Toward Room-Temperature Thermochromism of VO₂ by Nb Doping: Magnetic Investigations

Using a synthesis route based on carbon as the reducing agent mixed with Nb-doped V2O5 nanopowders, highly crystallized Nb-doped VO2 (M) particles, with tunable content of niobium (Nb), are successfully prepared. The morphology and the crystalline structure are first studied in regard to synthesis parameters and chemical composition for various thermal treatment temperatures/durations and niobium doping concentrations. The second part of this paper is devoted to the control, in Nb-doped VO2, of the phase transition temperature from monoclinic to rutile (M → R transition) versus the niobium doping concentration associated with thermochromic properties and different property changes characterized by differential scanning calorimetry and magnetic and electrical measurements. The niobium introduction allows the decrease of the thermochromic transition from 68 °C down to around room temperature for an effective Nb concentration of approximatively 6 mol % for the V0.94Nb0.06O2±δ composition. A significant result is the decrease of both the hysteresis width as well as the phase transition amplitude supported by latent heat, magnetic behavior, and electrical transport versus niobium concentration. These phenomena are correlated to the breaking of the V–V pairing occurring in the monoclinic form when niobium ions are introduced. Finally, a deep interpretation of the Nb-doped VO2 magnetic behavior is performed considering the impact of niobium concentration and crystallite sizes on the intensity of the Curie magnetic residue plus Van Vleck susceptibility in the low temperature form (M) and on the intensity of the Pauli magnetism of the high temperature form (R).