First principles study on the thermoelectric performance of CaAl$_2$Si$_2$-type Zintl phase compounds

Abstract: We investigate the thermoelectric properties of CaAl$2$Si$_2$-type Zintl phase compounds $AB_2X_2$ ($A$ = Mg, Ca, Sr, Ba, $B$ = Mg, Zn, Cd, and $X$ = P, As, Sb) using first principles band calculations within the Boltzmann transport theory assuming the constant relaxation time approximation. We introduce the effective degree of valley degeneracy $n{TE}$ to focus on the relationship between the thermoelectric properties and the multivalley character of the electronic band structure around the Fermi level. We also introduce a quantity $\gamma_{TE}$, which takes into account $n_{TE}$ and anisotropy of the valley structure, and it is found that $\gamma_{TE}$ enables us to well understand the overall trend of the material dependence of the power factor. We finally suggest promising thermoelectric materials, e.g. BaMg$_2$P$_2$ for PF $\sim 20\mu$W/cmK$^2$ and $ZT > 0.2$ at 300K and SrZn$_2$As$_2$ for PF $\sim 35\mu$W/cmK$^2$ and $ZT > 0.35$ at 300K assuming a relaxation time of 10 fs and a lattice thermal conductivity value of 2 W/mK.