Structure, room-temperature magnetic and optical properties of Mn-doped TiO2 nano powders prepared by the sol-gel process

TiO₂ nano powders with Mn concentration of 0 at%-12 at% were synthesized by the sol-gel process, and were annealed at 500 ℃ and 800 ℃ in air for 2 hrs. X-ray diffraction (XRD) measurements indicate that the Mn-TiO₂ nano powders with Mn concentration of 1 at% and 2 at% annealed at 500 and 800 ℃ are of pure anatase and rutile, respectively. The scanning electron microscope (SEM) observations reveal that the crystal grain size increases with the annealing temperature, and the high resolution transmission electron microscopy (HRTEM) investigations further indicate that the samples are well crystallized, confirming that Mn has doped into the TiO₂ crystal lattice effectively. The room temperature ferromagnetism, which could be explained within the scope of the bound magnetic polaron (BMP) theory, is detected in the Mn-TiO₂ samples with Mn concentration of 2 at%, and the magnetization of the powders annealed at 500 ℃ is stronger than that of the sample treated at 800 ℃. The UV-VIS diffuse reflectance spectra results demonstrate that the absorption of the TiO₂ powders could be enlarged by the enhanced trapped electron absorption caused by Mn doping.     

Structures and magnetic behaviours of TiO2—Mn—TiO2 multilayers

The TiO₂--Mn--TiO₂ multilayers are successfully grown on glass and silicon substrates by alternately using radio frequency reactive magnetron sputtering and direct current magnetron sputtering. The structures and the magnetic behaviours of these films are characterised with x-ray diffraction, transmission electron microscope (TEM), vibrating sample magnetometer, and superconducting quantum interference device (SQUID). It is shown that the multi-film consists of a mixture of anatase and rutile TiO₂ with an embedded Mn nano-film. It is found that there are two turning points from ferromagnetic phase to antiferromagnetic phase. One is at 42 K attributed to interface coupling between ferromagnetic Mn₃O₄ and antiferromagnetic Mn₂O₃, and the other is at 97 K owing to the interface coupling between ferromagnetic Mn and antiferromagnetic MnO. The samples are shown to have ferromagnetic behaviours at room temperature from hysteresis in the M--H loops, and their ferromagnetism is found to vary with the thickness of Mn nano-film. Moreover, the Mn nano-film has a critical thickness of about 18.5 nm, which makes the coercivity of the multi-film reach a maximum of about 3.965times 10 ^{- 2} T.