Influence of doping concentration on room-temperature ferromagnetism for Fe-doped BaTiO3 ceramics

Ba(Ti_1−xFe_x)O₃ ceramics (x=7, 30 and 70 at%) were prepared by solid-state reaction. All samples are single-phase with 6H-BaTiO₃-type hexagonal perovskite structure. Mössbauer spectra show all Fe atoms to be present as Fe³⁺ in BaTiO₃ lattice, occupying M1 octahedral and pentahedral sites. Room-temperature ferromagnetism is exhibited and saturation magnetization gradually decreases with increasing Fe content. The observed ferromagnetism is considered to be an intrinsic property of Ba(Ti_1−xFe_x)O₃, originating from super-exchange interactions between Fe³⁺ in different occupational sites associated with oxygen vacancies. The variation in magnetization with Fe content is related to the ratio of pentahedral to octahedral sites and oxygen vacancies.     

Role of defects in magnetic properties of Fe-doped SnO2 films fabricated by the Sol--Gel method

This paper obtains the room temperature ferromagnetism in Sn1 xFexO2 films fabricated by the Sol-Gel method.X-ray diffraction results show that Fe doping inhibits the growth of SnO2 and Fe3+ ions occupy the Sn sites.The measurement of resistance excludes the free carrier inducing ferromagnetism.Moreover,the temperature dependence of magnetization has been better fitted by the Curie-Weiss law and bound magnetic polaron(BMP) theory.An enhancement of ferromagnetism is achieved by annealing the samples with x = 7.1% in H2,and a decrease of oxygen flow rate.All these results prove that the BMP model depending on defects can explain ferromagnetism in diluted magnetic oxides.     

Effects of doping site and pre-sintering time on microstructure and magnetic properties of Fe-doped BaTiO3 ceramics

The A-site substituted BaTiO₃ ceramics were prepared by solid-state reaction via partial substitution of Fe for Ba²⁺. By comparison with the B-site substituted sample made under similar conditions, the effect of Fe doping site on microstructure and magnetism was investigated using X-ray diffraction, Mössbauer spectroscopy and vibrating sample magnetometer. It is found that A-site substitution can be realized to a certain extent at 7 at% Fe addition, whereas impurities are observed at higher Fe concentrations. In the nominal (Ba_0.93Fe_0.07)TiO₃ sample, the Fe ions are present as Fe²⁺ and Fe³⁺, respectively, replacing A-site Ba²⁺ and octahedral B-site Ti⁴⁺ in hexagonal perovskite lattice. The double-exchange Fe²⁺-O²⁻-Fe³⁺ interactions produce ferromagnetism well above room temperature, but the saturation magnetization and the Curie temperature are both obviously lower than those for B-site substitution due to different magnetic exchange mechanisms. In the B-site substituted sample Ba(Ti_0.93Fe_0.07)O₃, the super-exchange interactions between Fe³⁺ on pentahedral and octahedral Ti⁴⁺ sites are responsible for ferromagnetism. These results mean that B-site substitution is a better way for Fe-doped BaTiO₃ system to obtain high-Curie-temperature ferromagnetism. Moreover, increasing pre-sintering time can further improve the magnetism of B-site substituted samples, through which the saturation magnetization for Ba(Ti_0.93Fe_0.07)O₃ is enhanced ∼6 times.     

A close correlation between induced ferromagnetism and oxygen deficiency in Fe doped In2O3

We report on the reversible manipulation of room temperature ferromagnetism in Fe (5%) doped In₂O₃ polycrystalline magnetic semiconductor. The X-ray diffraction and photoemission measurements confirm that the Fe ions are well incorporated into the lattice, substituting the In³⁺ ions. The magnetization measurements show that the host In₂O₃ has a diamagnetic ground state, while it shows weak ferromagnetism at 300 K upon Fe doping. The as-prepared sample was then sequentially annealed in hydrogen, air, vacuum and finally in air. The ferromagnetic signal shoots up by hydrogenation as well as vacuum annealing and bounces back upon re-annealing the samples in air. The sequence of ferromagnetism shows a close inter-relationship with the behavior of oxygen vacancies (V_o). The Fe ions tend to a transform from 3+ to 2+ state during the giant ferromagnetic induction, as revealed by photoemission spectroscopy. A careful characterization of the structure, purity, magnetic, and transport properties confirms that the ferromagnetism is due to neither impurities nor clusters but directly related to the oxygen vacancies. The ferromagnetism can be reversibly controlled by these vacancies while a parallel variation of carrier concentration, as revealed by resistance measurements, appears to be a side effect of the oxygen vacancy variation.     

Dopant Spin States and Magnetic Interactions in Transition Metal (Fe3+)-Doped Semiconductor Nanoparticles: An EMR and Magnetometric Study

In this work, electron magnetic resonance (EMR) spectroscopy and magnetometry studies were employed to investigate the origin of the observed room-temperature ferromagnetism in chemically synthesized Sn_1?x Fe _x O₂ powders. EMR data clearly established the presence of two different types of signals due to the incorporated Fe ions: paramagnetic spectra due to isolated Fe³⁺ ions and broad ferromagnetic resonance (FMR) spectra due to magnetically coupled Fe³⁺ dopant ions. EMR data analysis and simulation suggested the presence of high-spin (S = 5/2) Fe³⁺ ions incorporated into the SnO₂ host lattice both at substitutional and at interstitial sites. The FMR signal intensity and the saturation magnetization M _s of the ferromagnetic component increased with increasing Fe concentration. For Sn_0.953Fe_0.047O₂ samples, well-defined EMR spectra revealing FMRs were observed only for samples prepared in the 350–600°C range, whereas for samples prepared at higher annealing temperatures up to 900°C, the FMRs and saturation magnetization were vanished due to diffusion and eventual expulsion of the Fe ions from the nanoparticles, in agreement with data obtained from Raman and X-ray photoelectron spectroscopy.     

Enhanced room temperature ferromagnetism in porous BiFeO3 prepared using cotton templates

Porous BiFeO₃ has been prepared using cotton templates. Strongly enhanced ferromagnetism with saturate magnetization of 3 emu/g at 300 K has been observed. An energy band gap of 2.21 eV was determined from the UV-visible diffuse reflectance spectrum. The Raman and X-ray photoelectron spectroscopy measurements indicate the existence of Fe²⁺ and the suppression of the oxygen octahedral tilts. The enhanced ferromagnetism has been attributed to the enhanced double exchange interaction with increased angle of Fe^{2 +}-O-Fe^{3 +}.     

Sol-gel synthesis and dilute magnetism of nano MgO powder doped with Fe

Mg oxides doped with 1 % ⁵⁷Fe were prepared by a sol-gel method, and annealed at various temperatures. Nano-size Mg oxides were characterized by Mössbauer spectrometry, magnetization and XRD measurements. The crystalline size of MgO increases with increase of annealing temperature. Samples annealed at 600 °C and 800 °C gave only doublet peaks of paramagnetic Fe³⁺ in Mössbauer spectra although Fe³⁺ doping into MgO induced a distorted structure and showed weak ferromagnetism. It is considered that the magnetic property is due to defect induced magnetism by doping Fe³⁺ into MgO. For a sample heated at 1000 °C, it is found from low temperature Mössbauer spectra that Fe³⁺ species are located at the core and shell of fine MgFe₂O₄ grains and diluted in MgO matrix.     

Effect of thermal treatment on room-temperature ferromagnetism in Co-doped ZnO powders

The Co-doped ZnO powders were synthesized by sol-gel method, and treated at different temperatures (673-873 K) in the presence or absence of NH₃ atmosphere for 0.5 and 2 h, respectively. X-ray diffraction (XRD) and vibrating sample magnetometer (VSM) show that better crystal structure can cause larger ferromagnetism and the second phase (Co₃O₄) is the reason for saturation magnetization decrease of the sample sintered at higher temperature in air. XPS and nuclear magnetic resonance (NMR) prove the existence of Co²⁺ ions in the Zn_0.9Co_0.1O and the absence of Co clusters, indicating intrinsic ferromagnetism of the samples treated in air. However, strong ferromagnetism of the samples annealed in NH₃ is ascribed to cobalt nitride formed during annealing.     

Effects of Mn substitution of Co and Fe in spinel CoFe2O4 thin films

Effects of Mn substitution for Co and Fe on the structural and magnetic properties of inverse-spinel CoFe₂O₄ have been investigated. Mn_xCo_1−xFe₂O₄ and Mn_yCoFe_2−yO₄ thin films were prepared by a sol–gel method. The observed increase of the lattice constant of Mn_xCo_1−xFe₂O₄ indicates that Mn²⁺ ions substitute the octahedral Co²⁺ sites. Conversion electron Mössbauer spectroscopy data indicate that a fraction of octahedral Co²⁺ ions exchange sites with tetrahedral Fe³⁺ ions through Mn doping. Vibrating-sample magnetometry data exhibit a large increase of saturation magnetization for both Mn_xCo_1−xFe₂O₄ and Mn_yCoFe_2−yO₄ films compared to that of the CoFe₂O₄ film. Such enhancement of magnetization can be explained in terms of a breaking of ferrimagnetic order induced by the Co²⁺ migration.     

Magnetic property and Mössbauer analysis of SrSn<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Fe<Subscript><Emphasis Type="Bold">x</Emphasis></Subscript>O<Subscript>3</Subscript> prepared by a sol-gel method

The dilute magnetic properties of SrSn_1?xFe_xO₃ (x = 0.01 ? 0.15) prepared by sol-gel and thermal decomposition methods were investigated by ⁵⁷Fe Mössbauer spectrometry, magnetometry, and X-ray diffractometry. It was found that SrSnO₃ doped with 2–8 % Fe show weak ferromagnetism although only paramagnetic doublets are observed in ⁵⁷Fe Mössbauer spectra at room temperature (RT), whereas SrSnO₃ doped with 10–15 % Fe show relatively strong ferromagnetism, and the sextets are additionally observed in the ⁵⁷Fe Mössbauer spectra at RT. The weak ferromagnetism by doping 2–8 % Fe is considered to be caused by the induced magnetic defects, and the ferromagnetism by doping 10–15 % Fe are considered mainly due to the magnetic coupling between dilute Fe ³⁺ partially substituted at Sn ⁴⁺ sites in the orthorhombic structure of SrSnO_3?δ accompanying the oxygen deficiencies. It is further remarkable that poor crystalline 8 % Fe doped SrSnO_3?δ obtained by annealing at 600 ^°C shows relatively high saturation magnetization and low coercivity.     

High temperature ferromagnetism of the vacuum-annealed (In1−xFex)2O3 powders

(In_1−xFe_x)₂O₃ (x = 0.02, 0.05, 0.2) powders were prepared by a solid state reaction method and a vacuum annealing process. A systematic study was done on the structural and magnetic properties of (In_1−xFe_x)₂O₃ powders as a function of Fe concentration and annealing temperature. The X-ray diffraction and high-resolution transmission electron microscopy results confirmed that there were not any Fe or Fe oxide secondary phases in vacuum-annealed (In_1−xFe_x)₂O₃ samples and the Fe element was incorporated into the indium oxide lattice by substituting the position of indium atoms. The X-ray photoelectron spectroscopy revealed that both Fe²⁺ and Fe³⁺ ions existed in the samples. Magnetic measurements indicated that all samples were ferromagnetic with the magnetic moment of 0.49-1.73 μ_B/Fe and the Curie temperature around 783 K. The appearance of ferromagnetism was attributed to the ferromagnetic coupling of Fe²⁺ and Fe³⁺ ions via an electron trapped in a bridging oxygen vacancy.     

Effect of thermal treatment in vacuum on Fe-doped SnO2 powders

A sample of 10 at% Fe-doped SnO₂ powder was prepared by mechanical alloying and then thermally treated at 773 K in vacuum. The fit of the diffraction patterns and X-ray absorption spectroscopy measurements revealed that the as milled sample was pure doped rutile. Fe dissolved into SnO₂ was found in Fe²⁺/Fe³⁺ ionic valence with mainly paramagnetic behavior. After the thermal treatment all techniques indicate the formation of the ternary Sn_0.36Fe_2.64O₄ spinel phase, which is responsible for the observed ferromagnetism.     

57Fe Mössbauer study of YBa4Cu2.95Fe0.05O8.5+y

⁵⁷Fe Mössbauer measurements were performed on the Fe-doped YBa₄Cu₃O_8.5+y compound as a function of annealing temperature in vacuum. Mössbauer spectra were analyzed using three different quadrupole split doublets. The resistance measurements showed that the compound is not superconducting. The possible identification of the Cu sites with their nearest neighbor oxygen sites in this compound is suggested. Comparison of the results with data of the presence of the superconductor YBa₂Cu₃O₇ allows us to suppose that the presence of the Cu-chain sites alone does not result in superconductivity.     

Magnetization of sol-gel prepared zinc ferrite nanoparticles: Effects of inversion and particle size

Nanoparticles of ZnFe₂O₄ have been prepared by using sol-gel method in two different mediums (acidic and basic) in order to observe the influence of the medium on the magnetic properties of the obtained nanoparticles. X-ray diffraction and Mössbauer studies of these samples show the presence of single-phase spinel structure. The average size of the particles as determined by X-ray diffraction increases with the annealing temperature from 18 to 52 nm. With the increase in particle size, magnetization decreases while the magnetization blocking temperature increases. Magnetization studies show that the samples prepared in basic medium have more ferrimagnetic nature as compared to those prepared in acidic medium. We understand this increase in magnetization as reflective of the increased degree of inversion (transfer of Fe³⁺ ions from octahedral to tetrahedral sites) in the particles of smaller size unit cells. From lattice parameter calculations on different particles it is determined that inversion is more favorable in the particles prepared in a basic medium than in the acidic medium due to the smaller cell size in the former.     

The change from paramagnetic resonance to ferromagnetic resonance for iron nanoparticles made by the sol-gel method

Sol-gel glass embedded with iron nanoparticles provides fascinating features inheriting paramagnetic, ferromagnetic, and superparamagnetic resonance properties under various compositional weight ratios and annealing conditions. Two spectra arising from paramagnetic Fe³⁺ ions and ferrimagnetic Fe₂O₃ particles both centered at g_e=2.0 compete with intensities as the annealing temperature T_A increases. Meanwhile, the resonance line width of Fe₂O₃ particles sharply decreases due to the strong exchange narrowing. The asymmetric line shape and the rather broad line width can be elucidated by the ferromagnetic resonance of the single domain Fe₂O₃ nanoparticles.     

Exchange coupled magnetic nanocomposites of Sm(Co1−xFex)5 / Fe3O4 with core/shell structure

Magnetic nanocomposites of Sm(Co_1−xFe_x)₅/Fe₃O₄ (x≈0.1) with the core/shell type structure were successfully fabricated using a two-step polyol process, where as-prepared SmCo_5(1−x) nanoparticles were used as seeds for the ferrite coating. The core/shell composites are quite stable in air and show a typical hysteric behavior of single component, yielding an enhanced coercivity of 2.2 kOe with a saturated magnetization of 130 emu/g at 5 T. The magnetization data clearly reveal the presence of effective exchange coupling between the hard-magnetic Sm(Co_1−xFe_x)₅ core and soft-magnetic Fe₃O₄ shell, suggestive of a single-phase structure rather than a distinctive two-phase one.     

Suppression of the Verwey Transition by Charge Trapping

The Verwey transition in Fe₃O₄ nanoparticles with a mean diameter of 6.3 nm is suppressed after capping the particles with a 3.5 nm thick shell of SiO₂. By X‐ray absorption spectroscopy and its associated X‐ray magnetic circular dichroism this suppression can be correlated to localized Fe²⁺ states and a reduced double exchange visible in different site‐specific magnetization behavior in high magnetic fields. The results are discussed in terms of charge trapping at defects in the Fe₃O₄/ SiO₂ interface and the consequent difficulties in the formation of the common phases of Fe₃O₄. By comparison to X‐ray absorption spectra of bare Fe₃O₄ nanoparticles in course of the Verwey transition, particular changes in the spectral shape could be correlated to changes in the number of unoccupied d states for Fe ions at different lattice sites. These findings are supported by density functional theory calculations.     

Simultaneous regulation of photoabsorption and ferromagnetism of NaTaO3 by Fe doping

NaTa_1-xFe_xO₃ (0 ≤ x ≤ 0.40) nanocubes were synthesized by a relatively low temperature hydrothermal method, using Ta₂O₅, FeCl₃ and NaOH as the precursors. The UV–vis diffuse reflectance spectra showed that NaTa_1-xFe_xO₃ had significant visible-light-absorbing capability, and the absorption edge of NaTaO₃ shifted to longer wavelength with the increase of Fe dopants. Moreover, NaTa_1-xFe_xO₃ exhibited room-temperature ferromagnetism when Fe³⁺ occupied Ta⁵⁺ sites in NaTaO₃ crystal lattice. The ferromagnetism is mainly attributed to the superexchange interactions between doped Fe³⁺, rather than the contribution of oxygen vacancies caused by Fe doping. Therefore, Fe doping can simultaneously regulate the optical and magnetic properties of NaTaO₃ semiconductor, which will enable its potential applications in multifunctional optical-electronics and optical-spintronics devices.     

A study of the new compound YBa4Fe3O11−y

The compound YBa₄Fe₃O _y was synthesized where the Fe atoms completely substituted for the Cu atoms in YBa₄Fe₃O _y . The X-ray phase analysis of the synthesized material showed that the diffraction pattern corresponds to the data for the compound YBa₄Fe₃O _y .⁵⁷Fe Mössbauer measurements of the compound were performed at room temperature after different heat treatments: high-temperature synthesis in an oxygen atmosphere and in air, and low-temperature annealing in oxygen and in vacuum. No magnetic components are observed after any heat treatments. The Fe atoms in the compound have two valence states, Fe³⁺ and Fe⁴⁺. The idealized model of the 1-4-3 Fe structure is discussed.