Skutterudite

Abstract: Skutterudites CoSb3 with multiple cofillers Ba, La, and Yb were synthesized and very high thermoelectric figure of merit ZT = 1.7 at 850 K was realized. X-ray diffraction of the densified multiple-filled bulk samples reveals all samples are phase pure. High-resolution scanning transmission electron microscopy (STEM) and energy dispersive X-ray spectroscopy (EDS) analysis confirm that multiple guest fillers occupy the nanoscale-cages in the skutterudites. The fillers are further shown to be uniformly distributed and the Co−Sb skutterudite framework is virtually unperturbed from atomic scale to a few micrometers. Our results firmly show that high power factors can be realized by adjusting the total filling fraction of fillers with different charge states to reach the optimum carrier density, at the same time, lattice thermal conductivity can also be significantly reduced, to values near the glass limit of these materials, through combining filler species of different rattling frequencies to achieve broad-fr...

Abstract: Crystallographic data, electrical and thermal transport measurements, and magnetic susceptibility values are reported for several compounds and alloys with the filled skutterudite structure, R{sub 1{minus}y}Fe{sub 4{minus}x}Co{sub x}Sb{sub 12} (R=La, Ce, or Th; 0{lt}y{lt}1; x=0,1). 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 (ZT) greater than 1 at elevated temperatures (700{endash}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 themore » hybridization caused by the proximity of the Ce 4f level to the Fermi energy, however, are evident at temperatures below 300 K. {copyright} {ital 1997} {ital The American Physical Society}« less

Abstract: A study of the thermoelectric properties of the skutterudite compound CoSb3 was carried out on single crystals grown by the Bridgman gradient freeze technique. p‐ and n‐type samples were obtained over a wide range of carrier concentration. Undoped As‐grown crystals show p‐type conductivity while n‐type samples were obtained by addition of Te or Pd. Samples were characterized by x‐ray diffractometry, electron microprobe analysis, and density measurements. The physical properties of CoSb3 such as linear thermal expansion coefficient, sound velocity, and Debye temperature were also determined and are presented. Seebeck coefficient, electrical resistivity, thermal conductivity, and Hall effect measurements were performed between room temperature and about 900 K. Exceptionally high Hall mobilities were obtained on p‐type samples with a maximum room‐temperature Hall mobility of 3300 cm2 V−1 s−1 at a carrier concentration of 1×1017 cm−3. The results of the transport property measurements are discussed and are in agreement with some recent predictions based on band structure calculations. The potential of CoSb3 for thermoelectric applications is evaluated.

Abstract: Polycrystalline samples of antimonides with the skutterudite crystal structure with La partially filling the voids have been prepared in an effort to quantify the impact of partial void filling on the lattice thermal conductivity of these compounds. It is observed that a relatively small concentration of La in the voids results in a relatively large decrease in the lattice thermal conductivity. In addition, the largest decrease in the lattice thermal conductivity, compared to ‘‘unfilled’’ CoSb 3 is not observed near 100% filling of the voids with La, as was previously believed. This suggests a point-defect-type phonon scattering effect due to the partial, random distribution of La in the voids as well as the ‘‘rattling’’ effect of the La ions, resulting in the scattering of a larger spectrum of phonons than in the case of 100% filling. An additional benefit of partial filling in thermoelectric materials is that it may be one way of adjusting the electronic properties of these compounds. Seebeck, resistivity, Hall effect and structural data for these skutterudite compounds are also presented. @S0163-1829~98!02926-9#