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.     

Electronic structure studies of Mg0.95Mn0.05Fe2−2xTi2xO4 (0x0.8)

The electronic structure of Mg_0.95Mn_0.05Fe_2−2xTi_2xO₄ (0x0.8) compound is investigated using near edge X-ray absorption fine structure, (NEXAFS) spectroscopy measurements, carried out at O K, Fe and Ti L_3,2-edges at room temperature. The O K-edge spectra indicate that the Fe 3d orbitals have been considerably modified and a new spectral feature start dominating in the pre-edge region at higher Ti doping. The Fe 2p NEXAFS spectra exhibit a mixed valent Fe²⁺/Fe³⁺ states apart from the conversion of Fe³⁺ to Fe²⁺ with the substitution of Ti ions. The Ti L_3,2-edge spectra indicate that Ti ions remain unchanged at 4+ state. These variations in the host electronic structure due to Ti substitution are consistent with the dielectric and transport properties of the material.     

Relationship between structural and magnetic properties in (Ti,Fe)O2 powders obtained by mechanical milling

Fe-doped TiO₂ samples with different Fe content were prepared by mechanical alloying starting from TiO₂ rutile and FeO. The samples were structurally and magnetically characterized by XRD, Mössbauer spectroscopy, X-ray absorption spectroscopy (XAS), AC-susceptibility and magnetization measurements. XAS results showed that Fe ions were incorporated into the rutile phase with oxygen coordination that was lower than that expected in this phase. The oxygen coordination number decreased with the increase of Fe²⁺ ions such as it was previously found in the milled samples of TiO₂ doped with hematite. The RT Mössbauer spectra were reproduced using two paramagnetic interactions, one corresponding to Fe²⁺ (δ∼0.87 mm/s) and the other to Fe³⁺ (δ∼0.31 mm/s). Magnetometry measurements showed the presence of paramagnetic and ferromagnetic-like interactions at room temperature. Although saturation and coercivity of the ferromagnetic phase increased with iron, the effective magnetic moment per iron atom decreased, probably due to the precipitation of Fe rich antiferromagnetic structures.     

Electron spin resonance investigation of the substitution of Fe3^＋ for Ti4^＋ ions in rutile TiO2 single crystal

A Fe doped rutile TiO 2 single crystal is grown in an O 2 atmosphere by the floating zone technique.Electron spin resonance (ESR) spectra clearly demonstrate that Fe 3+ ions are substituted for the Ti 4+ ions in the rutile TiO 2 matrix.Magnetization measurements reveal that the Fe:TiO 2 crystal shows paramagnetic behaviour in a temperature range from 5 K to 350 K.The Fe 3+ ions possess weak magnetic anisotropy with an easy axis along the c axis.The annealed Fe:TiO 2 crystal shows spin-glass-like behaviours due to the aggregation of the ferromagnetic clusters.     

Single-crystalline M-type Sr Hexaferrites studied by <Superscript>57</Superscript>Fe Mössbauer spectroscopy

The ⁵⁷Fe Mössbauer spectra of the single crystalline and the finely ground Sr_1?x La _x Fe_12?y Co _y O₁₉ (x = 0 : y = 0, x = 0.192 : y = 0.152 and x = 0.456 : y = 0.225) samples have been measured to investigate the La-Co substitution effects. All observed spectra at 150 K were well fitted using the five subspectra which correspond to the five crystallographical nonequivalent Fe sites in the M-type hexaferrite, indicating that the valence changes to Fe²⁺ ions in the Fe³⁺ ions were not observed in our Sr_1?x La _x Fe_12?y Co _y O₁₉ samples. In SrFe₁₂O₁₉, the relative absorption intensities in the five subspectra show the large anisotropies in the recoilless fractions at the five Fe sites whereas these anisotropies were not observed in Sr_0.544La_0.456Fe_11.775Co_0.225O₁₉. These results indicate the chemical compositional dependence on the anisotropies of the recoilless fractions at the five Fe sites. The substitution of a Co²⁺ ion for the Fe³⁺ ion changes the center shifts of the Fe³⁺ ions near the Co²⁺ ion by the perturbation of the Fe-O-Co hybridizations. Therefore, the Co²⁺ ions occupy the 4f ₁ and the 4f ₂ sites due to the chemical compositional dependences of the refined magnetic hyperfine field and center shifts of the Fe³⁺ ions.     

CEMS study on iron film oxidized in various oxygen pressures

In order to prepare the Fe_1?xO film, Fe metals evaporated on sapphire substrate were oxidized in the furnace for 2 hours at 800°C. The pressure of oxygen between 10^?14 and 10^?19 atm. was controlled by changing the flow rates of CO₂ and H₂ gases. After the oxidation, the conversion Mössbauer spectra for the samples were measured by a He+10%CH₄ proportional counter. It was found that at this temperature the usually accepted Fe_1?xO was not made for 2 hours, but the unknown oxidation state of Fe was formed at the oxygen pressure of 10^?16.5 alm.. Its isomer shift relative to α-Fe and quadrupole splitting are 0.92 mm/sec and 1.71 mm/sec. The normal Fe_1?xO was formed at the oxygen pressure of 10^?16.5 atm. when the oxidation time was extended to 6.5 hours, in addition to Fe₃O₄.     

Electric and magnetic properties of the perovskites Ba2(FeMo)O x (5.88 ≤ x 6.01)

The purpose of this work is to establish the relation between the magnetic, electric, and magnetotransport properties and the oxygen nonstoichiometry of the compounds Ba₂(FeMo)O _x (5.88 ≤ x ≤ 6.01). The investigations established the behavior of the magnetization, resistance, and magnetoresistance of samples in this series. It is shown that the behavior of the magnetization can be described by assuming that the iron ions become divalent (Fe³⁺→ Fe²⁺) as a result of the reduction of the samples and the molybdenum ions become hexavalent (Mo⁵⁺ → Mo₆₊) as a result the oxidation of the samples. It is established that there are two contributions to the magnetoresistance which arise as result of magnetic ordering of the intragranular interlayer and intergranular transfer of spin-polarized charge carriers. It is inferred that electric transport in samples of this series is determined by percolation processes between granules with metallic conductivity separated by a dielectric interlayers.     

Fe57 Mössbauer study in cobalt substituted magnetite

The Mössbauer effect has been studied in the mixed ferrites Co _x Fe_3–x O₄ (forx=0.8, 0.9 and 1) with the spinel structure in the temperature range between 78 and 380 K. The composition withx=1, showed an expected Zeeman spectrum with two overlapping magnetic hyperfine patterns related to the Fe³⁺ ions in tetrahedral and octahedral sites. While for samples withx=0.8 and 0.9 the Mössbauer spectrum for each compound was successfully analysed into three different patterns corresponding to the ferric ions placed at the tetrahedral and octahedral sites and ferrous ions at the octahedral sites, indicating no electron transfer between Fe³⁺ and Fe²⁺, where the quantity of cobalt is sufficiently large to be located at the six nearest neighbours to ferrous ions. The Mössbauer effect parameters were calculated for these observed sites and their variation with temperature reported. The reduced hyperfine magnetic fields of the Fe³⁺ (B) ions were found to follow the Brillouin curve forS=5/2 and one third power law. The magnetic ordering temperature was determined to be 815 K and the possible magnetic interactions were discussed.     

Photooxidation of different organic dyes (RB, MO, TB, and BG) using Fe(III)-doped TiO2 nanophotocatalyst prepared by novel chemical method

The nano-structured Fe(III)-doped TiO₂ photocatalysts with anatase phase have been developed for the oxidation of non-biodegradable different organic dyes like methyl orange (MO), rhodamine B (RB), thymol blue (TB) and bromocresol green (BG) using UV-Hg-lamp. The different compositions of Fe_xTi_1−xO₂ (x = 0.005, 0.01, 0.05, and 0.1) nanocatalysts synthesized by chemical method (CM), have been characterized by X-ray diffraction (XRD), UV-vis diffuse reflectance spectra, specific surface area (BET), transmission electronic microscopy (TEM) analysis, XPS, ESR and zeta potential. From XRD analysis, the results indicate that all the compositions of Fe(III) doped in TiO₂ catalysts gives only anatase phase not rutile phase. For complete degradation of all the solutions of the dyes (MO, RB, TB, and BG), the composition with x = 0.005 is more photoactive compared all other compositions of Fe_xTi_1−xO₂, and degussa P25. The decolorization rate of different dyes decreases as Fe(III) concentration in TiO₂ increases. The energy band gap of Fe(III)-doped TiO₂ is found to be 2.38 eV. The oxidation state of iron has been found to be 3+ from XPS and ESR show that Fe³⁺ is in low spin state.     

Mn-doped (Ba,Y)Fe12O19 hexaferrites: Crystal structure and oxidation states of Mn and Fe

We have fabricated Ba_0.95Y_0.05Fe_12-xMn_xO₁₉ samples with large Mn-doping amounts of x = 4 and 6, using the mechanical milling and heat treatment. X-ray diffraction analysis indicated the samples crystallized in the M-type hexaferrite structure. The Mn doping caused the modification, shift and broadening of some characteristic phonon-vibration modes, which were recorded by Raman spectroscopy. This is due to an incorporation of Mn ions into the M-type structure that disorders the periodic lattice and changes symmetry. Basing on X-ray absorption spectroscopy, we have found Fe in all samples stable with an oxidation state 3+ (Fe³⁺). Though Mn²⁺ and Mn³⁺ ions coexist, the concentration of Mn²⁺ in x = 4 is larger than that in x = 6. The analysis of Fourier-transform spectra have demonstrated the replacement of Mn^2+,3+ ions for Fe³⁺ in the M-type structure. The sites of Mn^2+,3+ ions in this structure have been discussed.     

Effect of Fe3+-doped Ca12Al14O33 cement on optical and thermal properties

This study aims to investigate the effect Fe ions doped into Ca₁₂Al₁₄O₃₃ (C12A7, 12CaO-7Al₂O₃) cement compound on its thermal and optical properties. Polycrystalline samples of Ca₁₂Al_14?xFe_xO₃₃ (where x?=?0.0, 0.5, and 1.0) were prepared via a solid state reaction in an oxygen atmosphere. The lattice constant of Ca₁₂Al₁₄O₃₃ determined using an XRD technique was in excellent agreement with first-principles calculations. With increasing Fe concentrations, the lattice constants were found to have increased. Additionally, the optical gaps of Ca₁₂Al_14?xFe_xO₃₃, (x?=?0, 0.25, 0.5, and 1.0) were 3.9?eV, 3.77?eV, 3.75?eV and 3.63?eV, respectively. It was clearly seen that the optical gap decreased with increasing Fe concentrations. As revealing by first-principles calculations, the optical gap was directly related to the electronic transition from the occupied electronic state of extra-framework O^2? ions (as free O^2? ions inside nano-cage) to the conduction band. Moreover, we also found that the thermal conductivity Ca₁₂Al_14?xFe_xO₃₃ was reduced when the larger atomic mass and atomic radii Fe was substituted into Al sites. Hence, this indicated that Fe³⁺-substitution into Al³⁺ sites of Ca₁₂Al₁₄O₃₃ cement directly affected both its optical gap and thermal conductivity.     

Coexistence of paramagnetism and ferromagnetism in Fe-TiO2 nanoparticle

Magnetic properties of pure and Fe doped rutile TiO₂ and TiO_2-ε are investigated using the first principle density functional theory. The results show that the considered systems are ferromagnetic. Furthermore, the origin of ferromagnetism is discussed and it is found that the double exchange and super-exchange are the main interactions in these compounds. Based on the calculations, the magnitude of the magnetic moment depends on the concentration of impurities and oxygen vacancies and the largest magnetic moment corresponds to the Fe_xTi_1-xO_2-ε. Moreover, using a model based on the bound magnetic polarons, the coexistence of ferromagnetic and paramagnetic phases can occur in Fe_xTi_1-xO₂ containing different impurity ions such as Fe⁺² and Fe⁺³ with different Curie temperatures. The finding may presents the potential application of the considered system as diluted magnetic semiconductor.     

Initial oxidation of polycrystalline Permalloy surface

X-ray photoelectron spectroscopy (XPS) and work-function measurements were used in combination to investigate the initial steps of Permalloy (Ni₈₀Fe₂₀) oxidation at room temperature. They showed that, after oxygen saturation, the surface is covered by nickel oxide (NiO), nickel hydroxide (Ni(OH)₂) and iron oxides (Fe_xO_y), and there is no preferential oxidation. Iron oxidation proceeds through the formation of FeO (Fe²⁺) followed with Fe₂O₃ growth (Fe³⁺). The oxidation is governed by a dissociative Langmuir-type oxidation: the sticking coefficient is decreasing over oxygen exposure. Oxidation continues by oxygen dissolution into the first layers to form a nano-oxide of about 8 Å in thickness.     

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.     

Mössbauer and optical investigation of Co3−x Fe x O4 thin films grown by sol–gel process

Structural transformation and the related variation in magnetic and optical properties of Co_3?x Fe _x O₄ thin films grown by a sol–gel method have been investigated as the Fe composition varies up to x?=?2. The normal spinel phase is dominant below x?=?0.55 and the inverse spinel phase grows as x increases further. Conversion electron Mössbauer spectroscopy (CEMS) measurements indicate that the normal spinel phase have octahedral Fe³⁺ ions mostly while the inverse spinel phase contain octahedral Fe²⁺ and tetrahedral Fe³⁺ ions. For higher Fe composition (x?>?1.22), Co²⁺ ions are found to substitute the octahedral Fe²⁺ sites. The measured optical absorption spectra for the Co_3?x Fe _x O₄ films by spectroscopic ellipsometry support the CEMS interpretation.     

Local states of iron in iron implanted hematite Fe2O3

Powder samples of⁵⁷Fe₂O₃ and⁵⁶Fe₂O₃ were implanted with⁵⁶Fe and⁵⁷Fe ions, respectively. By the use of Conversion Electron Mössbauer Spectroscopy it was possible to observe the local states of implanted ions (⁵⁷Fe in⁵⁶Fe₂O₃) or the states of iron atoms from the target which were displaced during implantation due to the ballistic processes (⁵⁶Fe in⁵⁷Fe₂O₃). The implanted and displaced iron atoms appear in three different states: (i) in regular substitutional positions of Fe₂O₃, (ii) as magnetite Fe₃O₄-type structures and (iii) paramagnetic FeO_1?x state. The observed fractions of each state agree rather well with the calculated values obtained from the local iron atom enrichment at the surface as well as from the analysis of the equilibrium phase diagram for the binary Fe?O system. However, in⁵⁷Fe implanted samples some enhancement of the FeO_1?x fraction was found in comparison with the⁵⁶Fe implanted hematite.     

Cationic behavior and the related magnetic and magnetotransport properties of manganese ferrite thin films

Manganese ferrite (Mn_xFe_3−xO₄) thin films have been prepared by a sol–gel method. The samples (x≤1.25) are polycrystalline containing well-defined grains and maintain cubic spinel structure with increasing lattice constant with x. The substituting Mn ions were found to have multi-valence, +2 and +3, by X-ray photoelectron spectroscopy. The saturation magnetization of the Mn-substituted films measured by vibrating sample magnetometry was found to increase from that of Fe₃O₄ at low x and then gradually decreases as x increases further. Such magnetic behavior can be explained in terms of the dominance of Mn²⁺ species over Mn³⁺ at low x and the gradual decrease in the population ratio Mn²⁺/Mn³⁺ as x increases. The observed decrease in the coercivity with increasing x implies the increase in octahedral Mn²⁺ population. The Mn-substituted samples exhibit magnetoresistance (MR) effect the maximum intensity of which is gradually reduced with x from that of Fe₃O₄. All samples show increasing MR with increasing external field (H), while their magnetization curves start to saturate near H=2 kOe. Such increasing MR with H can be explained in terms of the tunneling of spin-polarized carriers across grain boundaries. The reduction in the MR intensity with x can be partly explained in terms of the decrease in spin-polarized carrier density associated with octahedral occupation of Mn²⁺ ions.     

Mössbauer effect study of ZnAl x Fe2−x O4

⁵⁷Fe Mössbauer effect study in the polycrystalline solid solutions of ZnAl _x Fe_2?x O₄ (x=0.0 – 1.5) has been carried out at 78 and 300K. All the samples exhibited well resolved quadrupole doublets corresponding to Fe³⁺ ions at octahedral sites. A monotonic increase in the value of quadrupole splitting with increasing aluminium content is observed. This is attributed to the change in the oxygen parameter of the spinel structure with the addition of aluminium. Quadrupole splitting does not show any detectable change with temperature. The value of isomer shift has been found to be independent of substitution levelx which suggests that the s-electron charge distribution of Fe³⁺ ions is not influenced by Al³⁺ substitution.     

Coexistence of paramagnetism and ferromagnetism in Fe-TiO2 nanoparticle

Magnetic properties of pure and Fe doped rutile TiO₂ and TiO_2-ε are investigated using the first principle density functional theory. The results show that the considered systems are ferromagnetic. Furthermore, the origin of ferromagnetism is discussed and it is found that the double exchange and super-exchange are the main interactions in these compounds. Based on the calculations, the magnitude of the magnetic moment depends on the concentration of impurities and oxygen vacancies and the largest magnetic moment corresponds to the Fe_xTi_1?xO_2?ε. Moreover, using a model based on the bound magnetic polarons, the coexistence of ferromagnetic and paramagnetic phases can occur in Fe_xTi_1?xO₂ containing different impurity ions such as Fe⁺² and Fe⁺³ with different Curie temperatures. The finding may presents the potential application of the considered system as diluted magnetic semiconductor.     

The Influence of the Annealing Temperature on the Properties of Sn<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Fe<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript>2</Subscript> Powders Evidenced by EMR Spectroscopy

Electron magnetic resonance (EMR) investigations of Sn_{1− x} Fe _x O₂ (x = 0.07) powders annealed at different temperatures are reported. EMR spectra show the presence of both the isolated paramagnetic Fe³⁺ ions incorporated into the SnO₂ lattice and a ferromagnetically ordered component. By increasing the annealing temperature, the EMR spectrum attributed to the ferromagnetically coupled Fe³⁺ ions diminishes probably due to the migration of Fe ions and the formation of the second phase. The presence of the second phase was evidenced by X-ray diffraction measurements.