Controlled grain-size thermochromic VO2 coatings by the fast oxidation of sputtered vanadium or vanadium oxide films deposited at glancing angles

Abstract

An original, simple and cost-effective oxidation strategy to attain thermochromic vanadium dioxide thin films is reported. This two-step procedure comprises the initial deposition of DC magnetron-sputtered vanadium or vanadium oxide films by the combination of glancing angle deposition and, if needed, reactive gas pulsing process, followed by fast oxidation of such layers in air atmosphere at high temperatures. Thanks to the careful control of the thermal treatment parameters, and taking advantage of the superior reactivity of the high surface-to-volume porous deposited structures, the formation of pure VO2 (M1) layers was achieved. The comprehensive characterization of such oxidized systems by means of scanning electron microscopy, Raman spectroscopy and scanning-transmission electron microscopy techniques such as electron energy-loss spectroscopy, not only confirmed the presence of the VO2 (M1) phase, but also allowed to shed light on the key role that reaction time plays in the selective formation of vanadium dioxide films of adjustable grain size and crystallinity. The optimal conditions to stabilize thermochromic VO2 consists in using large deposition angles (85 degrees) and short oxygen pulses (<= 2 s) during the growth, followed by fast and short thermal treatments (<= 45 s with a heating rate of 42 degrees C s(-1)) in air atmosphere at 550 degrees C. The metal-to-insulator response of the accomplished VO2 layers was finally evaluated by means of temperature dependent Kelvin probe force microscopy measurements, evidencing surface potential drops at heating, greater than those reported in the literature to date for VO2 thin films.