Electron beam-induced structural transformations of MoO3 and MoO3−x crystalline nanostructures

Electron beam-induced damage and structural changes in MoO3 and MoO3−x single crystalline nanostructures were revealed by in situ transmission electron microscopy (TEM) examination (at 200 kV) after few minutes of concentrating the electron beam onto small areas (diameters between 25 and 200 nm) of the samples. The damage was evaluated recording TEM images, while the structural changes were revealed acquiring selected area electron diffraction patterns and high resolution transmission electron microscopy (HRTEM) images after different irradiation times. The as-received nanostructures of orthorhombic MoO3 were transformed to a Magnéli's phase of the oxide (γ-Mo4O11) after ∼10 min of electron beam irradiation. The oxygen loss from the oxide promoted structural changes. HRTEM observations showed that, in the first stage of the reduction, oxygen vacancies generated by the electron beam are accommodated by forming crystallographic shear planes. At a later stage of the reduction process, a polycrystalline structure was developed with highly oxygen-deficient grains. The structural changes can be attributed to the local heating of the irradiated zone combined with radiolysis.