119Sn and 57Fe M?ssbauer study of the local structure of perovskite-type ferrites CaFe2 ? x N x O5 ( N = Sc, Al) and manganite CaMn7O12

Anion-deficient substituted ferrites Ca₂Fe_{2 − x} N _x O₅ (N = Sc³⁺, Al³⁺) and mixed manganite CaMn₇O₁₂ have been investigated by ¹¹⁹Sn and ⁵⁷Fe probe M?ssbauer spectroscopy. The mechanism of charge compensation for heterovalent impurity Sn⁴⁺ ions in the structure of the ferrite Ca₂Fe₂O₅ has been established. The presence of nonequivalent crystallographic positions of manganese cations, caused by their charge ordering in the structure of the manganite CaMn₇O₁₂, is shown. Magnetic ordering of Mn³⁺ and Mn⁴⁺ cations in the octahedral sublattice of CaMn₇O₁₂ at T < T _M2 ≈ 90 K is established. Original Russian Text ? A.V. Sobolev, I.A. Presnyakov, K.V. Pokholok, V.S. Rusakov, T.V. Gubaidulina, A.V. Baranov, G. Demazeau, 2007, published in Izvestiya Rossiiskoi Akademii Nauk Seriya Fizicheskaya, 2007, Vol. 71, No. 9, pp. 1347–1354.     

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.     

Microstructure characterization and magnetic behavior of NiAlxFe2−xO4 and Ni1−yMnyAl0.2Fe1.8O4 ferrites

NiAl_xFe_2−xO₄ and Ni_1−yMn_yAl_0.2Fe_1.8O₄ ferrites were prepared by the conventional ceramic method and were characterized by X-ray diffraction, scanning electron microscopy, and magnetic measurements. The single spinel phase was confirmed for all prepared samples. A proper explanation of data is possible if the Al³⁺ ions are assumed to replace Fe³⁺ ions in the A and B sites simultaneously for NiAl_xFe_2−xO₄ ferrites, and if the Mn²⁺ ions are assumed to replace Ni²⁺ ions in the B sites for Ni_1−yMn_yAl_0.2Fe_1.8O₄ ferrites. Microstructural factors play an important role in the magnetic behavior of Ni_1−yMn_yAl_0.2Fe_1.8O₄ ferrites with large Mn²⁺ content.     

The coordination of Co2+ions in Co substituted magnetites,Fe3−xCoxO4, with x⩽0.04

⁵⁷Fe Mössbauer spectra at room temperature, both with and without external magnetic field, indicate that Co²⁺ ions in Co_xFe_3?xO₄spinels (x?0.04) are situated on the octahedral B sites. The Mössbauer parameters are listed and the existence of unpaired Fe³⁺ ions is evidenced.     

Simulation of Al/Fe disorder in Ca2FexAl2−xO5

A method is described which is capable of simulating disorder across a range of composition. It is used to study the disorder of iron and aluminium on the octahedral and tetrahedral cation sites in the Brownmillerite phase Ca₂Fe_xAl_2−xO₅. The arrangements with the lowest lattice energies are those that maximize the number of Fe³⁺ on octahedral sites throughout the composition range. An exchange of one Fe³⁺ with one Al³⁺, which results in a decrease in the number of iron ions on octahedral sites, increases the lattice energy by an amount that is dependent on x but is independent of the number of exchanges. The exchange of trivalent cations also results in an expansion in the b lattice direction, accompanied by a decrease in the a and c directions across the full range of composition.     

Microstructure, magnetic and optical properties of sputtered polycrystalline ZnO films with Fe addition

Microstructure, magnetic and optical properties of polycrystalline Fe-doped ZnO films fabricated by cosputtering with different Fe atomic fractions (x_Fe) have been examined systematically. Fe addition could affect the growth of ZnO grains and surface morphology of the films. As x_Fe is larger than 7.0%, ZnFe₂O₄ grains appear in the films. All the films are ferromagnetic. The ferromagnetism comes from the ferromagnetic interaction activated by defects between the Fe ions that replace Zn ions. The average moment per Fe ion reaches a maximum value of 1.61 μ_B at x_Fe = 4.8%. With further increase in x_Fe, the average moment per Fe ion decreases because the antiferromagnetic energy is lower than the ferromagnetic one due to the reduced distance between the adjacent Fe ions. The optical band gap value decreases from 3.245 to 3.010 eV as x_Fe increases from 0% to 10%. Photoluminescence spectra analyses indicate that many defects that affect the optical and magnetic properties exist in the films.     

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.     

Site occupancy and magnetic study of Al and Cr co-substituted Y3Fe5O12

Single-phased polycrystalline Y₃Fe_5−2xAl_xCr_xO₁₂ garnet samples (x=0, 0.2, 0.4 and 0.6) have been prepared by the conventional ceramic technique. Rietveld refinement of X-ray diffraction patterns of the samples shows them to crystallize in the Ia3d space group and the corresponding lattice constant to decrease with increasing Al³⁺ and Cr³⁺ contents (x). Mössbauer results indicate that Cr³⁺ substitutes for Fe³⁺ at the octahedral sites whilst Al³⁺ essentially replaces Fe³⁺ at the tetrahedral sites. This result indicates that co-doping of Y₃Fe₅O₁₂ does not affect the preferential site occupancy for separate individual substitution of either Cr³⁺ or Al³⁺. The magnetization measurements reveal that the Curie temperature (T_c) monotonically decreases with increasing x while the magnetic moment per unit formula decreases up to x=0.4 and then slightly increases for x=0.6. This reflects a progressive weakening of the ferrimagnetic exchange interaction between the Fe³⁺ ions at octahedral and tetrahedral sites due to co-substitution. The magnetic moment was calculated using the cations distribution inferred from the Mössbauer data and the collinear ferrimagnetic model, and was found to agree reasonably with the experimentally measured value. The phenomenological amplitude crossover, characterized by the temperature T*, has also been observed in the doped YIG and briefly discussed.     

Fe掺杂CaCu3Ti4O12陶瓷的介电性能与弛豫特性研究

采用固相反应法制备了CaCu₃Ti_4-xFe_xO₁₂(0≤x≤0.2)陶瓷,通过X射线衍射、扫描电子显微镜、介电频谱和阻抗谱等手段研究了Fe对CaCu₃Ti₄O₁₂陶瓷的结构和介电性能的影响.研究发现：CaCu₃Ti_4-xFe_{x关键词： 巨介电常数 双阻挡层电容模型 界面极化}     

Ce4+离子在Ca2SnO4一维结构基质中的电荷迁移光谱研究

利用高温固相反应法制备了Ca₂Sn_1-xCe_xO₄和Ca_2-ySr_ySn_1-xCe_xO₄一维结构发光体. XPS结果显示 Ca₂SnO₄拥有两种结合能分别为5277 eV和5293 关键词： 2Sn_1-xCe_xO₄')" href="#">Ca₂Sn_1-xCe_xO₄ 2-ySr_ySn_1-xCe_xO₄')" href="#">Ca_2-ySr_ySn_1-xCe_xO₄ 一维结构 电荷迁移光谱     

Y1-xCaxBa2Cu3-xMxO7-δ (M=Fe,Ni)体系的超导电性

本文报道,通过对Y_1-xCa_xBa₂Cu_3-xMxO_7-δ(M=Fe,Ni)体系样品的晶体结构、氧含量、正常态电阻率与温度的关系,以及超导转变温度等测量,并与YBa₂Cu_3-xMxO_7-δ(M=Fe,Ni)体系进行比较,发现Y_1-xCa_xBa₂Cu_3-xFe_xO_7-δ体系的T_c显著地高于相应x值的YBa₂Cu_3-xFe_xO_7-δ体系,而Y_1-xCa_xBa₂Cu_3-xNi_xO_7-δ体系则相反,T_c低于仅Ni替代的体系,表明Ca和Fe同时替代时两者引起的载流子浓度(n_H)变化相互补偿,抑制了仅Fe替代时引起的n_H和T_c急剧下降;而作Ca和Ni同时替代时主要的不是两者引起载流子浓度变化的相互补偿,Ca和Ni替代效应之间的关联较弱。作者认为,对Y_1-xCa_xBa₂Cu_3-xFe_xO_7-δ体系属于CuO₂平面外的元素替代,这时载流子浓度是决定Tc的主要因素;而对Y_1-xCa_xBa₂Cu_3-xNi_xO_7-δ体系,由于Ni²⁺离子主要占据Cu(Ⅱ)位,它导致磁拆对效应,Ni²⁺离子的拆对效应是引起T_c下降的直接原因。 关键词：     

Magnetic and optical properties of spinel FexCo3−xO4 thin films

Magnetic and optical properties of Fe_xCo_3−xO₄ thin films grown by sol–gel method have been investigated as the Fe composition (x  ) increases from 0 to 2. X-ray diffraction measurements revealed that the normal- and inverse-spinel phases coexist for 0.76?x?0.93$0.76?x?0.93$. The normal-spinel phase is dominant below x=0.76$x=0.76$ while the inverse-spinel phase above x=0.93$x=0.93$. The lattice constant of the inverse-spinel phase is found to be larger than that of the normal-spinel phase. For both phases the lattice constant increases with increasing x. The Fe_xCo_3−xO₄ films containing the inverse-spinel phase exhibit net magnetization that increases with increasing x  . Conversion electron Mössbauer spectrum measured on the x=0.93$x=0.93$ sample showed that Fe²⁺ ions prefer the octahedral sites, indicating the formation of the inverse-spinel phase. Analysis on the measured optical absorption spectra for the samples by spectroscopic ellipsometry indicates a dominance of the normal-spinel phase for low x in which Fe³⁺ ions mostly occupy the octahedral sites. Observation of a crystal-field transition at 1.6 eV originating from tetrahedral Fe³⁺ ion confirms the existence of the inverse-spinel phase for high x.     

Redox reactions of K3[Fe(CN)6] during mechanochemically stimulated phase transitions of AlOOH

Thermally induced redox reactions of K₃[Fe(CN)₆] (1) were investigated for a broad temperature range by thermal methods and structure analytical methods (ESR and Mößbauer spectroscopy, X-ray Powder diffraction and XANES). Based on the influence of the mechanically activated and transforming matrices 2 and 3, redox processes can be tuned to form doped Al₂O₃ systems which contain either isolated Fe³⁺ centres or redox active phases and precursors like (Al_1−xFe_x)₂O₃ (4), (Al_3−xFe_x)O₄ (5), Fe₃O₄, Fe₂O₃ and Fe⁰. The phase Fe₃C and the chemically reactive C-species were detected during the reaction of 1. The final composition of the doped products of α-Al₂O₃ is mainly influenced by the chemical nature of the Fe doping component, the applied temperature and time regime, and the composition of the gas phase (N₂, N₂/O₂ or N₂/H₂). From the solid state chemistry point of view it is interesting that the transforming matrix (2 and 3) possesses both oxidative and protective properties and that the incorporation of the Fe species can be performed systematically.     

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.     

Effect of Fe/Pb molar ratio on the structure,magnetic and dielectric properties of PbFe12O19 nanoparticles

In this paper, lead hexaferrite (PbFe₁₂O₁₉) nanoparticles were synthesized by sol-gel method. In order to prepare PbFe₁₂O₁₉ nanoparticles, the metal nitrates with Fe/Pb?=?8, 10, 11, 12, 14 ratios and citric acid were used. The structure, morphology, magnetic, and dielectric properties of PbFe₁₂O₁₉ nanoparticles were characterized by X-ray diffraction (XRD), field emission scanning electron microscope (FESEM), vibrating sample magnetometer (VSM) and LCR meter. XRD results revealed that the samples with Fe/Pb?≤?10 and Fe/Pb?>?10 have single-phase hexaferrite and hematite (α- Fe₂O₃) structures, respectively. As a result, the sample with Fe/Pb?=?10 is single-phase and shows the highest values of the saturation magnetization and remanence magnetization. We found that the values of dielectric constant (ε′) and dielectric loss (ε″) increase with an increase in the Fe/Pb molar ratio from 8 to 12 and then decreases with an increase of Fe/Pb molar ratio to 14. The variation of ac conductivity (σ_ac) with frequency ranging from 1?kHz to 200?kHz showed that electrical conductivity in these ferrites is mainly due to the electron hopping mechanism.     

Valence states of iron ions in nanostructured yttrium iron garnet Y3Fe5O12 studied by means of soft X-ray absorption spectroscopy

Nanostructured samples of yttrium iron garnet Y₃Fe₅O₁₂ obtained by plastic deformation method (high-pressure torsion) were studied with help of soft X-ray absorption spectroscopy using Fe 2p and O 1s spectra. Experimental spectra were compared with crystal field multiplet calculations for Fe ions. Some amount of Fe²⁺ ions in nanostructured Y₃Fe₅O₁₂ was found. The concentration of Fe²⁺ ions was found to be increased with the increase of the degree of plastic deformation.     

Magnetic properties of the garnets Bi0·8Ca2χT2·2-2.χFe5-χVχ]O12

The behaviour of the magnetization, Curie temperature, Mössbauer spectra, and lattice parameter is studied in the garnet series Bi_0·8Ca_2.χT_2·2-2.χFe_5-χV_χ]O₁₂. The shape of magnetization vs temperature curves shows only a minor dependence on x. The hyperfine field at the octahedral ⁵⁷Fe nuclei at 5°K decreases linearly with x (12·5kOe per substituted V neighbour), while that at the tetrahedral ⁵⁷Fe nuclei is not affected. The dependence of the Curie temperatures and hyperfine fields on x is discussed in relation to the Fe-O-V-O-Fe exchange. The influence of Bi substitution is consistent with the idea of a geometric effect.     

Electronic conductivity and thermopower of Ca2NaMg2V3O12−x garnet

Results are reported from conductivity and thermoelectric power measurements on partially reduced Ca₂NaMg₂V₃O_12?x, with x < 5.10^?2, at temperatures of 300–1100 K. The conductivity is thermally activated with activation energies 0.26 ? E_a ? 1.28 eV for differently reduced samples. The thermopower is temperature independent in the 300–800 K region. These results are shown to be consistent with the adiabatic hopping of small polarons localised on the vanadium sublattice, where defect interactions result in the formation of multiple conduction pathways.     

Spectroscopic study of ZnO doped CeO2-PbO-B2O3 glasses

Glass samples of compositions xZnO-xCeO₂-(30−x)PbO-(70−x)B₂O₃ with x varying from 2% to 10% mole fraction are prepared by the melt quench technique. The structural and optical analysis of glasses is carried out by XRD, FTIR, density and UV-visible spectroscopic measurement techniques. The FTIR spectral analysis indicates that with the addition of ZnO contents in glass network, structural units of BO₃ are transformed into BO₄. It has been observed in our previous work that band gap decreases from 2.89 to 2.30 eV for CeO₂-PbO-B₂O₃ glasses with cerium content varying from 0% to 10% [Gurinder Pal Singh, Davinder Paul Singh, Physica B 406(3) (2011) 640-644]. With the incorporation of zinc in CeO₂-PbO-B₂O₃ glasses, the optical band gap energy decreases further from 2.38 to 2.03 eV. This causes more compaction of the borate network, which results in an increase of density (3.39-4.02 g/cm³). Transmittance shows that ZnO in glass samples acts as a reducing agent thathelps to convert Ce⁴⁺→Ce³⁺ ions.     

Optical,magneto-optical and mössbauer spectroscopy on Co3+ substituted cobalt ferrite Co2+Fe2−xCo3+xO4(0 ⩽ x ⩽ 2)

The magneto-optical spectra of Co_1+xFe_2?xO₄ show with increasing Co³⁺ content an increasing intensity of the 4A₂ ? 4T₁(F) and 4A₂ ? 4T₁(P) transition of Co²⁺ at 0.8 and 2.0 eV. A decrease in the Co²⁺-Fe³⁺ charge transfer transitions on octahedral sites is found. In the optical spectra a strong increase in optical absorption is found with dominant transitions at 0.8, 1.6 and 2.6 eV due to Co³⁺ crystal field transitions on octahedral sites and a Co²⁺-Co³⁺ charge transfer. Conversion Electron Mössbauer Spectroscopy has been used to determine the cation distribution in the surface layer of the samples. The results indicate a shift of Co²⁺ from octahedral to tetrahedral sites when Co³⁺ is substituted in CoFe₂O₄. This results in enhanced optical absorption, enhanced magneto-optical effects and a lower Curie temperature.