−phonon coupling; intrinsic nanostructure; thermoelectric figure of merit.