Effect of annealing temperature on the structural, electronic and magnetic properties of Co doped TiO2 nanoparticles: An investigation by synchrotron-based experimental techniques.

The present study examines the effect of annealing temperature on the structural, electronic and magnetic properties of Co-doped TiO 2 (TCO) nanoparticles (NPs) synthesized by the sol-gel method. X-ray powder diffractograms of TCO NPs annealed at 400, 600 and 800 °C exhibited the monophasic anatase, diphase (anatase and rutile) and monophasic rutile structures respectively. A morphological investigation using high-resolution scanning electron microscopy (HR-SEM) reveals the presence of nanoparticles with diameters ranging from ∼11 to ∼51 nm. The widening and shifting of the most intense E g peak in Raman studies and SEM images of TCO NPs suggest Co incorporation in the TiO 2 matrix and the formation of oxygen vacancies. Magnetic measurements of TCO at room temperature demonstrate ferromagnetic behaviour which is caused by the existence of oxygen vacancies and the doped Co content. Element specific technique, soft X-ray magnetic circular dichroism (XMCD) was used to study the magnetism in Co doped TiO 2 samples. The estimated total magnetic moment by XMCD was in the range of ∼1.3 ± 0.1–2.3 ± 0.2 μ B /Co. This huge magnetization was first time observed by the surface-sensitive Total Electron Yield (TEY) mode. The estimated saturation magnetic moment is in the range of 1.0–1.5 μ B /Co, also consistent with XMCD analysis and cluster model calculation. The results obtained by XMCD recommend an intrinsic behaviour of ferromagnetism. The X-ray absorption spectra (XAS) of Co-doped TiO 2 nanoparticles at Ti L 2,3 and Co L 2,3 -edge in TEY mode concludes that the valence states of Co and Ti ions are in 2 + and 4 + respectively. Cluster model calculation also confirmed that Co ions are in a 2 + valence state with D 2 h high spin crystal-field symmetry at the surface while a random crystal field symmetry in bulk has been observed which is well consistent with experimental data. [Display omitted] • XRD of TCO NPs annealed at 400, 600 and 800°C exhibited the anatase, mix and rutile structures respectively. • The widening and shifting of the E g peak in Raman studies of TCO NPs suggest the formation of oxygen vacancies. • Magnetization of TCO at RT demonstrate FM behaviour, caused by the existence of oxygen vacancies and the doped Co content. • The estimated Ms is in the range of 1.0–1.5 μ B /Co, also consistent with the XMCD and cluster model calculation. • The results obtained by XMCD recommend an intrinsic behaviour of ferromagnetism. • The XAS of TCO NPs at Ti and Co L 2,3 -edge in TEY concludes that Co and Ti ions are in 2 + and 4 + valence states. [ABSTRACT FROM AUTHOR]