Orbital Alignment for High Performance Thermoelectric YbCd₂Sb₂ Alloys

As a typical class of Zintl thermoelectrics, AB2C2 (A = Eu, Yb, Ba, Ca, Mg; B = Zn, Cd, Mg, and C = Sb, Bi) compounds have shown a superior thermoelectric performance, largely stemming from the existence of multiple transporting bands in both conduction types. Being similar to many III–V and elemental semiconductors, the transport of holes in AB2C2 Zintls usually involves multiple valence bands with extrema at the Brillouin zone center Γ. However, these valence bands, originating from different orbitals, are unnecessarily aligned in energy due to the crystal field splitting. Formation of solid solutions between constituent compounds having opposite arrangements in energy of band orbitals is believed to be particularly helpful for thermoelectric enhancements, because orbital alignment increases band degeneracy while alloy defects scatter phonons. These effects are simultaneously realized in this work, where the p orbitals of anions in YbCd2–xZnxSb2 alloys are well-aligned for maximizing the electronic performance, and meanwhile high-concentration Cd/Zn substitutions are introduced for minimizing the lattice thermal conductivity. As a result, a significantly enhanced thermoelectric figure of merit, zT ∼ 1.3, is achieved, being a record among AB2C2 Zintls in p-type. This work demonstrates not only YbCd2–xZnxSb2 alloys as efficient thermoelectrics but also orbital alignment as an effective strategy for advancing thermoelectrics.