Large Closed-Circuit Seebeck Current in Quaternary (Ti,Zr)NiSn Heusler Alloys

In the (Ti _x ,Zr _y )Ni _w Sn _z quaternary system with a composition near (x + y):w:z = 1:1:1 the existence of the half-Heusler (HH) phase has been confirmed, where Ti and Zr occupy one of the three lattice positions substitutionally. The goal of this study is to characterize the thermoelectric (TE) properties of such materials. TE properties were measured at large temperature differences up to ΔT = 800 K, exhibiting Seebeck voltages of about ±50 mV corresponding to Seebeck coefficients above 0.07 mV/K, with the highest value measured for the (Ti_0.4Zr_0.6)Ni_0.9Sn_1.1 composition. Fe and Mn doping could not improve these values further. Measurements under closed-circuit conditions showed very high currents of 0.4 mA for specimens at this particular composition. According to the composition, interfaces between full-Heusler and HH phases are responsible for an electron pull-out phenomenon due to the electric field at their interfaces. First-principle calculations of the electronic band structure confirm this explanation for why (TiZr)NiSn and CrNiSn are p-type TEs whereas NbNiSn is an n-type TE. These considerations will be useful in the search for other such systems.