Theoretical Investigation on the Effect of multinary Isoelectronic Substitution on TiCoSb based half-Heusler alloys

TL;DR

This theoretical study investigates how multinary isoelectronic substitution affects the electronic and thermoelectric properties of TiCoSb-based half-Heusler alloys, revealing limited ZT improvement with dual-site substitution.

Contribution

It provides a systematic theoretical analysis of isoelectronic substitution effects on band structure and thermoelectric properties in TiCoSb alloys, highlighting the limited impact on ZT.

Findings

Substitution shifts Fermi level and tunes band gap.

Small ZT increase observed with dual-site substitution.

Band structure analysis reveals semiconducting behavior with varying band gaps.

Abstract

To understand the effect of isoelectronic substitution on thermoelectric properties of TiCoSb based half - Heusler (HH) alloys, we have systematically studied the transport properties with substitution of Zr at Ti and Bi at Sb sites. The electronic structure of TixZr1-xCoSbxBi1-x (x = 0.25, 0.5, 0.75) and parent TiCoSb are investigated using the full potential linearized augmented plane wave method and the thermoelectric transport properties are calculated on the basis of semiclassical Boltzmann transport theory. The band analysis of the calculated band structures reveal that TixZr1-xCoSbxBi1-x has semiconducting behavior with indirect band gap at x = 0.25, 0.5 concentration and direct band gap behavior at x = 0.75 concentration. The TixZr1-xCoSbxBi1-x (x = 0.25, 0.5, 0.75) compounds show smaller band gap values as compared to the pure TiCoSb. The d electrons of Ti/Zr and Co dominate the electronic transport properties of TixZr1-xCoSbxBi1-x system. All these systems follow the empirical rule of 18 valence-electron content to bring semiconductivity in HH alloys. The isoelectronic substitution in TiCoSb can tune the band structure by shifting the Fermi level. This provides us lot of possibilities to get the desired band gap values for designing thermoelectrics with high efficiency. In this study we have showed that the isoelectronic substitution at both Ti and Sb site of TiCoSb has very small effect for increasing the ZT values and one should go for isoelectronic substitution at any one sites of TiCoSb HH alloys alone to improve ZT.