Effect of Ni doping on the microstructure and high Curie temperature ferromagnetism in sol–gel derived titania powders

Undoped, 0.05 and 0.5 mol% Ni-doped TiO2 powders were prepared by a modified sol–gel route. The doping effects on the microstructure and magnetism for the powdered samples have been systematically investigated. Doping of Ni in TiO2 inhibited rutile crystal growth. The probable reason for this is discussed on the basis of band calculation based analysis of electronic structures of 3d transition metal-doped TiO2 and the energetic, transformation kinetics and phase stability of anatase over rutile as the function of particle size. Room temperature ferromagnetism (RTFM) with the saturation magnetization of 12 m emu g−1 and Curie temperature as high as 820 K is observed only in case of 0.05 mol% Ni:TiO2 powdered sample, whereas undoped TiO2 was diamagnetic and 0.5 mol% Ni:TiO2 was paramagnetic in nature. The role of any magnetic impurity or any Ni metal in the origin of the RTFM has been ruled out by energy dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and high resolution TEM (HRTEM) analysis, whereas magnetic force microscopy (MFM) established the presence of magnetic domains, supporting the intrinsic diluted magnetic semiconductor behavior. The observed ferromagnetism has been attributed to the spin ordering through exchange interaction between holes trapped in oxygen orbitals adjacent to Ni substitutional sites.

► Doping of Ni in TiO2 inhibited rutile crystal growth.
► Explanation on the basis of anatase phase stability as function of particle size.
► Only 0.05 mol% Ni doped TiO2 ferromagnetic with so far highest reported TC ∼ 810 K.
► No Ni magnetic impurity, detected NiO antiferromagnetic and NiTiO3 paramagnetic.
► MFM confirms magnetic domains not dopant clusters supporting intrinsic DMS behavior.