In this study, we have investigated a behavior of particle with diameter several ten nanometers size at the time of heating on an atomic scale by numerical analysis using the molecular dynamics (MD) simulation. On solving the equation of motion, the Langevin equation was adopted. The Finnis-Sinclair potential, which can well reproduce the mechanical properties of a BCC-metal, was used as the interatomic force. We determined the relationship between the melting point (Tm) of the nano-sized particles and its diameter by MD simulations. We have also investigated the self-diffusion coefficient of each atom-forming at a temperature larger or less than Tm of the submicron-size metal particles . As a result, even in case of heating at a temperature larger than Tm, the mean self-diffusion coefficient at the center of a particle was 10-7–10-6 cm2/sec. On the other hand, at the surface layer of the particle was two to three orders of magnitude larger than that at the center. Those particles were in a quasi-molten state. It is conceivable that the thickness of the surface layer can explain a phenomenon that sintering progresses as the heating temperature increases.

Seebeck effect is widely used for the energy harvesting from wasted heat. In the Seebeck effect, the electric power can be generated by the temperature difference between both ends of the thermoelectric materials. However, low conversion efficiency is caused by heat flux from hot side to cold side of sample. In this paper, we have proposed a new thermal power generation mechanism with no temperature difference. We investigated the band structure of Ba8AuxSi46-x clathrate single crystal synthesized by Czochralski method. The single crystal has a gradient of the gold contents along the growth direction. According to the results of Seebeck coefficient, the electrical properties of the Ba8AuxSi46-x clathrate dramatically changed depending on the gold contents. In the case of gold content of lower than 5.33, the Ba8AuxSi46-x clathrate showed a n-type semiconductor. In the case of gold content of higher than 5.33, the Ba8AuxSi46-x clathrate showed a p-type semiconductor. The band gap of the n-type and p-type Ba8AuxSi46-x clathrate were wider than the intrinsic semiconductor. We can successfully synthesize a n-p junction single crystal, which obtaining energy band curve generated from the difference of Fermi level between p- and n- type semiconductors. The single crystal was heated under the uniform temperature and able to obtain generated electric voltage of around 0.6 mV at 400°C. These results suggested that the obtained electric voltage can be generated from the separation of hole-electron pair excited by heating at the intrinsic part with a narrow band gap along to the energy band curve formed by p-n junction.

We prepared the type-I Ba8AuxSi46-x (x=5.5, 5.4 and 5.33) clathrates with p-type conduction by arc-melting and subsequent annealing. The Seebeck coefficients of all as-synthesized samples were negative. After annealing, in the case of x=5.4 and 5.5, the Seebeck coefficients changed to positive, and in the case of x=5.33, this value was negative for the annealed sample. The chemical composition revealed that Au content in the Ba8AuxSi46-x clathrates increased after the annealing process. The backscattered electron images showed that there were many Au-excess regions which were not clathrate structure in the as-synthesized samples, and these regions decreased and even disappeared after the annealing process. The disappearing of Au-excess regions can be explained by the diffusion of Au atoms from the Au-excess regions into the clathrates. Based on these results, annealing treatment can be used to tune the carrier conduction by controlling the content of Au for type-I Ba8AuxSi46-xclathrates.