Phase transformation and room temperature stabilization of various Bi₂O₃ nano-polymorphs: effect of oxygen-vacancy defects and reduced surface energy due to adsorbed carbon species

Abstract

We report the grain growth from the nanoscale to microscale and a transformation sequence from Bi →β-Bi₂O₃→γ-Bi₂O₃→α-Bi₂O₃ with the increase of annealing temperature. The room temperature (RT) stabilization of β-Bi₂O₃ nanoparticles (NPs) was attributed to the effect of reduced surface energy due to adsorbed carbon species, and oxygen vacancy defects may have played a significant role in the RT stabilization of γ-Bi₂O₃ NPs. An enhanced red emission band was evident from all the samples attributed to oxygen-vacancy defects formed during the growth process in contrast with the observed white emission band from the air annealed Bi ingots. Based on our experimental findings, the air annealing induced oxidation of Bi NPs and transformation mechanism within various Bi₂O₃ nano-polymorphs are presented. The outcome of this study suggests that oxygen vacancy defects at the nanoscale play a significant role in both structural stabilization and phase transformation within various Bi₂O₃ nano-polymorphs, which is significant from theoretical consideration.