Localized and mixed valence state of Ce 4f in superconducting and ferromagnetic CeO1-x FxBiS2 revealed by x-ray absorption and photoemission spectroscopy

We have performed Ce L3-edge x-ray absorption spectroscopy (XAS) and Ce 4d-4f resonant photoemission spectroscopy (PES) on single crystals of CeO1−xFxBiS2 for x = 0.0 and 0.5 in order to investigate the Ce 4f electronic states. In Ce L3-edge XAS, a mixed valence of Ce was found in the x = 0.0 sample, and F doping suppressed it, which is consistent with the results on polycrystalline samples. As for resonant PES, we found that the Ce 4f electrons in both x = 0.0 and 0.5 systems respectively formed a flat band at 1.0 and 1.4 eV below the Fermi level and there was no contribution to the Fermi surfaces. Interestingly, Ce valence in CeOBiS2 deviates from Ce3+ even though Ce 4f electrons are localized, indicating the Ce valence is not in a typical valence fluctuation regime. We assume that localized Ce 4f in CeOBiS2 is mixed with unoccupied Bi 6pz, which is consistent with a previous local structural study. Based on the analysis of the Ce L3-edge XAS spectra using Anderson’s impurity model calculation, we found that the transfer integral becomes smaller, increasing the number of Ce 4f electrons upon the F substitution for O.