Lawrence Berkeley National Laboratory

Niobium oxide exists in several crystal phases and valence states, yielding a variety of properties. Phase transitions between polymorphs significantly alter the properties of functional niobium oxide nanostructures, which are applied in many different renewable energy applications. This study uses environmental transmission electron microscopy to investigate the oxidation of NbO nanowires to T-Nb2O5. Small oxygen partial pressures (<1 mbar) suffice to initiate the oxidation which initially causes the destruction of the lattice ordering prior to the crystallization of the new phase. Different oxygen partial pressures and temperatures are used to manipulate the reaction kinetics. The crystallization is slow at room temperature and confined to the nanowire surface. Elevated temperatures accelerate the crystallization, resulting in the transformation of the complete nanowire. The transformation proceeds via dislocations, yielding the woven-like structure of the transformed nanowire. Despite the dramatic changes of the atomic composition of the material, an orientation relationship between the different phases is preserved. The phase transformation of NbO to T-Nb2O5 observed in situ complies with ex situ phase diagrams. This illustrates the importance of environmental transmission electron microscopy for the investigation of oxidation and reduction reactions of metal oxide nanostructures to identify the impact of shape and intrinsic defects.