Analytical electron microscopy analysis of insulating and metallic phases in nanostructured vanadium dioxide

Vanadium dioxide (VO₂) is a strongly correlated material that exhibits the insulator-to-metal transition (IMT) near room temperature, which makes it a promising candidate for applications in nanophotonics or optoelectronics. However, creating VO₂ nanostructures with the desired functionality can be challenging due to microscopic inhomogeneities that can significantly impact the local optical and electronic properties. Thin lamellas, produced by focused ion beam milling from a homogeneous layer, provide a useful prototype for studying VO₂ at the truly microscopic level using a scanning transmission electron microscope (STEM). High-resolution imaging is used to identify structural inhomogeneities while electron energy-loss spectroscopy (EELS) supported by statistical analysis helps to detect V _<i>x</i> O _<i>y</i> stoichiometries with a reduced oxidation number of vanadium at the areas of thickness below 70 nm. On the other hand, the thicker areas are dominated by vanadium dioxide, where the signatures of the IMT are detected in both core-loss and low-loss EELS experiments with <i>in situ</i> heating. The experimental results are interpreted with <i>ab initio</i> and semi-classical calculations. This work shows that structural inhomogeneities such as pores and cracks present no harm to the desired optical properties of VO₂ samples.