Microstructures of Annealed TiNiSn-Based Alloy Ribbons

The thermoelectric half-Heusler compounds Ti _x NiSn_0.998Sb_0.002 (x = 1.0 to 1.2) and Ti _y Zr_0.25Hf_0.25NiSn_0.998Sb_0.002 (y = 0.5 to 0.65) with nonstoichiometric nominal compositions were prepared by spin-casting and subsequent annealing at 1073 K for 24 h. The dimensionless figure of merit ZT at room temperature was maximized at x = 1.1 and y = 0.6 in Ti-rich compounds through an increase in absolute Seebeck coefficients despite a decrease in electrical conductivities. ZT reached 0.07 at x = 1.1 and 0.14 at y = 0.6. In powder x-ray diffraction analysis, minor phases of β-Sn, TiNi, Ti₂Sn, and Ti₅Sn₃ were observed in addition to a major phase of half-Heusler. The quantity of the minor phases was minimized at x = 1.1 and y = 0.55, where the absolute Seebeck coefficients are maximized. In transmission electron microscopic (TEM) analysis of Ti_0.55Zr_0.25Hf_0.25NiSn_0.998Sb_0.002, crystal grains of the half-Heusler phase, from several hundred nanometers to several micrometers in size, were observed. TEM energy-dispersive spectroscopy measurements indicated that fluctuations of Ti, Zr, and Hf compositions within the Ti-site in the half-Heusler phase may occur. Thermoelectric properties were improved at x = 1.1 and y = 0.6 rather than at the stoichiometric compositions of x = 1.0 and y = 0.5 due to minimization of the precipitate quantities.