Effect of high oxygen deficiency in nano-confined bismuth sesquioxide

Bismuth sesquioxidein its cubic form, i.e.delta-Bi2O3,is the fastest oxygen ionic conductor knownwith important applications in energy technologies.However, the material is unstable asit undergoes to high-density polymorphic transitionsand degradation. In this work, we show that delta-Bi2O3can be stabilized both at high and low temperatures (T < 775°C) under low oxygen partial pressure (pO2< 10-5atm), where the material is nanostructured in multi-layered thin film coherent heterostructures with yttriumstabilized zirconia(YSZ).DFT calculation confirms sucha form of metastability, also showingthat highoxygen defect concentration favorsthe cubic phase.Moreover, high oxygen deficiencyin the nanoionics leadsto an unexpected“two-regime” conductivitywith high values(sigma> 1 S cm-1at 600 °C)at high pO2and lowerionic conductivity (sigma~0.1 S cm-1at 600 °C) at low pO2.Ionic conductivity at low pO2occurs with high activation energy (Ea > 1.5 eV), suggestingthusa drastic decrease in mobility for high concentration of defects.