Reversible ferromagnetism in rutile TiO2 single crystals induced by nickel impurities
TL;DR: In this paper, a Ni impurity induced reversible ferromagnetism and surface conduction in rutile TiO2 crystals subjected to specific thermal annealing was reported.
Abstract: We report a Ni impurity induced reversible ferromagnetism and surface conduction in rutile TiO2 crystals subjected to specific thermal annealing. For annealing in vacuum at 800 °C, a growing ferromagnetic signal is seen with time while for a similar annealing in air, the magnetism vanishes. The magnetism is concomitant with a surface conductivity which at low temperatures shows tunneling characteristics. Here, we show that Ni magnetic impurity (in TiO2 crystals at <100 ppm) under vacuum annealing segregates to the surface over a 50 nm layer where the Ni concentration exceeds 10%–20% and drops with subsequent air annealing.
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TL;DR: In this article, the effects of transition metal doping to metal-oxide nanoparticles (TiO2) were studied using a variety of characterization techniques, including X-ray diffraction, Fourier transform-infrared (FTIR), ultraviolet-visible (UV-Vis) spectroscopy, field-emission scanning electron microscopy (FESEM), and vibrating sample magnetometer (VSM).
Abstract: In this research, the effects of transition metal (Ni) doping to metal-oxide nanoparticles (TiO2) were studied. Various weight ratios (5, 10, 15, and 20%) of Ni-to-TiO2 nanoparticles were synthesized using the sol–gel technique. These doped nanoparticles were prepared using titanium butoxide and nickel nitrate as precursors and methanol as a solvent. The effects of Ni doping to TiO2 were examined using a variety of characterization techniques, X-ray diffraction (XRD), Fourier-transform-infrared (FTIR) spectroscopy, ultraviolet–visible (UV–Vis) spectroscopy, field-emission scanning electron microscopy (FESEM), and vibrating sample magnetometer (VSM). The XRD reveals that the Ni-doped TiO2 crystallizes in a tetragonal structure with anatase phase. The particle size and lattice strain were calculated by Williamson–Hall equation. The presence of strong chemical bonding and functional groups at the interface of TiO2 nanoparticles was confirmed by FTIR. The optical properties of undoped and doped samples were recorded by UV–Vis spectroscopy. The saturation magnetization (Ms) was found higher for undoped as compared to doped samples. The surface morphology and the element structure of the Ni-doped TiO2 nanoparticles were examined by FESEM.
70 citations
TL;DR: In this paper, Ni doping catalyzes the anatase-to-rutile transformation (ART) of TiO 2 films, which is due to the decrease of the ART activation energy.
62 citations
TL;DR: It is found that the magnetizations of the TM-doped TiO2 films decrease with increasing dopant content, which is related to electric disorder due to the ART.
Abstract: Transition metal (TM)-doped TiO2 films (TM = Co, Ni, and Fe) were deposited on Si(100) substrates by a sol–gel method. With the same dopant content, Co dopants catalyze the anatase-to-rutile transformation (ART) more obviously than Ni and Fe doping. This is attributed to the different strain energy induced by the different dopants. The optical properties of TM-doped TiO2 films were studied with spectroscopic ellipsometry data. With increasing dopant content, the optical band gap (EOBG) shifts to lower energy. With the same dopant content, the EOBG of Co-doped TiO2 film is the smallest and that of Fe-doped TiO2 film is the largest. The results are related to electric disorder due to the ART. Ferromagnetic behaviors were clearly observed for TM-doped TiO2 films except the undoped TiO2 film which is weakly magnetic. Additionally, it is found that the magnetizations of the TM-doped TiO2 films decrease with increasing dopant content.
52 citations
Cites background from "Reversible ferromagnetism in rutile..."
...These magnetic phenomena are extraordinary and different from the magnetic results of the literature [7-11,21], which suggest that there are complex magnetisms in these samples....
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...Recently, roomtemperature FM [9] and reversible FM [10] in undoped...
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TL;DR: The band-gap narrowing and the enhanced magnetic moment observed in Ni-doped TiO2 reveal the potential of this semiconductor for advanced functional applications such as magneto-optics and spintronics.
Abstract: Dilute magnetic semiconductors based on TiO2 nanocrystals are the most promising class of materials exhibiting unique optical and magnetic properties. In the present investigation, we have performed a systematic study on the structural, morphological, optical and magnetic behavior of Ni-doped TiO2, synthesized via a simple, cost-effective sol-gel route. X-ray diffraction patterns together with Raman spectra confirmed the tetragonal anatase phase of Ni-doped TiO2. High-resolution transmission electron microscopy images indicated the formation of highly crystalline nanocrystals, and the compositional homogeneity of all the samples was confirmed from energy dispersive X-ray fluorescence spectroscopic studies. The functional groups in the samples were identified by Fourier transform infrared spectroscopy. UV-visible and photoluminescence (PL) spectroscopy were performed to provide an insight into the band-gap narrowing in the Ni-doped TiO2 nanocrystals. X-ray photoelectron spectroscopy results signified the existence of Ti4+ and Ni2+ in all the prepared samples. A decrease in coercivity was observed with Ni substitution, and at lower Ni concentration, the magnetic behavior was attributed to the bound magnetic polarons associated with the oxygen vacancy defects arising during the synthesis procedure. PL analysis revealed the presence of defects in the system and Langevin fitting was employed to estimate the concentration of bound magnetic polarons arising as a result of these defects. The band-gap narrowing and the enhanced magnetic moment observed in Ni-doped TiO2 reveal the potential of this semiconductor for advanced functional applications such as magneto-optics and spintronics.
31 citations
TL;DR: In this paper, the anatase lattice parameters, analyzed by means of powder X-ray diffractometry, depend on the nanometer grain size of the nanoparticles (increase and decrease, respectively, of the tetragonal a and c lattice parameter with respect to the bulk values).
20 citations
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TL;DR: Titanium dioxide is the most investigated single-crystalline system in the surface science of metal oxides, and the literature on rutile (1.1) and anatase surfaces is reviewed in this paper.
7,056 citations
IBM1
TL;DR: In this article, an extension of percolation theory to treat transport is described, and a general expression for the conductance of such networks is derived, which relates to the spin-stiffness coefficient of dilute ferromagnet.
Abstract: Extensions of percolation theory to treat transport are described. Resistor networks, from which resistors are removed at random, provide the natural generalization of the lattice models for which percolation thresholds and percolation probabilities have previously been considered. The normalized conductance, $G$, of such networks proves to be a sharply defined quantity with a characteristic concentration dependence near threshold which appears sensitive only to dimensionality. Numerical results are presented for several families of $3D$ and $2D$ network models. Except close to threshold, the models based on bond percolation are accurately described by a simple effective medium theory, which can also treat continuous media or situations less drastic than the percolation models, for example, materials in which local conductivity has a continuous distribution of values. The present calculations provide the first quantitative test of this theory. A "Green's function" derivation of the effective medium theory, which makes contact with similar treatments of disordered alloys, is presented. Finally, a general expression for the conductance of a percolation model is obtained which relates $G$ to the spin-stiffness coefficient, $D$, of an appropriately defined model dilute ferromagnet. We use this relationship to argue that the "percolation channels" through which the current flows above threshold must be regarded as three dimensional.
4,342 citations
TL;DR: The observation of transparent ferromagnetism in cobalt-doped anatase thin films with the concentration of cobalt between 0 and 8% is reported, indicating the existence of ferromagnetic long-range ordering.
Abstract: Dilute magnetic semiconductors and wide gap oxide semiconductors are appealing materials for magnetooptical devices. From a combinatorial screening approach looking at the solid solubility of transition metals in titanium dioxides and of their magnetic properties, we report on the observation of transparent ferromagnetism in cobalt-doped anatase thin films with the concentration of cobalt between 0 and 8%. Magnetic microscopy images reveal a magnetic domain structure in the films, indicating the existence of ferromagnetic long-range ordering. The materials remain ferromagnetic above room temperature with a magnetic moment of 0.32 Bohr magnetons per cobalt atom. The film is conductive and exhibits a positive magnetoresistance of 60% at 2 kelvin.
2,302 citations
TL;DR: The occurrence of room temperature ferromagnetism is demonstrated in pulsed laser deposited thin films of Sn(1-x)Co(x)O(2-delta) (x<0.3) and a giant magnetic moment of 7.5+/-0.5 micro(B)/Co, not yet reported in any diluted magnetic semiconductor system.
Abstract: The occurrence of room temperature ferromagnetism is demonstrated in pulsed laser deposited thin films of Sn(1-x)Co(x)O(2-delta) (x<0.3). Interestingly, films of Sn(0.95)Co(0.05)O(2-delta) grown on R-plane sapphire not only exhibit ferromagnetism with a Curie temperature close to 650 K, but also a giant magnetic moment of 7.5+/-0.5 micro(B)/Co, not yet reported in any diluted magnetic semiconductor system. The films are semiconducting and optically highly transparent.
803 citations
TL;DR: The results strongly suggest that the observed ferromagnetic phase is oxygen-vacancy-stabilized Mn2−xZnxO3−δ, rather than by carrier-induced interaction between separated Mn atoms in ZnO.
Abstract: The recent discovery of ferromagnetism above room temperature in low-temperature-processed MnO2–ZnO has generated significant interest. Using suitably designed bulk and thin-film studies, we demonstrate that the ferromagnetism in this system originates in a metastable phase rather than by carrier-induced interaction between separated Mn atoms in ZnO. The ferromagnetism persists up to ∼980 K, and further heating transforms the metastable phase and kills the ferromagnetism. By studying the interface diffusion and reaction between thin-film bilayers of Mn and Zn oxides, we show that a uniform solution of Mn in ZnO does not form under low-temperature processing. Instead, a metastable ferromagnetic phase develops by Zn diffusion into the Mn oxide. Direct low-temperature film growth of Zn-incorporated Mn oxide by pulsed laser deposition shows ferromagnetism at low Zn concentration for an optimum oxygen growth pressure. Our results strongly suggest that the observed ferromagnetic phase is oxygen-vacancy-stabilized Mn2−xZnxO3−δ.
466 citations