Unequal bonding in Ag-CuInSe-based solid solutions responsible for reduction in lattice thermal conductivity and improvement in thermoelectric performance.

Owing to their unique crystal and band structures, in thermoelectrics increasing attention has recently been paid to compounds of the ternary I-III-VI chalcopyrite family. In this work, unequal bonding between cation and anion pairs in Cu Ag InSeTe solid solutions, which can be effectively used to disturb phonon transport, has been proposed. The unequal bonding, which is represented by the difference of bond lengths Δ, Δ = - and anion position displacement from its equilibrium position Δ = - 0.25, is created by the isoelectronic substitution of Ag for Cu. At = 0.2 both the Δ and Δ values reach their maxima, resulting in a remarkable reduction in lattice thermal conductivity ( ) and an improvement in TE performance. However, as the value increase to 0.3 both Δ and Δ values decrease, causing the value to increase and the ZT value to decrease from 0.5 to 0.24 at 930 K. Accordingly, unequal bonding might be an alternative way to improve the TE performance of ternary chalcopyrites.