Abstract
CoSb3 is a very promising thermoelectric semiconductor with narrow gap and good electrical transport properties. It is also a special compound with an intrinsically caged crystal structure. By taking void filling in the intrinsic cages and impurity substitution for Co in the skutterudites as examples, a few phase-diagram-related problems in thermoelectric materials are discussed. The first topic shows that the filling fraction limit for an impurity in the crystal voids could be taken as a phase-diagram-related issue to be solved by first-principles energetic calculations. But the partial void filling also reveals that the structural integrity of a compound with special structure is very sensitive to electron filling and its influence on chemical bonding, which needs further study. This is assumed to be a general problem linking with the group of compounds with special 2-D layered or 3-D caged structures, a focus of current thermoelectric research. The second topic relates to the solid solution problem when mixing CoSb3 with IrSb3 (or RhSb3) to realize new materials with random distribution of Ir or Rh at Co sites. By going through most of the currently state-of-the-art thermoelectric compounds including CoSb3/IrSb3, PbTe/(Ag,Sb)Te2, MgSi2/MgSn2/MgGe2, and ZrNiSn/HfNiSn, it is found that their mixing enthalpies are usually slightly positive, implying the possibility of mixing 2- or 3-similar compounds to realize nanocomposites with low internal strain for promising performance. Related experimental and theoretical issues on nanocomposite thermoelectrics are briefly discussed.
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