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Knowledge of the electronic band structure of multiferroic oxides, crucialfor the understanding and tuning of photo-induced effects, remains very limitedeven in the model and thoroughly studied BiFeO3. Here, we investigate theelectronic band structure of BiFeO3 using Raman scattering with twelvedifferent excitation wavelengths ranging from the blue to the near infrared. Weshow that resonant Raman signatures can be assigned to direct and indirectelectronic transitions, as well as in-gap electronic levels, most likelyassociated to oxygen vacancies. Their temperature evolution establishes thatthe remarkable and intriguing variation of the optical band-gap can be relatedto the shrinking of an indirect electronic band-gap, while the energies fordirect electronic transitions remains nearly temperature independent.

Temperature evolution of the band-gap in BiFeO3 traced by resonant Raman scattering