Rational Design of 3d Transition-Metal Compounds for Thermoelectric Properties by Using Periodic Trends in Electron-Correlation Modulation
I. Ohkubo, Takao Mori
Abstract
The electronic structures in solid-state transition-metal compounds can be represented by two parameters: the charge-transfer energy (Δ), which is the energy difference between the p-band of an anion and an upper Hubbard band contributed by transition-metal d-orbitals, and the onsite Coulomb repulsion energy (U), which represents the energy difference between lower and upper Hubbard bands composed of split d-orbitals in transition metals. These parameters can facilitate the classification of various types of electronic structures. In this study, the dependences of anion species (N3–, P3–, As3–, O2–, S2–, Se2–, Te2–, F–, Cl–, Br–, and I–) on Δ and U of 566 different binary and ternary 3d transition-metal compounds were investigated using ionic-model calculations. We were able to identify the systematic chemical trends in the variations in Δ and U values with the anion species of 11 different families of 3d transition-metal compounds in a comprehensive manner. The effective use of Δ−U diagrams given here, to facilitate the discovery and development of functional compounds, was demonstrated on thermoelectric compounds by classifying the thermoelectric properties of 3d transition-metal compounds and by predicting unrealized high-performance thermoelectric compounds.