Nanostructured bulk Si for thermoelectrics synthesized by surface diffusion/sintering doping

Nanostructured bulk silicon (bulk nano-Si) has attracted attention as an advanced thermoelectric (TE) material due to its abundance and low toxicity. However, oxidization will occur easily when bulk nano-Si is synthesized by a conventional method, which deteriorates the TE performance. Various methods to prevent such oxidation have been proposed but they need specific techniques and are thus expensive. Here, we propose a simple and cost-effective method named Surface Diffusion/Sintering Doping (SDSD) to synthesize bulk nano-Si for TEs. SDSD utilizes Si nanoparticles whose surface is coated with a native thin oxide layer. SDSD is composed of two steps, (1) a molecular precursor containing a doping element is added onto the oxide layer of Si nanoparticles and (2) the nanoparticles are sintered into a bulk state. During sintering, the doping element diffuses through the oxide layer forming conductive paths, which results in a high carrier concentration as well as high mobility. Furthermore, owing to the nanostructures, low lattice thermal conductivity (κ _lat) is also achieved, which is an ideal situation for TEs. In this study, we show that P-doped bulk nano-Si synthesized by SDSD shows good TE performance due to its high carrier concentration, high carrier mobility, and low κ _lat. Since SDSD takes advantage of oxidization, it is cost-effective and suitable for mass production to synthesize bulk nano-Si for TEs.