Thermoelectric properties of pnictogen-substituted skutterudites with alkaline-earth fillers using first-principles calculations.

First-principles calculations have been performed to investigate electronic band structures, vibrational characters, and related transport properties of pnictogen-substituted skutterudites filled with alkaline-earth elements (MxCo4A6B6, where M=Ca, Sr, or Ba, A=Ge or Sn, B=Se or Te, and x=0.5 or 1). Electronic transport properties related to thermoelectricity, including the Seebeck coefficient and the electrical conductivity, are computed by using the Boltzmann transport formalism within the constant-relaxation-time approximation. The results are compared against the corresponding properties of the unfilled pnictogen-substituted ternary skutterudites (CoA1.5B1.5) to identify the effects of filling to estimate the potential for thermoelectric applications. The changes in the ionic character of the interatomic bonding between the Group 14 (A) and Group 16 (B) elements, which was suspected to be a major scattering source in unfilled pnictogen-substituted ternary skutterudites, are probed by analyzing the projected density of states, the charge densities, and the Born effective charges, in an attempt to identify a potential path for improvement of the thermoelectric performance. Our computational results suggest that the analyzed performance of the filled pnictogen-substituted skutterudites should exhibit no significant improvement over that of the corresponding unfilled pnictogen-substituted ternary skutterudites, unless significant reduction in thermal conductivity is achieved by the rattling motion of the filler atoms. [ABSTRACT FROM AUTHOR]