High temperature thermoelectric properties of Zr and Hf based transition metal dichalcogenides: A first principles study

We investigate the electronic and thermal transport properties of bulk MX₂ compounds (M = Zr, Hf and X = S, Se) by first-principles calculations and semi-classical Boltzmann transport theory. The band structure shows the confinement of heavy and light bands along the out of plane and in-plane directions, respectively. This results in high electrical conductivity (σ) and large thermopower leading to a high power factor (S²σ) for moderate n-type doping. The phonon dispersion demonstrates low frequency flat acoustical modes, which results in low group velocities (v_g). Consequently, lowering the lattice thermal conductivity (κ_latt) below 2 W/m K. Low κ_latt combined with high power factor results in ZT > 0.8 for all the bulk MX₂ compounds at high temperature of 1200 K. In particular, the ZT_max of HfSe₂ exceeds 1 at 1400 K. Our results show that Hf/Zr based dichalcogenides are very promising for high temperature thermoelectric application.