Enargite Cu3PS4: A Cu–S‐Based Thermoelectric Material with a Wurtzite‐Derivative Structure

Abstract

AbstractCompound semiconductors derived from ZnS (zincblende and wurtzite) with tetrahedral framework structures have functions for various applications. Examples of such materials include Cu–S‐based materials with zincblende‐derivative structures, which have attracted attention as thermoelectric (TE) materials over the past decade. This study illuminates superior TE performance in polycrystalline samples of enargite Cu3P1−xGexS4 with a wurtzite‐derivative structure. The substitution of Ge for P dopes holes into the top of the valence band composed of Cu‐3d and S‐3p, whereby its multiband characteristic leads to a high TE power factor. Furthermore, a reduction in the grain size to 50–300 nm can effectively decrease phonon mean free paths, leading to low thermal conductivity. These features result in a dimensionless TE figure of merit ZT of 0.5 at 673 K for the x = 0.2 sample. Environmentally benign and low‐cost characteristics of the constituent elements of Cu3PS4, as well as its high‐performance thermoelectricity, make it a promising candidate for large‐scale TE applications. Furthermore, this finding extends the development field of Cu–S‐based TE materials to those with wurtzite‐derivative structures.