Effects of doping on the transport properties of CoSb3 have been systematically investigated using Ni, Pd, and Pt as donor impurities. It is shown that the Hall mobility, the Seebeck coefficient, and the electrical conductivity depend strongly not only on the carrier concentration but also on these donor impurities. Our theoretical analysis suggests that the electron effective mass and the conduction band deformation potential are significantly affected by both the doping levels and the donor impurities. These doping effects in CoSb3 can be attributed to (1) the changes in the electronic structure with doping and (2) the specific nature of the conduction band structure, in particular, the nonparabolicity of the band which can be explained in terms of a two-band Kane model. The observed changes in the electronic properties with doping are also consistent with the predictions of a recent band structure calculation of CoSb3. On the other hand, the lattice thermal conductivity decreases markedly with increasing carrier concentration, and is almost independent of the donor impurities. Our analysis based on the Debye model indicates that the coupling of the point-defect (alloy) scattering with the electron-phonon scattering plays an important role in reducing the lattice thermal conductivity in heavily doped n-type CoSb3. The effects of doping on the phonon scattering are also discussed on the basis of a model calculation as a function of the electronic properties and the impurity properties (atomic mass and size). As a result, it is found that the strength of the electron-lattice interaction (the electron-phonon coupling), which is closely related to the effective mass and the deformation potential, is an important factor affecting the scattering of phonons as well as charge carriers in heavily doped n-type CoSb3.

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The structural and electronic transport properties of polycrystalline p-type CoSb3 with different grain sizes (about 3 and 3×102 μm) were investigated. The magnetic susceptibility was also measured. Samples were characterized by x-ray diffractometry, electron-probe microanalysis, and optical microscope observation. Samples were found to be stoichiometric and homogeneous. The Hall carrier concentration of the samples is of the order of 1018 cm−3 and weakly dependent on the temperature. The temperature dependence of the Hall mobility suggests that the predominant scattering mechanism drastically changes depending on grain size: for large grain size a combination of the neutral impurity scattering and the acoustic phonon scattering, and for small grain size the ionized impurity scattering. The magnetic susceptibility was found to be essentially diamagnetic independently of grain size, and to vary slightly with temperature. The weak temperature dependence of the susceptibility can be explained by taking into account the three contributions of ion cores, conduction electrons, and trace amounts of magnetic impurities. From the analysis of the susceptibility due to conduction electrons, the band gap energy was determined to be about 70–80 meV, consistent with a recent band structure calculation. Although the effects of nonmagnetic impurity phases segregated (Sb, etc.) on the scattering mechanism are not clear, the grain size is one of the key factors determining the transport properties of polycrystalline CoSb3.

We have prepared polycrystalline n-type Ba 8 Cu x Ga y Ge 46ÀxÀy (x ¼ 0{5, y ¼ 16 À 3x) clathrate compounds by arc melting and spark plasma sintering techniques and investigated the effect of Cu substitution for Ge on their thermoelectric properties. The Hall carrier concentration for Cu-substituted compounds is almost constant at the order of 10 20 cm À3 , which is comparable to that for Ba 8 Ga 16 Ge 30 stoichiometric compounds. The Seebeck coefficient for these compounds is comparable to that for n-Ba 8 Ga y Ge 46Ày compounds. From the analysis of the properties, the effective mass of the conduction band is estimated to be about 1.4 m 0 , which is equivalent to or slightly smaller than that of n-Ba 8 Ga y Ge 46Ày compounds. The Hall mobility increases as the Cu composition increases. Its temperature dependence obeys approximately T À1=2 dependence in the range of 80-300 K, indicating the dominance of the alloy disorder scattering. Two models are discussed to account for the reduction in the alloy disorder scattering by Cu substitution.