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Nanoscale CeO2 (nanoceria) is a prototypical system that presents d0ferromagnetism. Using a combination of x-ray absorption spectroscopy, x-raymagnetic circular dichroism and modelling, we show that nanostructure, defectsand disorder, and non-stoichiometry create magnetically polarized Ce 4f and O2p hybridized states captured by the vacancy orbitals (Vorb) that are vital toferromagnetism. Further, we demonstrate that foreign ions (Fe and Co) enhancethe moment at Ce 4f sites while the number of Vorb is unchanged, pointingclearly to the mechanism of orbital hybridization being key missing ingredientto understanding the unexpected ferromagnetism in many nanoscale dilutemagnetic oxides and semiconductors.

Role of Ce 4f hybridization in the origin of magnetism in nanoceria