High temperature thermoelectric properties of the type-I clathrate Ba8NixGe46-x-y□y.

Polycrystalline samples of the type-I clathrate Ba(8)Ni(x)Ge(46-x-y)□(y) were synthesized for 0.2 ⩽ x ⩽ 3.5 by melt quenching and for 3.5<x ⩽ 6.0 by melting with subsequent annealing at 700 °C. The maximum Ni content in the clathrate framework at this temperature was found to be x ≈ 4.2 atoms per unit cell. Thermoelectric and thermodynamic properties of the type-I clathrate were investigated from 300 to 700 K by means of electrical resistivity, thermopower, thermal conductivity and specific heat measurements. As the Ni content increases, the electronic properties gradually evolve from a metallic character (x < 3.5) towards a highly doped semiconducting state (x ⩾ 3.5). Below x ≈ 4.0 transport is dominated by electrons, while further addition of Ni (x ≈ 4.2) switches the electrical conduction to p-type. Maximum value of the dimensionless thermoelectric figure of merit ZT ≈ 0.2 was achieved at 500 K and 650 K for x ≈ 2.0 and x ≈ 3.8, respectively.