Thermoelectric properties of (Ba,K)CdAs crystallized in the CaAlSi-type structure.

As-Based Zintl compounds Ba1-xKxCd2As2 crystallized in the CaAl2Si2-type structure (space group P3[combining macron]m1) were prepared using solid-state reactions followed by hot-pressing. We have successfully substituted K for Ba up to x = 0.08, producing hole-carrier doping with concentrations up to 1.60 × 1020 cm-3. We have determined the band-gap value of non-doped BaCd2As2 to be 0.40 eV from the temperature dependence of the electrical resistivity. Both the electrical resistivity and the Seebeck coefficient decrease with hole doping, leading to a power factor value of 1.28 mW m-1 K-2 at 762 K for x = 0.04. A first-principles band calculation shows that the relatively large power factor mainly originates from the two-fold degeneracy of the bands comprising As px,y orbitals and from the anisotropic band structure at the valence-band maximum. The lattice thermal conductivity is suppressed by the K doping to 0.46 W m-1 K-1 at 773 K for x = 0.08, presumably due to randomness. The effect of randomness is compensated by an increase in the electronic thermal conductivity, which keeps the total thermal conductivity approximately constant. In consequence, the dimensionless figure-of-merit ZT reaches a maximum value of 0.81 at 762 K for x = 0.04.