Compositions and thermoelectric properties of XNiSn (X = Ti, Zr, Hf) half-Heusler alloys

Rietveld analysis of neutron powder diffraction data has been used to investigate the compositions of XNiSn (X = Ti, Zr, Hf) half-Heusler alloys prepared by solid state reactions. All samples containing Ti have 2-3% excess Ni, whereas the samples with X = Zr, Hf are almost stoichiometric. Samples with mixed X-metals are characterised by the presence of 3-4 distinct X1-xX’xNi1+ySn half-Heusler phases. Variable temperature and time dependent neutron powder diffraction for X = Ti and X = Ti0.5Hf0.5 demonstrates that both the amount of excess Ni and the phase distribution are stable up to at least 600 C. Debye temperatures of 367(2) K and 317(2) K were obtained from the thermal displacement parameters. The samples containing Ti are characterised by a ~0.15 eV bandgap and a monotonously decreasing Seebeck coefficient. The compositions with Zr and Hf have similar bandgap values but show ambipolar transitions. Analysis of the thermoelectric transport data of degenerately doped Ti0.5Zr0.5NiSn1-zSbz samples using a single parabolic band model demonstrates that the transport is limited by alloy scattering and yielded an effective carrier mass of 2.5(1) me.