Infrared study on the electronic structure of the alkaline-earth-filled skutteruditesAM4Sb12(A=Sr,Ba;M=Fe,Ru,Os)

The optical conductivity [$\sigma(\omega)$] spectra of alkaline-earth-filled skutterudites with the chemical formula $A^{2+}M_{4}$Sb$_{12}$ ($A$ = Sr, Ba, $M$ = Fe, Ru, Os) and a reference material La$^{3+}$Fe$_{4}$Sb$_{12}$ were obtained and compared with the corresponding band structure calculations and with calculated $\sigma(\omega)$ spectra to investigate their electronic structures. At high temperatures, the energy of the plasma edge decreased with the increasing valence of the guest atoms $A$ in the Fe$_{4}$Sb$_{12}$ cage indicating hole-type conduction. A narrow peak with a pseudogap of 25 meV was observed in SrFe$_{4}$Sb$_{12}$, while the corresponding peak were located at 200 and 100 meV in the Ru- and Os-counterparts, respectively. The order of the peak energy in these compounds is consistent with the thermodynamical properties in which the Os-compound is located between the Fe- and Ru-compounds. This indicated that the electronic structure observed in the infrared $\sigma(\omega)$ spectra directly affects the thermodynamical properties. The band structure calculation implies the different electronic structure among these compounds originates from the different $d$ states of the $M$ ions.