Systematic Study of Lattice Specific Heat of Filled Skutterudites

Abstract

The lattice specific heat C lat of La-based filled skutterudites La T 4 X 12 ( T = Fe, Ru and Os; X = P, As, and Sb) has been systematically studied, and both the Debye temperature Θ D and the Einstein temperature Θ E of La T 4 X 12 were carefully estimated. We confirmed that a correlation exists between Θ D and the reciprocal of the square root of average atomic mass for La T 4 P 12 , La T 4 As 12 , and La T 4 Sb 12 . The Θ D of filled skutterudites was found to depend mainly on the nature of the species X forming the cage. The temperature dependence of C lat / T 3 for La T 4 X 12 exhibited a large broad maximum at low temperatures (10–30 K), which suggests a nearly dispersionless low-energy optical mode characterized by Einstein specific heat. Since no such broad maximum exists for the unfilled skutterudite RhP 3 , the low-energy optical modes are associated with vibration involving La ions in the X 12 cage (the so-called "guest ion modes"). The Θ E of filled skutterudites was found to roughly correspond to the energy of low-energy guest ion optical modes. Furthermore, a good correlation was shown to exist between Θ E and r R–X - r R3+ , where r R–X is the R – X distance and r R3+ is the effective ionic radius of R 3+ . As r R–X - r R3+ increased, Θ E was found to decrease.