Pd₂Se₃ Monolayer: A Promising Two-Dimensional Thermoelectric Material with Ultralow Lattice Thermal Conductivity and High Power Factor

A high power factor and low lattice thermal conductivity are two essential ingredients of highly efficient thermoelectric materials. Although monolayers of transition-metal dichalcogenides possess high power factors, high lattice thermal conductivities significantly impede their practical applications. Our first-principles calculations show that these two ingredients are well fulfilled in the recently synthesized Pd2Se3 monolayer, whose crystal structure is composed of [Se2]2– dimers, Se2– anions, and Pd2+ cations coordinated in a square-planar manner. Our detailed analysis of third-order interatomic force constants reveals that the anharmonicity and soft phonon modes associated with covalently bonded [Se2]2– dimers lead to ultralow lattice thermal conductivities in Pd2Se3 monolayers (1.5 and 2.9 W m–1 K–1 along the a- and b-axes at 300 K, respectively), which are comparable to those of high-performance bulk thermoelectric materials such as PbTe. Moreover, the “pudding-mold” type band structure, caused by Pd2+ (d8) cations coordinated in a square-planar crystal field, leads to high power factors in Pd2Se3 monolayers. Consequently, both electron- and hole-doped thermoelectric materials with a considerably high zT can be achieved at moderate carrier concentrations, suggesting that Pd2Se3 is a promising two-dimensional thermoelectric material. Our results suggest that hierarchical chemical bonds, that is, coexistence of different types of chemical bonds, combined with a square-planar crystal field is a promising route for designing high-efficiency thermoelectric materials