Bismuth sesquioxide in its cubic form, i.e. δ-Bi 2 O 3 , is the fastest oxygen ionic conductor known which has important applications in energy technologies. However, the material is unstable as it undergoes high-density polymorphic transitions and degradation. In this work, we show that δ-Bi 2 O 3 can be stabilized both at high and low temperatures (T<775°C) under low oxygen partial pressure (pO 2 <10 −5 atm), where the material is nanostructured in multilayered thin film coherent heterostructures with yttrium stabilized zirconia. Density Functional Theory calculation confirms such a form of metastability, also showing that high oxygen defect concentration favors the cubic phase. Moreover, high oxygen deficiency in the nanoionics leads to an unexpected 'two-regime' conductivity with high values (σ>1 S cm −1 at 600°C) at high pO 2 and lower ionic conductivity (σ∼0.1 S cm −1 at 600°C) at low pO 2 . Ionic conductivity at low pO 2 occurs with high activation energy (Ea>1.5 eV), suggesting a drastic decrease in mobility for high concentration of defects.
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