Metallic Oxides and the Overlooked Role of Bandwidth

Abstract

Oxides exhibiting metallic conduction are crucial for various applications, including fuel cells, battery electrodes, resistive and magnetoresistive materials, electrocatalysts, transparent conductors, and high-temperature superconductors. Oxides that approach metallicity also play significant roles in switching applications, where the metal-insulator transition phenomenon is utilized across a range of technologies. This perspective, motivated by the question of when oxides are metallic, employs electronic structure calculations on metallic oxides to identify the typical feature in the electronic structures that promote metallic behavior. The critical factor of the bandwidth of the electronic energy bands near the Fermi energy is emphasized since it has been somewhat overlooked in the literature. For example, bandwidth considerations would suggest that the recently proposed phosphate "LK-99" would never be a suitable target for superconductivity. From the analysis performed here, we learn that if the width of the conduction band as obtained from density functional theory-based electronic structure calculations is less than 1 eV, then the likelihood of obtaining a metallic compound is vanishingly small. This survey of representative oxide metals highlights the essential elements of extended covalency that lead to wide bands. A key takeaway is that oxyanion compounds such as borates, carbonates, silicates, sulfates, nitrates, and phosphates are unlikely to exhibit metallic conduction at ambient pressure. While the focus here is on oxides, the general findings should apply across various material families, extending to organic crystals, polymers, and framework materials.