尖晶石铁氧体TixNi1-xFe2O4中阳离子分布和Ti离子磁矩的实验研究

采用固相反应法制备了系列样品Ti_xNi_1-xFe₂O₄ (x=0.0, 0.1, 0.2, 0.3, 0.4). 室温下的X射线衍射谱表明样品全部为(A)[B]₂O₄型单相立方尖晶石结构, 属于空间群Fd3m. 样品的晶格常数随Ti掺杂量的增加而增大. 样品在10 K温度下的比饱和磁化强度σ_S随着Ti掺杂量x的增加逐渐减小. 研究发现, 当Ti掺杂量x≥ 0.2时, 磁化强度σ随温度T的变化曲线出现两个转变温度T_L和T_N. 当温度低于T_N时, 磁化强度明显减小; 当温度达到T_N时, dσ/dT具有最大值. σ-T曲线的这些特征表明, 由于Ti掺杂在样品中出现了附加的反铁磁结构. 这说明样品中的Ti离子不是无磁性的+4价离子, 而是以+2和+3价态存在, 其离子磁矩的方向与Fe和Ni离子的磁矩方向相反. 利用本课题组提出的量子力学方势垒模型拟合样品在10 K温度下的磁矩, 得到了Ti, Fe和Ni三种阳离子在(A)位和[B]位的分布情况, 并发现在所有掺杂样品中, 80%的Ti离子以+2价态占据尖晶石结构的[B]位.     

Magnetic and magneto-transport properties of (Ba0.8Sr0.2)2−xNdxFeMoO6

The variation in structural, magnetic and magneto-transport properties of the double perovskite system (Ba_0.8Sr_0.2)_2?xNd_xFeMoO₆ {0.0<X<0.5} induced by Nd³⁺ doping (electron doping) has been studied and compared. The samples were prepared by standard solid state reaction method in a reducing atmosphere. The parent compound showed a saturation magnetic moment value of 3.75 μ_B/f.u. at an applied field of 0.5 T and a change in magnetoresistance value up to 26% (77 K, 0.8 T). The Rietveld refinement of the X-ray diffraction data showed a continuous decrease in lattice parameters and Fe–Mo ordering with increasing Nd³⁺ doping. The Curie temperature was found to increase with Nd³⁺ doping (3 K per % of Nd) while the saturation magnetic moment values and magnetoresistance values were found to decrease. The observed variations in magnetic and magneto-transport properties of the system are explained on the basis of increasing antisite disorder defects and band filling effects induced by electron doping. We have observed the dominant role of band filling in determining the low field magnetoresistance of these systems.     

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.     

Structure and magnetism of semiconductor crystals of the (Ga1 ? xMnx)2Se3 (x = 0?0.04) compounds

Neutron diffraction and magnetic measurements have been used to study the effect of doping with Mn³⁺ ions on the fine crystal structure of the Ga₂Se₃ monoclinic compound. It has been established that the structural state of the crystals is changed even at a relatively low doping level (x = 0.04). Arguments in favor of the fact that local Jahn-Teller distortions are responsible for the formation of the fine structure and magnetism in compounds of this class are presented.     

Synthesis of Fe-doped NiO nanofibers using electrospinning method and their ferromagnetic properties

To make p-type diluted magnetic semiconductor (DMS), Ni_1−xFe_xO nanofibers with different Fe doping concentrations have been successfully synthesized by electrospinning method using polyvinyl alcohol (PVA) and Ni(CH₃COO)₂·4H₂O as starting materials. The nanofibers were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy, superconductivity quantum interference device (SQUID) and X-ray photoelectron spectroscopy (XPS) test. The results show that Fe doping has no influence on the diameter and surface morphology of NiO nanofibers, and the nanofibers are polycrystalline with NaCl structure. All Fe-doped samples show obvious ferromagnetic properties and the saturation magnetization is enhanced with increase of the doping concentration of Fe, which indicates that the doped Fe has been incorporated into the NiO host and results in room-temperature ferromagnetism in the Ni_1−xFe_xO nanofibers.     

Experimental and theoretical assessment of Fe-doped indium-oxide-based dilute magnetic semiconductors

Specimens of iron-doped indium oxide (In_1-xFe_x)₂O₃ with x?=?0.015, 0.03, 0.045 and 0.06, amalgamated through a traditional solid-state reaction method followed by H₂/air sintering, were characterised using an X-ray diffractometer (XRD), a vibrating sample magnetometer (VSM), and a scanning electron microscope (SEM) to investigate their structural, magnetic and morphological properties respectively. According to XRD plots, all the specimens exhibit cubic bixbyite structures along with ancillary phases. Magnetic assessment showed that In₂O₃ has a negative susceptibility, exhibiting diamagnetic behaviour at room temperature. The doping of Fe ions induces ferromagnetic (FM) ordering, which is enhanced with increasing doping content. The strength of the magnetisation increases when the specimens are exposed to H₂ but is reduced on further air sintering. A bound magnetic polaron (BMP) model is successfully fitted to the observed FM data involving localised carriers and magnetic cations. A multivariate assessment viz. a hierarchical cluster analysis (HCA) was used to corroborate and strengthen the experimental determined magnetic properties. A homogeneous particle distribution was observed in all SEM micrographs and is validated through MATLAB-based simulation by applying a watershed segmentation algorithm. Surface plots also confirm the change in magnetic properties with increase in doping concentration.     

Effect of ion irradiation on magnetic property of exchange coupled interfacial structures of Fe/NiO and NiO/Fe on Si substrates

The role of defects on the magnetic behaviour of exchange coupled interfacial structures of Fe/NiO and NiO/Fe on Si substrates has been studied. For introduction of defects in the structures, swift (～ 100 MeV) heavy ion irradiation has been used, which is known to cause structural and microstructural modifications. In our earlier study [Srivastava, N; Srivastava, P.C. J. Appl. Phys. 2012, 111, 123909] on similar structures, the significant magnetic behaviour (of exchange bias (EB) and coercivity) for Fe/NiO/nSi interfacial structure was observed and discussed in the realm of interfacial structural modification in the antiferromagnetic layer of the structure. The irradiated interfacial structures have been characterized from X-ray diffraction and M–H characteristics. Structural investigation has shown the formation of various silicide and oxide phases due to the irradiation-induced interfacial intermixing. A significant enhancement in EB field and coercivity has been observed for Fe/NiO/nSi interfacial structure on the irradiation (as compared to unirradiated ones). The observed enhanced EB and coercivity on the irradiation has been understood due to the creation of domain wall pinning centres across the interface as a result of ion irradiation. Moreover, the present study confirms the role of defects in the antiferromagnetic layer to cause the significant change in EB and coercivity. The observation supports the domain state model of EB in the exchange-coupled structures.     

Mössbauer emission study of57Co: YBa2Cu3O7−y HTSC

Mössbauer emission spectroscopy is performed on⁵⁷Co:YBa₂Cu₃O_7–y oxides in a temperature range from 300 K to 77 K. The spectra show, at least two different location for the⁵⁷Co(⁵⁷Fe) impurities. The isomer shift and quadrupole splitting values of the⁵⁷Fe daughter are coincident with those observed in⁵⁷Fe absorption experiments. From the analysis of theIS andQS values as well as from the relative location of Fe impurity levels in the HTSC matrix it is argued that:a) Co impurities enters into the lattice mainly in the Cu1 sites, but some of them have a higher coordination number.b) The daughter⁵⁷Fe exists as localized Fe⁴⁺ state.c) The parent⁵⁷Co enter as a localized Co³⁺ state. These conclusions appear consistent with the observed increase ofN(0) on doping with Fe or Co ions and with the existence of localized magnetic moments as determined from paramagnetic susceptibility measurements.     

Low temperature magnetic ordering in Fe-doped TiO 2 samples

Fe-doped TiO₂ samples with different Fe content prepared by mechanical alloying have been investigated by means of Mössbauer spectroscopy at 300 and 4.2 K. The results indicate the coexistence of Fe^2?+? and Fe^3?+? ions in paramagnetic states at room temperatures in the rutile structure. All samples present magnetic order at 4.3 K. When the Fe concentration increases the Fe ions in the rutile matrix became closer giving the possibility of strong magnetic interactions between them. The temperature evolution of the magnetic order was followed for the 15 at.% of Fe sample. The Fe-doped oxide formed for this composition orders below 20 K reaching an almost totally magnetic ordered state at 4.3 K.     

Role of Ga-doping in ironben gallium alloy clusters

The structural and magnetic properties of Fe_n-mGa_m (n=3～6, m=0～2; n=13, m=0～3) alloy clusters have been studied using density functional theory. The substitutional doping is favourable for small clusters with up to six atoms at low Ga concentration and substitutional Ga atoms in 13-atom clusters prefer surface sites. The Ga-doping generally could reduce the energetic stability but enhance the electronic stability of Fe clusters, along with a decrease of the local magnetic moments of Fe atoms around Ga dopants. These findings provide a microscopic insight into Fe-Ga alloys which are well-known magnetostriction materials.     

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.     

Nd2Fe14B的价电子结构分析和磁性计算

应用固体与分子经验电子理论计算了Nd₂Fe₁₄B的价电子结构、磁矩和居里温度,计算结果与实验值相符.计算表明:该合金的磁性与3d磁电子数成正比.从Fe(c)晶位到Fe(k₂)晶位磁矩增加,其机理源于价电子、哑对电子和3d磁电子之间的转化,有78%的哑对电子和18%的3d共价电子转化成了磁电子.居里温度和磁矩与Fe原子配位数成正比,与加权等同键数I^σ成反比,Nd原子 关键词： 2Fe₁₄B')" href="#">Nd₂Fe₁₄B 价电子结构 居里温度     

Role of holes states on metal to insulator transition and collapse of magnetic ordering in LaFe1−xNixO3 (x = 0.0–0.5)

Polycrystalline LaFe_1?xNi_xO₃ (x = 0.0, 0.1, 0.3 and 0.5) have been prepared by the standard solid state reactions method. The phase formation has been confirmed by the powerful synchrotron X-ray diffraction experiment. In order to investigate the effects of Ni doping on the oxidation state, spin state and the magnetic ordering of the iron cations, ⁵⁷Fe Mössbauer Spectroscopy has been carried out at room temperature. Iron is present as Fe³⁺ in high spin state in LaFeO₃. Ni doping has no effect on the spin state of the Fe³⁺ cations. However, a progressive increase in the concentration of Fe⁴⁺ cations has been inferred. Relatively stronger covalent character of the Fe⁴⁺–O^?2 bond causes a progressive collapse in the magnetic ordering and delocalization of the hole states.     

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.     

Hard mode infrared spectroscopy of CaTiO3—CaFeO2.5 perovskites

Abstract

Powder-absorption infrared (IR) spectra of perovskites CaFe_xTi_1?x O_3?x/2 (0≤x≤1) annealed at different temperatures were investigated at room temperature in the range 135–2000 cm^?1. The spectra change as a function of composition, annealing temperature and structural state (order-disorder of oxygen vacancies). Autocorrelation analysis has been used to determine variations of average line widths of groups of peaks in the primary IR spectra. The band widths increase on increasing Fe content in the region of the structures with disordered oxygen vacancies and they decrease on going through the order-disorder boundary. High degrees of local structural heterogeneity are suggested by the effective line widths of the phases at intermediate compositions. The intensity of bands at ～150 and ～443 cm^?1 decreases with increasing Fe content in the compositional range of the disordered structures. Finally, for every annealing temperature, the frequency of the band at ～600cm^?1 systematically shifts to higher values on increasing Fe content, these values decreasing again for the fully ordered structures.     

Enhanced multiferroic characteristics in Fe-doped Bi4Ti3O12 ceramics

Modification of Bi₄Ti₃O₁₂ multiferroic ceramics prepared by a conventional solid state reaction method were investigated by substituting Ti partly with Fe. The introduction of Fe does not change the layered perovskite structure of Bi₄Ti₃O₁₂. Upon increasing Fe content, the remnant polarization of the samples is enhanced. The magnetism of the ceramics at room temperature develops from diamagnetism to weak ferromagnetism with increasing Fe doping. The largest variations of 15% and 6% in remnant polarization and magnetization, achieved in a Bi₄Ti₁Fe₂O_12?δ sample after poling it in a magnetic field at 1 T and a DC electric field at 30 kV/cm for 10 min, are evidence of magnetoelectric coupling between the electric dipoles and magnetic dipoles at room temperature. The present results suggest a new candidate for a room temperature multiferroic material with enhanced properties.     

Studies of absorption spectra and the photovoltaic effect in LiNbO3:Mg:Fe crystals

The absorption spectra, photoconductivities and photovoltaic currents of LiNbO₃:Fe crystals with different Mg doping levels and Li/Nb ratios in the oxidized state have been investigated at room temperature. The Fe²⁺ ions in LiNbO₃:Mg:Fe with Mg content above a critical value are more easily oxidized than in crystals with Mg content below a critical value. The photoconductivity of LiNbO₃:Mg:Fe crystals with Mg content above a critical value is one order of magnitude higher than those with Mg content below a critical value, however, the photovoltaic current of the former is one order of magnitude lower than the latter. The differences are postulated to be due to different sites of Fe in these two classes of crystals.     

Co掺杂Bi5Ti3FeO15多铁陶瓷的磁电性能

采用了传统的固相烧结工艺制备出Bi₅Fe_1-xCo _{x Ti3O15(BFCT-x,x=0.0—0.6)多铁陶瓷样品,研究了Co掺杂对Bi5FeTi3O15(BFTO)微观结构、铁电和磁性能的影响.X射线衍射谱显示样品均已形成四层铋系层状钙钛矿相,且随着掺杂量的增加发生了结构变化.拉曼光谱进一步证实掺入的Co占据了< 关键词： 固相烧结 多铁陶瓷 剩余磁化 剩余极化}     

Influence of magnetic (Fe) and non-magnetic (Ga) ion doping at Mn-site on the transport and magnetic properties of La0.7Ca0.3MnO3

The modifications in electrical and magnetic properties of polycrystalline bulk La_0.7Ca_0.3Mn_1−xT_xO₃ (T=Fe, Ga) samples at relatively higher doping concentration (x=0.08-0.12) are investigated. All the synthesized, single phase samples were subjected to resistivity measurements in the temperature range 50-300 K. No insulator-metal transition (T_P) was observed for Fe doped samples with x=0.12. For all the other samples the transition temperature decreased with increase in doping concentration. The small polaron hoping energy was found to increase, rather slowly, with increase in doping concentration. The effect on magnetic properties is also prominently observed with respect to doping element and doping concentration. Interestingly, with the increase in doping concentration, the Curie temperature (T_C) and T_P separate out significantly indicating decoupling of electric and magnetic properties. Changes in these properties have been analyzed on the basis of magnetic disorder introduced in the system due to the magnetic and nonmagnetic nature of these ions rather than strong lattice effects which is insignificant due to similar ionic radii of Fe⁺³ and Ga⁺³ when compared to that of Mn⁺³.     

第一性原理计算ZrnFe(n=2—13)团簇的基态结构及其磁性

从第一性原理出发，利用密度泛函理论中的广义梯度近似对Zr_nFe(n=2—13)团簇进行了结构优化、能量和频率计算.在充分考虑自旋多重度的前提下，对每一具体尺寸的团簇，得到了多个平衡构型，并根据能量高低确定了团簇的基态结构.综合团簇的结合能、二阶能量差分以及团簇的最高占据轨道和最低未占据轨道间的能隙可知Zr₅Fe，Zr₇Fe和Zr₁₂Fe团簇的稳定性相对较高，Zr₁₂Fe团簇的结构是具有I_h对称性的正二十面体，而且Zr₁₂Fe的稳定性在所有团簇中是最高的.另外，不仅Zr₅Fe，Zr₇Fe和Zr₁₂Fe团簇的稳定性相对较高，而且它们均为磁性团簇(而Zr_n团簇的磁矩在n≥5时已经发生了淬灭)，由此可知通过选择合适的掺杂元素可能得到高稳定的磁性团簇.从Mulliken布居分析结果可知，除了在Zr₁₂Fe团簇中Fe原子失去少量电荷外，其他团簇中Fe原子均从Zr原子那里得到了一定量电荷，即Fe原子在Zr_nFe(n=2—13，n≠12)团簇中是电子受体.