Anharmonicity Driven by Vacancy Ordering Unlocks High-Performance Thermoelectric Conversion in Defective Chalcopyrites II-III 2 -VI 4

Abstract Defective chalcopyrites have recently emerged as promising thermoelectric materials because their ordered intrinsic vacancies can profoundly reshape both lattice dynamics and electronic structure. Here, we present a comprehensive theoretical investigation of the lattice thermal and carrier transport properties of II-III 2 -VI 4 defective chalcopyrites by combining first-principles calculations with machine-learning interatomic potentials. We show that vacancy ordering enhances lattice distortion, leading to strong anharmonicity and metavalent bonding. The interplay of soft low-frequency phonons, strongly negative Grüneisen parameters, and a substantially enlarged four-phonon-scattering phase space strongly regulates heat transport, yielding an ultralow lattice thermal conductivity. Meanwhile, systematic anion substitution at the VI-site provides an effective route to tune the electronic structure: reduced anion electronegativity weakens metal-anion hybridization, shifts anion p states upward, narrows the band gap, and thereby improves electrical transport. Benefiting from this synergy between vacancy-induced phonon suppression and anion-regulated electronic optimization, CdGa 2 Te 4 exhibits an ultralow lattice thermal conductivity of 0.19 W·m −1 ·K −1 and a high room-temperature ZT of 0.689. This work not only predicts defective chalcopyrites as a promising platform for high-performance thermoelectrics but also provides a practical design strategy by integrating vacancy ordering, higher-order phonon scattering, and anion-dependent band engineering.