Oxidation of Amorphous Porous VO_x at Low Temperatures for the Formation of Thermochromic VO₂ Films

Thermochromic VO₂ crystalline domains have been formed in amorphous nanocolumnar VO_x films by means of a low-temperature oxidation process. The oxidation of an amorphous film with [O]/[V] below 1.9 favors the formation of VO₂, V₃O₇, and V₂O₅ crystalline domains in the material for temperatures as low as 260 °C, while values above 1.9 lead to the sole formation of the V₂O₅ phase. It is found that the absorption of oxygen also causes a relevant film volume expansion that makes pores shrink. Under some specific conditions, low-temperature oxidation causes the near disappearance of the amorphous regions, clearly improving the overall transparency and optimizing the optical and electrical modulation capabilities associated with the presence of crystalline VO₂ domains. The best thermochromic performance was found when the original stoichiometry was [O]/[V] = 1.5 and the oxidation temperature was 280 °C. These conditions yield a relatively transparent coating in the visible range that presents an optical modulation in the near-infrared range of nearly 50% and a drop of electrical resistivity of more than two orders of magnitude, with a transition temperature of 50.3 °C. A tentative model based on the volume expansion experienced by the film upon oxidation is proposed, which links the structural/chemical features of the material and the formation of the crystalline domains at such relatively low temperatures.