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.     

Dielectric and piezoelectric properties of Fe2O3-doped (Na0.5K0.5)0.96Li0.04Nb0.86Ta0.1Sb0.04O3 lead-free ceramics

The effect of a small amount Fe₂O₃ (0.1-2 mol%) doping on the electrical properties of (Na_0.5K_0.5)_0.96Li_0.04Nb_0.86Ta_0.1Sb_0.04O₃ (NKLNTS) ceramics was investigated. It was found that the B-site substitution of Fe³⁺ does not change the crystal structure within the studied doping level and all modified ceramics have a pure tetragonal perovskite structure at room temperature. The addition of Fe₂O₃ can promote the sintering of NKLNTS ceramics, and simultaneously cause the grain growth so that Fe³⁺-doped NKLNTS compositions show degraded densification at higher doping level. Furthermore, the dielectric properties of the NKLNTS ceramics do not show a significant change by Fe₂O₃ doping. However, the addition of Fe₂O₃ was found to have a significant influence on the electric fatigue resistance and the durability against water. The presence of oxygen vacancies caused by the replacement of Fe³⁺ for B-site ions makes the NKLNTS ceramics harder.     

Evolution of microstructure and dielectric properties of (LiCe)-doped Na0.5Bi2.5Nb2O9 Aurivillius type ceramics

Aurivillius type (NaBi)_0.5?x(LiCe)_xBi₂Nb₂O₉ ceramics were prepared by the standard ceramics route. The single crystal structural ceramics were achieved for all compositions and lattice distortion was decreased by (LiCe) dopants. The temperature dependent dielectric properties revealed that all compositions possess a high Curie-temperature (>780 °C). A modified Curie–Weiss relationship is used to study the diffuseness behavior of a ferroelectric phase transition indicating the degree of diffuseness of NBN-based ceramics increased with (LiCe) modifications. The degradation of resistance implied a plausible model that Ce⁴⁺ ions entered into the B-site of the pseudo-perovskite structure and acted as acceptor doping. Further investigation demonstrated that both electrical conduction and dielectric relaxation processes were associated with the oxygen vacancies produced by the substitution of Nb⁵⁺ ions by the Ce⁴⁺ ions.     

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.     

Fe掺杂对自旋梯状化合物Sr14(Cu1－yFey)24O41的结构和电输运性质的影响

采用常规的固相合成法分别制备了Fe³⁺掺杂和2/3Fe³⁺+1/3Fe²⁺混合Fe离子掺杂的两组Sr₁₄(Cu_1-yFe_y)₂₄O₄₁系列样品.X射线衍射分析显示，当Fe³⁺离子的掺杂量y≤0.03以及2/3Fe³⁺+1/3Fe²⁺混合Fe离子掺杂量y≤0.02时，样 关键词： 强关联电子系统 自旋梯状结构化合物 晶体结构 电输运性质     

The effects of oxygen vacancies on the electrical properties of W,Ti doped CaBi2Nb2O9 piezoceramics

Different type doped CaBi₂Nb₂O₉ (CBN) ceramics were prepared by a conventional solid state sintering method. The number of oxygen vacancies were decreased or increased by the introduction of W⁶⁺ and Ti⁴⁺ doping in CBN ceramics. The influence of W⁶⁺, Ti⁴⁺ and W⁶⁺/Ti⁴⁺ dopants on the microstructures and electrical properties of CBN-based ceramics was investigated. The voids and spherical morphology in the SEM image of W, Ti co-doped ceramics indicate that W, Ti co-doping could change the microstructure of CBN-based ceramics. Impedance analysis results show that the electrical properties of CBN-based ceramics have a close relationship with the number of oxygen vacancies. W doping and W, Ti co-doping decrease the oxygen vacancies, as a result, the resistance and piezoelectric properties were increased and the frequency dispersion of dielectric properties were restrained.     

Local structure of the rhombic Fe3+ center in KTaO3

A study is reported of the effect of high-temperature annealing in oxygen, an inert gas, and water vapor on EPR spectra of the Fe³⁺ center of different local symmetries in the incipient ferroelectric KTaO₃. An analysis of the relations obtained permits one to propose and substantiate a model of the rhombic Fe³⁺ center, by which Fe³⁺ substitutes for Ta⁵⁺ near two oxygen vacancies (Fe³⁺-2V _O). Calculations of the crystal-field parameters performed within the Newman superposition model showed in the rhombic center the Fe³⁺ ion is displaced along [011] from the Ta⁵⁺ position it occupies within the tetrahedron formed by four oxygens, to a distance of about 0.25 Å. Some of the recent results obtained in second-harmonic light scattering in iron-doped KTaO₃ samples are interpreted. It is shown that, within the temperature range of 4.2–300 K, rhombic Fe³⁺ centers are static electric dipoles, and that they cannot therefore be a source of dielectric losses in KTaO₃ at T≈40 K, as suggested earlier in some publications.     

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.     

Microstructure and dielectric study of pure BST and doped BSTF ceramic materials by broadband dielectric spectroscopy

Pure BST and doped BSTF (with BSTF2: Fe₂O₃ 2 wt % and BSTF4: Fe₂O₃ 4 wt %) ceramics were prepared by solid state reaction. XRD pattern showed the different phases were formed depend on the weight percent of Fe₂O₃. The crystal size and lattice parameters increased while the lattice strain decreased. The topography of the sintered samples shows increase of the grain size with increasing Fe₂O₃ ratio and hence enhances the compaction of ceramics. Broadband dielectric spectroscopy was employed to investigate the effect of magnetite nanoparticle on the dielectric properties of the pure BST ceramic. The interfacial polarization and the conductivity contribution reflect the high values of permittivity and its gradual increase as frequency decreases. The two BSTF samples show relaxation peak dynamic originated from presence of immobile species/electrons at low temperatures and defects/vacancies results from the formation of oxygen vacancies originates from the spontaneous change in oxidation states of Fe ions (Fe ^3+/Fe²⁺) at high temperatures. The relaxation rate obeys Arrhenius law at high temperatures in case of BST sample with activation energy 225 kJ/mol. This high value of activation energy at higher temperatures reflects and confirms the slowed down of the dynamics at the interphase and the decoupling nature of the OH-dynamic and the interfacial polarization.     

Recent developments in the formation and structure of tin-iron oxides by laser pyrolysis

Complex oxides demonstrate specific electric and magnetic properties which make them suitable for a wide variety of applications, including dilute magnetic semiconductors for spin electronics. A tin-iron oxide Sn_1−xFe_xO₂ nanoparticulate material has been successfully synthesized by using the laser pyrolysis of tetramethyl tin-iron pentacarbonyl-air mixtures. Fe doping of SnO₂ nanoparticles has been varied systematically in the 3-10 at% range. As determined by EDAX, the Fe/Sn ratio (in at%) in powders varied between 0.14 and 0.64. XRD studies of Sn_1−xFe_xO₂ nanoscale powders, revealed only structurally modified SnO₂ due to the incorporation of Fe into the lattice mainly by substitutional changes. The substitution of Fe³⁺ in the Sn⁴⁺ positions (Fe³⁺ has smaller ionic radius as compared to the ionic radius of 0.69 Å for Sn⁴⁺) with the formation of a mixed oxide Sn_1−xFe_xO₂ is suggested. A lattice contraction consistent with the determined Fe/Sn atomic ratios was observed. The nanoparticle size decreases with the Fe doping (about 7 nm for the highest Fe content). Temperature dependent ⁵⁷Fe Mössbauer spectroscopy data point to the additional presence of defected Fe³⁺-based oxide nanoclusters with blocking temperatures below 60 K. A new Fe phase presenting magnetic order at substantially higher temperatures was evidenced and assigned to a new type of magnetism relating to the dispersed Fe ions into the SnO₂ matrix.     

Effect of Sm,Co codoping on the dielectric and magnetoelectric properties of BiFeO3 polycrystalline ceramics

Multiferroic Bi_0.95Sm_0.05Fe_1−xCo_xO₃ (x=0−0.1) ceramics were prepared by the rapid liquid phase sintering method. For all the samples studied, the dielectric constant and dielectric loss decrease with increasing frequency in the range from 1 kHz to 1 MHz. It shows that the dielectric constant of Bi_0.95Sm_0.05FeO₃ at 10 kHz is about forty times larger than that of pure BiFeO₃. This dramatic change in the dielectric properties of Bi_0.95Sm_0.05Fe_1−xCo_xO₃ (x=0−0.1) samples can be understood in terms of the space charge limited conduction associated with crystal defects, which was indicated by the increase of magnetoelectric effect with doping Co³⁺ under applied magnetic field from 1 to 8 kOe. It was believed that the ferroelectric polarization enhancement comes from the exchange interaction between the Sm³⁺ and Fe³⁺ or Co³⁺ ions for Bi_0.95Sm_0.05Fe_0.95Co_0.05O₃ at room temperature.     

Studying local structural, valence, and magnetic states of iron ions in Bi0.9Ca0.1FeO3 perovskite

Mössbauer method was used to study a perovskite compound Bi_0.9Ca_0.1FeO₃ at T = 295 K and at temperature above T _N . It has been established that Bi_0.9Ca_0.1FeO₃ has a rhombohedral crystal structure similar to that of BiFeO₃. The substitution of Ca²⁺ for Bi³⁺ ions leads to the formation of three states of Fe³⁺ ions with an octahedral surroundings and one state with a tetrahedral oxygen surroundings with substantially different hyperfine magnetic fields. All Fe ions are in a trivalent state; the compensation of the charge deficit occurs via the formation of oxygen vacancies. Above T _N , two structurally nonequivalent states of Fe³⁺ ions exist in the Bi_0.9Ca_0.1FeO₃ sample, which correspond to the Fe³⁺ ions with an octahedral and tetrahedral oxygen coordination.     

Dielectric relaxations in Tb0.91Yb1.38Bi0.71Fe5O12 ceramics

Dielectric relaxations of Tb_0.91Yb_1.38Bi_0.71Fe₅O₁₂ ceramics were investigated. A Debye-type relaxation was observed in the temperature range of 125-620 K with an activation energy of 0.29 eV. This activation energy agreed well with that of carriers hopping between Fe²⁺ and Fe³⁺, indicating that this relaxation might be a dipolar-type relaxation associated with the hopping carries. A high relaxorlike dielectric peak with a very strong frequency dispersion in the high temperature range of 400-620 K might be originate from the oxygen vacancies related dielectric relaxation.     

Etude De La Conductivite Electrique Des Ferrites Oxyfluores A Structure Spinelle

An investigation of the electrical conductivity of some oxyfluoride spinels of formula Zn_x²⁺Fe_1?x³⁺[M²⁺ Fe³⁺]O_4?xF_x (M = Fe, Co, Ni) and Fe³⁺[N_x²⁺Fe²⁺Fe_1?x³⁺]O_4?xF_x (N = Fe, Ni) shows that the conduction depends on the composition of the B sites: the activation energy increases, the conductivity and the Fe₃O₄ transition temperature decrease as the substitution rate of Fe³⁺ by N²⁺ in the B sites increases. The authors conclude to a hopping mechanism between the B cations; the anionic sublattice and the cationic A sublattice do not participate in the conduction.     

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.     

Colossal permittivity in (Li + Nb) co-doped Fe2O3 ceramics

(Li + Nb) co-doped (Li + Nb)_xFe_2-xO₃ (with x = 0.0005, 0.005, 0.05, and 0.1) ceramics were prepared by sol-gel method. Their structural, dielectric, humidity, and magnetic properties were investigated. Colossal permittivity (~10⁴) was approached or achieved in all doped samples even with a very small doping level of x = 0.0005. The colossal permittivity behavior is composed of two dielectric relaxations with the low-temperature one being a polaron relaxation due to electrons hopping between Fe³⁺ and Fe⁴⁺ ions and the high-temperature one being a Maxwell-Wagner relaxation caused by humidity-sensing properties.     

Effect of chemical modification on the structure and dielectric and magnetic properties of multiferroic (1 – x)BiFeO3-xDyFeO3 solid solution

The solid solution of (1-x)BiFeO₃-xDyFeO₃ was prepared by solid state reactions in the form of ceramics. The effects of chemical modification by means of aliovalent ionic substitution of Ti⁴⁺ for Fe³⁺ on the structure and dielectric properties were investigated. A morphotropic phase boundary bridging the perovskite rhombohedral phase and the orthoferrite orthorhombic phase was identified at x around 0.1. The chemical modification was found to stabilize the perovsite phase. The dielectric performance of the solid solution was improved by the substitution of Ti⁴⁺ for Fe³⁺, which decreased the electric conductivity by reducing oxygen vacancies, as evidenced by the decrease in loss tangent values. Magnetic hysteresis and large saturated magnetization (0.5 μ_B/f.u.) were realized in 0.92BiFeO₃-0.08DyFeO₃ with 2% substitution of Ti⁴⁺ for Fe³⁺, which is believed to arise from the disruption of the spiral spin modulation after structural modification, and the interaction between the spins of the Dy³⁺ and Fe³⁺ at low temperatures which decouples the antiferromagnetic order between the Fe³⁺ ions.     

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.     

The relationship between magnetic behaviour and local structure around Fe ions in Fe-doped TiO2 rutile

The magnetic and structural characterization of Ti_1−xFe_xO₂ (x=0.025, 0.05, 0.07, 0.125, and 0.15) samples prepared by mechano-synthesis using TiO₂ and Fe₂O₃ as starting materials are reported. XANES measurements performed at the Fe K-edge show that Fe ions are in 3+ oxidation state in the 7 at% Fe-doped sample and in a mixture of 2+ and 3+ oxidation states in the other samples. EXAFS results show the incorporation of Fe ions substituting Ti ones in the rutile TiO₂ structure. They also reveal a strong correlation between the number of oxygen nearest neighbours and the Fe²⁺ fraction, i.e the number of oxygen near neighbours decreases when the Fe²⁺ fraction increases. All samples present ferromagnetic-like behaviour at room temperature. We found a clear dependence between saturation magnetization and coercivity with the fraction of Fe²⁺ and/or the number of Fe near neighbour oxygen vacancies.     

Enhancement of ferromagnetism and multiferroicity in Ho doped Fe rich BiFeO3

Crystalline solid solution of BiHo_XFe_1+XO₃ (X=0, 0.05, 0.1, and 0.15) ceramics have been successfully synthesized by slow step sintering schedule. At particular value of X (X=0.1) the sample showed good crystallinity with almost impurity free phases. It was observed that at particular concentration of X (X=0.1), the sample showed enhanced M–H loop by Ho doping in presence of excess Fe. Furthermore, the M–H loop gets reduced with the increase in value of X (X=0.15). Compared to the pure BFO, the dielectric properties for X=0.1 composition are improved due to the decreased oxygen vacancies by the stabilized oxygen octahedron. Raman spectra over the frequency range of 100–1500 cm^?1 have been systematically investigated with different concentrations of X. Besides the changes of the peak position and the line width of the all modes, the prominent frequency shift, the line broadening and variation of the intensity for the two-phonon mode between 1270 and 1280 cm^?1 were observed with increase in value of X. All these results indicate the existence of strong spin–phonon coupling in Ho doped Fe rich BFO.