Optical absorption and spectral photoconductivity in α-(Fe_1−<i>x</i>Cr_<i>x</i>)₂O₃ solid-solution thin films

Abstract

Hematite, α-Fe2O3, is an attractive narrow gap oxide for consideration as an efficient visible light photocatalyst, with significant potential for band gap engineering via doping. We examine optical absorption in α-(Fe1-xCrx)2O3 epitaxial films and explain the observed excitations, and the nature of the band gap dependence on x, through first-principles calculations. The calculated and measured optical band gap becomes smaller than that of bulk α-Fe2O3 and reaches a minimum as the Cr cation fraction increases to 50%. The lowest energy transitions in the mixed-metal alloys involve electron excitation from occupied Cr 3d orbitals to unoccupied Fe 3d orbitals, and they result in a measurable photocurrent. The onset of α-Fe2O3 photoconductivity can be reduced by nearly 0.5 eV (to 1.60 eV) through addition of Cr.