The change of multivalence band structure configuration between rhombodedral and cubic phase in GeTe offers additional dimension to modify its thermoelectric properties. Here, we report the synergetic optimization of electronic and thermal transport properties in rhombohedral GeTe doped with transition metal Ti. The Seebeck coefficient of Ge 1-x Ti x Te is significantly increased and the corresponding thermal conductivity is decreased. The structure refinement shows that Ti doping could reduce the lattice constant c/a ratio. Density functional theory calculations demonstrate that the affected crystal field rather than Ti orbitals is contributing to the valence band convergence and a Seebeck coefficient enhancement. Further optimization incorporates the effects of Bi substitution for reducing the carrier concentrations and introducing more point defects. This work not only confirms the transition metal elements as promising dopants for GeTe-based materials, but also indicates that the strategy of manipulating the crystal field effect can be exploited as a direct but effective route for improving thermoelectric performance.

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The structural and thermoelectric properties of the filled skutterudite (Sm,Gd)y(FexNi1-x)4Sb12 were investigated and critically compared to the ones in the Sm-containing system with the aim of unravelling the effect of double filling on filling fraction and thermal conductivity. Several samples (x = 0.50–0.90 and y = 0.15–0.48) were prepared by melting-sintering, and two of them were densified by spark plasma sintering in order to study their thermoelectric features. The crystallographic study enables the recognition of the role of the filler size in ruling the filling fraction and the compositional location of the p/n crossover: It has been found that the former lowers and the latter moves toward lower x values with the reduction of the filler ionic size, as a consequence of the progressively weaker interaction of the filler with the Sb12 cavity. The analysis of thermoelectric properties indicates that, despite the Sm3+/Gd3+ small mass difference, the contemporary presence of these ions in the 2a site significantly affects the thermal conductivity of both p- and n-compositions. This occurs by reducing its value with respect to the Sm-filled compound at each temperature considered, and making the overall thermoelectric performance of the system comparable to several multi-filled (Fe, Ni)-based skutterudites described in the literature.

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