Occurrence and stability of ferromagnetism in chemically synthesized cobalt doped TiO2

We report the development of ferromagnetism in ∼30 nm sized well-characterized Ti1−xCoxO2 powders with x = 0.00015–0.006 and its absence for x > 0.006. In addition, these studies show the effect of Co doping on the structural stability and anatase to rutile phase transformation. X-ray diffraction data of samples synthesized by a wet chemical method and annealed at 450 °C indicate a limited solubility of ∼1.2% for Co in the anatase TiO2 matrix, and with further increase, the CoTiO3 phase is formed along with increased presence of rutile TiO2. The bandgap (∼3.23 eV) of the anatase TiO2 remained almost unchanged for x < 0.006, but decreased rapidly for x ≥ 0.006 approaching 2.8 eV for x = 0.03. The magnetic data from Ti1−xCoxO2 samples with x = 0.006 showed a coercivity Hc ∼ 150 Oe and a weak magnetic moment of 0.2 μB/ion at 300 K. The ferromagnetism of Ti0.994Co0.006O2 with open hysteresis loops continue up to a high superparamagnetic blocking temperature TB ∼ 675 K, above which a superparamagnetic behavior was observed. Systematic changes in the structural, magnetic and optical properties suggest that Co doping is an excellent method to tailor the physical properties of TiO2 nanoparticles.