Electronic and optical properties of the fully and partially inverse CoFe$_{2}$O$_{4}$ spinel from first principles calculations including many-body effects

Abstract

Using density functional theory (DFT) calculations and state-of-the-art many-body perturbation theory, we investigate the electronic and optical properties of the inverse spinel CoFe$_{2}$O$_{4}$, a common anode material for photocatalytic water splitting. Starting with different exchange-correlation functionals, at the independent particle level we obtain a direct band gap of 1.38~eV (PBE+$U$) and 1.69 eV (SCAN+$U$), whereas HSE06 renders an indirect band gap of 2.02~eV. Including quasiparticle effects within $G_{0}W_{0}$, a larger and indirect band gap is obtained for all functionals: 1.78~eV (PBE+$U$), 1.95~eV (SCAN+$U$) and 2.17~eV (HSE06), higher than the independent particle (IP) band gap. Excitonic effects, taken into account by solving the Bethe-Salpeter equation (BSE) lead to a redshift of the optical band gap to 1.50 (SCAN+$U$) and 1.61~eV (HSE06), in good agreement with the reported experimental values. The lowest optical transitions in the visible range, identified by means of oscillator strength, are at 2.0, 3.5, and 5.0~eV, consistent with experimental observations. We also explored the effect of the degree of inversion: the band gap is found to decrease from 1.69 ($x=1$) to 1.45 ($x=0.5$), and 1.19~eV ($x=0)$ within the IP approximation with SCAN+$U$. This trend is reversed after the inclusion of excitonic effects, resulting in a band gap of 1.50, 1.57, and 1.64~eV for $x$ = 1.0, 0.5, and 0.0, respectively. The oscillator strength analysis of the BSE calculations indicates that both $x$ = 0.0 and $x$ = 0.5 exhibit transitions below 1~eV with extremely small oscillator strengths that are absent in the inverse spinel. This corroborates previous suggestions that these transitions are due to the presence of Co$^{2+}$ cations at the tetrahedral sites.