Improving thermoelectric performance of TiNiSn by mixing MnNiSb in the half-Heusler structure.

The thermoelectric properties of the n-type semiconductor TiNiSn were optimized by partial substitution with metallic MnNiSb in the half Heusler structure. Herein, we study the transport properties and intrinsic phase separation in the Ti1-xMnxNiSn1-xSbx system. The alloys were prepared by arc-melting and annealed at temperatures obtained from differential thermal analysis and differential scanning calorimetry results. The phases were characterized using powder X-ray diffraction patterns, energy-dispersive X-ray spectroscopy, and differential scanning calorimetry. After annealing, the majority phase was TiNiSn with some Ni-rich sites, and the minority phases were primarily Ti6Sn5, Sn and MnSn2. The Ni-rich sites were caused by Frenkel defects; this led to metal-like behavior in the semiconductor specimens at low temperature. For x ≤ 0.05 the samples showed an activated conduction, whereas for x > 0.05 they showed metallic character. The figure of merit for x = 0.05 was increased by 61% (zT = 0.45) in comparison with the pure TiNiSn.

Long-term stability of phase-separated half-Heusler compounds.

Half-Heusler (HH) compounds have shown high figure of merit up to 1.5. Here, we address the long-term stability of n- and p-type HH materials. For this purpose, we investigated HH materials based on the Ti0.3Zr0.35Hf0.35NiSn-system after 500 cycles (1700 h) from 373 to 873 K. Both compounds exhibit a maximum Seebeck coefficient of |α|≈ 210 µV K(-1) and a phase separation into two HH phases. The dendritic microstructure is temperature resistant and upon cycling the changes in the microstructure are so marginal that the low thermal conductivity values (κ < 4 W m(-1) K(-1)) could be maintained. Our results emphasize that phase-separated HH compounds are suitable low cost materials and can lead to enhanced thermoelectric efficiencies beyond the set benchmark for industrial applications.

Evidence for localized moment picture in Mn-based Heusler compounds.

X-ray absorption spectroscopy (XAS) and X-ray magnetic circular dichroism (XMCD) were used to probe the electronic structure and magnetic moment of Mn in Heusler compounds with different crystallographic structure. The results were compared with theoretical calculations of the magnetic and electronic properties, and it was found that in full and half Heusler alloys, Mn is metallic on both sublattices. The magnetic moment is large and localized when octahedrally coordinated by the main group element, consistent with previous theoretical work, and reduced when the main group coordination is tetrahedral. The magnetic and electronic properties of Mn in full and half Heusler compounds are strongly dependent on the structure and sublattice, a fact that can be exploited to design new materials.