Magnetic properties of BiFe<Subscript>0.93</Subscript>Mn<Subscript>0.07</Subscript>O<Subscript>3</Subscript> powders obtained by ultrasonic spray pyrolysis

Samples of BiFe_0.93Mn_0.07O₃ with different specific surface area were synthesized for the first time by ultrasonic spray pyrolysis. The resulting powders consist of porous particles of a spherical shape of medium size ~0.5 μm and have record values of residual magnetization and coercive force. It is found that the magnetic properties of the porous powder particles are determined by the distortion of the crystal lattice and the presence of uncompensated magnetic moments of iron ions on the surface.     

State of iron atoms in SiO2·xFe2O3 gels

Mössbauer studies are made of ⁵⁷Fe nuclei in dry SiO₂·xFe₂O₃ gels at low temperatures in external magnetic fields. It is shown that the state of the iron atoms in the gels depends significantly on their concentration. In dry gels with an iron content exceeding 0.01Fe₂O₃, the Fe atoms belong to finely dispersed particles of the oxide with maximum sizes of ～80 Å in a superparamagnetic state. For lower iron contents, the Fe atoms are in the form of a highly diluted paramagnetic impurity of trivalent ions in a diamagnetic matrix. It is assumed that clusters develop from a small number of iron and oxygen ions dispersed in the gel matrix. Here spin-lattice relaxation of the magnetic moments of the iron atoms is observed.     

Pressure-Induced Decrease in the Curie Temperature of Gd<Subscript>2</Subscript>Fe<Subscript>17</Subscript>: LSDA+U Calculations

To explain the magnetic properties of advanced ferromagnetic intermetallic compounds of the R₂Fe₁₇ (R is a rare-earth element) class, experimentalists often use the hypothesis of competition between ferromagnetic exchange and antiferromagnetic exchange between four types of the nearest iron atoms in nonequivalent lattice sites. For the rhombohedral Gd₂Fe₁₇ ferromagnet, we calculate the magnetic moments of iron and gadolinium ions, the parameters of exchange between Fe atoms, and Curie temperature T_C at a zero pressure and during hydrostatic lattice compression. The magnetic moment of the unit cell of Gd₂Fe₁₇ is shown to decrease under pressure, and this decrease is almost completely associated with a decrease in the magnetic moments of Fe rather than Gd ions, the pressure dependence of the magnetic moments of which is weaker by an order of magnitude. In contrast to the hypothesis regarding the competition of exchange interactions between different kinds of Fe atoms, the parameters of exchange between the nearest iron atoms in different crystallographic sites are found to be positive ferromagnetic (at a zero pressure and during compression), and a ferromagnetic character of interaction is shown to remain unchanged under pressure even for Fe atoms in the so-called dumbbell sites with the nearest interatomic distances. The Curie temperature T_C of Gd₂Fe₁₇ is shown to decrease with increasing pressure. The changes in the exchange parameters and the magnetic moments of Gd₂Fe₁₇ during compression are found to be mainly related to a change in the position of energy spectrum branches with respect to each other and the Fermi level ?_F rather than to a change in the overlapping of wavefunctions, which play a minor role.     

Influence of the ion energy on the structure of Bi and Fe2O3 thin films

Compounds containing bismuth, iron and oxygen (BFO) can result in materials with important magnetic and electrical properties for high-technology applications. We plan to prepare such compounds using the simultaneous ablation of bismuth and iron oxide targets. For that reason in the first part of this work we study the plasmas and the materials produced by ablation of bismuth or Fe₂O₃ targets, and then the two plasmas are combined in order to deposit the BFO compounds. The individual plasmas were characterized using a Langmuir probe, in order to measure the mean kinetic ion energy (E _p) and plasma density (N _p). Bismuth and magnetite-Fe₃O₄ thin films were obtained in high vacuum (2.7×10^?4 Pa). Meanwhile for the deposition of α-Fe₂O₃ (hematite) or amorphous bismuth oxide thin films a reactive atmosphere (Ar/O₂=80/20) was used. All depositions were made at room temperature. The bismuth thin films crystallized in the rhombohedral metallic system with preferential orientations that depended on the Bi-ion energy used. Bismuth oxide phases were only obtained after annealing of the Bi thin films at different temperatures. Iron oxide thin films reproducing the target stoichiometry were obtained at a certain value of iron-ion energy. Preliminary structural results of the BFO thin films obtained by the combination of the individual plasmas are presented.     

Atomic physics at the planned new RIKEN facility

Combining Mössbauer spectroscopy with magnetic property measurement, we have studied Fe-N and (Fe, Ni)-N powders for magnetic recording. The typical particles of the core (α-Fe)/shell (γ′-Fe₄N) structure have been successfully prepared. All the products are stabilized in a multi-organic solution. It has been found that the coercivity can be changed from 300 to 800 Oe by adjusting the shape of the particles. The special saturation magnetization of the particles can be adjusted from 120 to 180emu/g and their chemical stability is improved by substituting nickel for iron in γ′-Fe₄N. Following experiments for corrosion resistance, it is expected that (Fe, Ni)-N and the core/shell particles will be applied as recording media in the near future.     

Study of ferromagnetism in Bi2S3 and ZnS nanocrystalline powders

Results of magnetic measurements suggested that Bi₂S₃ and ZnS nanocrystalline powders prepared by hydrothermal method could possibly exhibit room temperature ferromagnetism. The measured saturation magnetization of the powders increases with an increase of annealing temperature from 300 to 500 °C. Ab initio calculations suggested that the cation vacancies on the surface of Bi₂S₃ and ZnS nanograins could be responsible for the observed magnetic moments. Heat-treatment of Bi₂S₃ or ZnS nanocrystalline powders in Bi or Zn vapor could bring about an enhancement of ferromagnetism. The calculation results indicated that the interstitial Bi or Zn atoms in Bi₂S₃ (0 0 1) or ZnS (0 0 1) surface could induce magnetic moments.     

A new hard magnetic phase in binary Nd-Fe and Pr-Fe alloys

A new magnetic phase has been observed in as-cast and melt-spun Nd-Fe and Pr-Fe alloys with a Curie temperature around 265°C. SEM studies show the presence of this phase in the form of spherical and elongated particles 5 μ m in size with a composition having a ratio of Fe/Nd=4:1. This phase is believed to be a ternary Nd-Fe-O phase stabilized with oxygen. The phase appears to have a high anisotropy leading to coercivities of about 6 kOe in as-cast samples at room temperature. The Mössbauer spectra of this phase can be fitted to four Fe sites with magnetic moments ranging from 1.7 to 2.54μ_B.     

Single step thermal decomposition approach to prepare supported γ-Fe2O3 nanoparticles

γ-Fe₂O₃ nanoparticles supported on MgO (macro-crystalline and nanocrystalline) were prepared by an easy single step thermal decomposition method. Thermal decomposition of iron acetylacetonate in diphenyl ether, in the presence of the supports followed by calcination, leads to iron oxide nanoparticles supported on MgO. The X-ray diffraction results indicate the stability of γ-Fe₂O₃ phase on MgO (macro-crystalline and nanocrystalline) up to 1150 °C. The scanning electron microscopy images show that the supported iron oxide nanoparticles are agglomerated while the energy dispersive X-ray analysis indicates the presence of iron, magnesium and oxygen in the samples. Transmission electron microscopy images indicate the presence of smaller γ-Fe₂O₃ nanoparticles on nanocrystalline MgO. The magnetic properties of the supported magnetic nanoparticles at various calcination temperatures (350-1150 °C) were studied using a superconducting quantum interference device which indicates superparamagnetic behavior.     

Structure and magnetism on iron oxide clusters Fe nO m ( n = 1-5): Calculation from first principles

We have studied structural and magnetic properties in small iron oxide clusters, Fe_nO_m (n = 1-5), by means of the first-principles calculation based on the density functional theory. We have used not only the usual spin polarized scheme, but also the scheme for noncollinear magnetism to carry out efficient optimization in magnetic structure. The result of FeO_m (m = 1-4) is in good agreement with the previous work. We found the stable adduct clusters in FeO₅ and FeO₆. The bridge site of oxygen atom is more favorable in energy than any other site for the clusters of Fe_nO (n = 2-5). As increasing the number of oxygen atoms, the alignment of Fe magnetic moments changes from ferromagnetic configuration to antiferromagnetic one at Fe_nO_n (n = 2-4). Received 10 September 2002 Published online 3 July 2003     

Polarized neutron study of covalency effects in yttrium iron garnet

Magnetic structure amplitudes of 170 reflections up to sin $\text{θ}\text{λ}\text{= 1.0}\text{A}\text{?}{}^{\mathrm{?1}}$ were measured by polarized neutron diffraction at T = 295K on yttrium iron garnet. The data set was completed by model calculations and the magnetization density was determined. The magnetic moments obtained by integration and refinement are considerably reduced on both iron sites due to charge density transferred from intervening ligand ions. A residual moment of uncancelled spin of (0.032 ±0.004) μ_B is observed on the oxygen ion. Evidence for magnetization density on the oxygen atom and between oxygen and tetrahedral iron was found. A qualitative discussion in terms of a molecular orbital model is given. A further data set collected at 4.2K showed equally a magnetic moment lower than expected for the free ion.     

Ferro-and antiferromagnetic ordering in LaMnO3+δ

A neutron diffraction study of the crystalline structure and magnetic state of LaMnO_3+δ samples with different deviations from oxygen stoichiometry has been made at 4.2 K. It is shown that annealing at reduced oxygen pressure is accompanied by transformation of the magnetic structure from ferromagnetic, with magnetic moments parallel to the b axis, to antiferromagnetic, with the wave vector k=0 and the moments along the a axis (space group Pnma). A comparison of experimental with expected Mn ion moments suggests that magnetic order does not extend throughout the sample volume. Part of the Mn ions form magnetic clusters ～20 Å in size.     

Giant magnetic moments in ferromagnetic oxide semiconductors

Concentration dependence of the specific magnetic moment of Co-and Fe-doped titanium oxide semiconductors has been studied at room temperature. A sharp increase in the magnetic moment has been found at low concentrations of a magnetic impurity. A giant value of 22.9 μ_B per impurity atom has been detected in TiO₂ with a Co concentration of 0.15 at %, which has never been observed in oxide systems. The giant magnetic moments observed at low impurity concentration are attributed to the polarization of a crystal lattice. Comparison with the literature data indicates that the concentration dependences of magnetization are different in different oxide matrices.     

Combustion synthesis of nickel ferrite powders: Effect of NaClO4 content on their characteristics and magnetic properties

Magnetic powders of nickel ferrite (NiFe₂O₄) were successfully synthesized by combustion synthesis in air using iron (Fe), iron oxide (Fe₂O₃), and nickel oxide (NiO) as reactants and sodium perchlorate (NaClO₄) as fuel (or oxidizing agent). The thermal behaviors were characterized using thermogravimetric analysis (TG) and differential thermal analysis (DSC). The as-combusted and final nickel ferrite powders were characterized in terms of chemical composition and morphology by X-Ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), and scanning electron microscopy (SEM) coupled with energy dispersive X-Ray spectroscopy (EDX). In addition, magnetic properties were examined by vibrating sample magnetometer (VSM). The results of TG/DSC analysis indicated that increasing the content of NaClO₄ increased the exothermicity of combustion reaction. XRD indicated that the final nickel ferrite powders formed a single spinel NiFe₂O₄ phase when the amount of NaClO₄ used was 0.08 or 0.10 mol. SEM revealed roughly octahedron particles with sizes in a sub-micrometer range (∼500 nm). All final products exhibited soft magnetism and, synthesis that included 0.1 mol of NaClO₄ produced pure NiFe₂O₄ powders that had a saturation magnetization (M_s) of 58.93 emu/g, which is higher than the reported value (55 emu/g) for the bulk product.     

Mössbauer structural investigation of Fe2O3−TiO2 gels

Fe₂O₃?TiO₂ powders were obtained by the sol-gel method through hydrolysis and polycondensation of titanium n-butoxide and different iron compounds in alcoholic solutions. As iron oxide precursors, Fe(III)ethoxide, Fe(III)acetylacetonate and Fe(NO₃)₃·9H₂O were employed. The gels were dried and heat treated in air and in nitrogen atmosphere at different temperatures. It was demonstrated by means of Mössbauer spectroscopy that the use of different iron precursors can slightly affect the oxidation state of iron and the nature of the crystalline phases developed only when the heat treatment is performed in a non-oxidizing atmosphere. The results are discussed also in connection with previous X-ray diffraction data.     

Ferrimagnetism and hyperfine interactions in RFe5Al7(R = rare earth)

Magnetization and Mössbauer (⁵⁷Fe, ¹⁵⁵Gd) studies of RFe₅Al₇(R = Y, Sm to Lu, ThMn₁₂ crystal structure) in magnetic fields up to 50 kOe and temperatures 4.1 to 500 K have been performed. The Mössbauer studies yield the distribution of the iron ions among the various inequivalent crystallographic and magnetic sites, the hyperfine fields and their temperature dependence. The magnetization curves display a great variety of unusual magnetic phenomena. Among those; strong anisotropy, magnetic and thermal hysteresis (H_c = 24 kOe for DyFe₅Al₇ at 4.1 K), negative magnetization at low temperatures when the sample is cooled in a magnetic field (even in 1 Oe), compensation points, maxima points and time-dependent magnetization. Most of the phenomena observed can be explained in terms of a spin structure previously suggested for the RFe₆Al₆ compounds, composed of 4 magnetic sublattices. The rare earth moments lie antiparallel to the iron moments in the (j) site and to the ferromagnetic component of a canted antiferromagnetic structure of iron in the (f) site. Iron in the (i) site is nonmagnetic.     

Synthesis of monodisperse In2O3 nanoparticles and their d0 ferromagnetism

Monodisperse indium oxide (In₂O₃) nanoparticles (NPs) with the average diameter of 11 nm were prepared by a solvothermal method. The In₂O₃ NPs were characterized by X-ray diffraction, Raman and transmission electron microscopy. The intrinsic nature of ferromagnetism in In₂O₃ NPs has been established with the experimental observation of magnetic hysteresis loop. Photoluminescence and UV–visible studies were employed to evidence the presence of oxygen vacancies and revealed that the oxygen vacancies contribute to the ferromagnetism. The origin of ferromagnetism in In₂O₃ NPs may be due to exchange interactions among localized electron spin moments resulting from oxygen vacancies.     

Initial oxidation stages on FeCr(100) and FeCr(110) surfaces

Simultaneous LEED and AES are used to follow early stages of oxidation of monocrystalline FeCr(100) and (110) between 700 and 900 K in the oxygen pressure range 10^?9–10^?6 Torr. A chromium-rich oxide region at the alloy/oxide interface is observed, which exhibits different surface structures on oxidized FeCr(100) and FeCr(110). The chromium concentration in this initially formed oxide film is found to be enhanced by low oxygen pressures or high temperatures. During further oxidation different behaviours are observed on FeCr(100) and FeCr(110), which are explained by assuming different ion permeabilities through the initial chromium rich oxide regions on the two surface planes. On FeCr(110) surfaces oxidation is initiated on chromium enriched (100) facets at 800 K or below. At 900 K a film consisting of rhombohedral Cr₂O₃ or (Fe, Cr)₂O₃ is epitaxially growing with its (001) plane parallel to the alloy (110) face. On FeCr(100) surfaces the chromium rich oxide region next to the substrate is of fcc type. As soon as the diffusion of iron from the alloy to the gas/oxide interface is observable, a spinel type oxide is formed and connected with the location of iron in tetrahedral lattice sites. Closer to the fcc lattice the spinel oxide consists of FeCr₂O₄ or a solid solution of FeCr₂O₄ and Fe₃O₄ whereas next to the gas phase the oxide is pure Fe₃O₄.     

Oxygen on Fe(1 1 0): magnetic properties of the adsorbate system

Investigations concerning the electronic and magnetic properties of oxygen adsorbed on magnetized iron films were carried out by means of angle and spin resolving photoelectron spectroscopy. Iron(1 1 0), epitaxially grown on a W(1 1 0) crystal, served as the ferromagnetic substrate. Exchange splittings of the O 2p_x derived level were detected demonstrating a magnetic coupling between the chemisorbate and the iron layer. This observation indicates the presence of an induced magnetic moment within the adsorbate overlayer. Variations of the exchange splitting occurred as a function of the oxygen coverage, energy of the exciting radiation, and detection angle of the emitted photoelectrons pointing to a k₆-dependent exchange splitting. High oxygen exposures lead to a FeO overlayer at the surface, showing vanishing peak separations due to the antiferromagnetic behavior of iron oxide.     

Vacancy-like defects in nanocrystalline SnO2: influence of the annealing treatment under different atmospheres

The study of electronic and chemical properties of semiconductor oxides is motivated by their several applications. In particular, tin oxide is widely used as a solid state gas sensor material. In this regard, the defect structure has been proposed to be crucial in determining the resulting film conductivity and then its sensitivity. Here, the characteristics of vacancy-like defects in nanocrystalline commercial high-purity tin oxide powders and the influence of the annealing treatment under different atmospheres are presented. Specifically, SnO₂ nanopowders were annealed at 330 °C under three different types of atmospheres: inert (vacuum), oxidative (oxygen) and reductive (hydrogen). The obtained experimental results are discussed in terms of the vacancy-like defects detected, shedding light to the basic conduction mechanisms, which are responsible for gas detection.     

Toroidal moments as indicator for magneto-electric coupling: the case of BiFeO<Subscript>3</Subscript> versus FeTiO<Subscript>3</Subscript>

In this paper we present an analysis of the magnetic toroidal moment and its relation to the various structural modes in R3c-distorted perovskites with magnetic cations on either the perovskite A or B site. We evaluate the toroidal moment in the limit of localized magnetic moments and show that the full magnetic symmetry can be taken into account by considering small induced magnetic moments on the oxygen sites. Our results give a transparent picture of the possible coupling between magnetization, electric polarization, and toroidal moment, thereby highlighting the different roles played by the various structural distortions in multiferroic BiFeO₃ and in the recently discussed isostructural material FeTiO₃, which has been predicted to exhibit electric field-induced magnetization switching.