Crystallographic data, electrical and thermal transport measurements, and magnetic susceptibility values are reported for several compounds and alloys with the filled skutterudite structure, ( Ce, or Th; 1). Room-temperature velocity of sound data is also reported. These materials are of interest because of their potential in thermoelectric power generation and refrigeration applications. The transport properties of both filled and unfilled skutterudite compounds are analyzed using standard semiconductor transport models. Filled skutterudite antimonides appear to be a good approximation of an idealized solid with the good electrical transport properties of a crystal but the poor heat conduction characteristics of a glass. The incoherent rattling of the weakly bound rare-earth atoms in these materials lowers the thermal conductivity at room temperature to values comparable to that of vitreous silica. Relative to the analogous unfilled compounds, the filled skutterudites exhibit larger effective masses and smaller mobilities. Good overall electrical transport is maintained, however, as evidenced by values for the figure of merit greater than 1 at elevated temperatures (700–1000 K). Above room temperature, there is very little difference in the electrical and thermal transport behavior between the La and Ce filled compounds. The effects of the hybridization caused by the proximity of the Ce level to the Fermi energy, however, are evident at temperatures below 300 K.
Thermoelectrics is an old field. In 1823, Thomas Seebeck discovered that a voltage drop appears across a sample that has a temperature gradient. This phenomenon provided the basis for thermocouples used for measuring temperature and for thermoelectric power generators. In 1838, Heinrich Lenz placed a drop of water on the junction of metal wires made of bismuth and antimony. Passing an electric current through the junction in one direction caused the water to freeze, and reversing the current caused the ice to quickly melt; thus thermoelectric refrigeration was demonstrated (figure 1).
A grand challenge in materials research is to understand complex electronic correlation and non-equilibrium atomic interactions, and how such intrinsic properties and dynamic processes affect energy transfer and defect evolution in irradiated materials. Here we report that chemical disorder, with an increasing number of principal elements and/or altered concentrations of specific elements, in single-phase concentrated solid solution alloys can lead to substantial reduction in electron mean free path and orders of magnitude decrease in electrical and thermal conductivity. The subsequently slow energy dissipation affects defect dynamics at the early stages, and consequentially may result in less deleterious defects. Suppressed damage accumulation with increasing chemical disorder from pure nickel to binary and to more complex quaternary solid solutions is observed. Understanding and controlling energy dissipation and defect dynamics by altering alloy complexity may pave the way for new design principles of radiation-tolerant structural alloys for energy applications.