Oxygen vacancy and dopant concentration dependent magnetic properties of Mn doped TiO2 nanoparticle

Mn doped TiO2 nanoparticles are synthesized by sol–gel method. Incorporation of Mn shifts the diffraction peak of TiO2 to lower angle. The position and width of the Raman peak and photoluminescence intensity of the doped nanoparticles varies with oxygen vacancy and Mn doping level. The electron spin resonance spectra of the Mn doped TiO2 show peaks at g = 1.99 and 4.39, characteristic of Mn2+ state. Reduction in the emission intensity, on Mn doping, is owing to the increase of nonradiative oxygen vacancy centers. Mn doped TiO2, with 2% Mn, shows ferromagnetic ordering at low applied field. Paramagnetic contribution increases as Mn loading increases to 4% and 6%. Temperature dependent magnetic measurement shows a small kink in the ZFC curve at about 40 K, characteristic of Mn3O4. The ferromagnetic ordering is possibly due to the interaction of the neighboring Mn2+ ions via oxygen vacancy (F+ center). Increase in Mn concentration increases the fraction of Mn3O4 phase and thereby increases the paramagnetic ordering.

► Mn doping TiO2 nanoparticles exhibit ferromagnetism with some paramagnetic contribution.
► The paramagnetic contribution is due to the formation of Mn3O4 phase.
► The interactions of oxygen vacancies with Mn2+ impart ferromagnetism.