Antiferromagnetism and spin-glass transition in the FeInxCr2−xSe4 series of selenides

The magnetic behavior of the FeIn_xCr_2−xSe₄ system (with x=0.0, 0.2 and 0.4) has been investigated by magnetic and Mössbauer spectroscopy. Hyperfine parameters indicate that iron is in the Fe²⁺ oxidation state, with a minor (∼9%) Fe³⁺ fraction, located at different layers in the structure. Low-field magnetization curves as a function of temperature showed that the antiferromagnetic (AFM) order temperature is T_N=208(2) K for FeCr₂Se₄ and decreases to 174(3) K for FeIn_0.4Cr_1.6Se₄. The effective magnetic moment μ_eff decreases with increasing In contents, and shows agreement with the expected values from the contribution of Fe²⁺ (⁵D) and Cr³⁺ (⁴F) electronic states. A second, low-temperature transition is observed at T_G∼13 K, which has been assigned to the onset of a glassy state.     

Magnetic study of Mg0.95Mn0.05Fe2O4 ferrite nanoparticles

The magnetic properties of Mg_0.95Mn_0.05Fe₂O₄ ferrite samples with an average particle size of ∼6.0±0.6 nm have been studied using X-ray diffraction, Mössbauer spectroscopy, dc magnetization and frequency dependent real χ^′(T) and imaginary χ^″(T) parts of ac susceptibility measurements. A magnetic transition to an ordered state is observed at about 195 K from Mössbauer measurements. The zero-field-cooled (ZFC) and field-cooled (FC) magnetization have been recorded at low field and show the typical behavior of a small particle system. The ZFC curve displays a broad maximum at , a temperature which depends upon the distribution of particle volumes in the sample. The FC curve was nearly flat below , as compared with monotonically increasing characteristics of non-interacting superparamagnetic systems indicating the existence of strong interactions among the nanoparticles. A frequency-dependent peak observed in χ^′(T) is well described by Vogel-Fulcher law, yielding a relaxation time and an interaction parameter . Such values show the strong interactions and rule out the possibility of spin-glass (SG) features among the nanoparticle system. On the other hand fitting with the Néel-Brown model and the power law yields an unphysical large value of τ₀ (∼6×10⁻⁶⁹ and 1.2×10⁻²² s respectively).     

Magnetic properties of ZnFe2O4 nanoparticles produced by a low-temperature solid-state reaction method

ZnFe₂O₄ nanoparticles with average grain size ranging from 40 to 60 nm behaving superparamagnetic at room temperature have been produced using a low-temperature solid-state reaction (LTSSR) method without ball-milling process. Abnormal magnetic properties such as S-shape hysteresis loops and non-zero magnetic moments were observed. ZnFe₂O₄ nanoparticles were also synthesized using a NaOH coprecipitation method and a PVA sol-gel method to study the relationship between the preparation processes and the magnetic properties. Spin-glass behavior was observed in the low temperature solid-state reaction produced Zn ferrite in the zero-field cooled (ZFC) measurement. Our work proves that the various preparation methods will to some extent determine the properties of magnetic nanoparticles.     

Morphology and magnetic properties of Co0.8Fe2.2O4 films prepared by the chemical solution deposition

Co_0.8Fe_2.2O₄ ferrite thin films have been prepared on Si(0 0 1) substrates by the chemical solution deposition. Structural characteristics indicate all films are single phase with spinel structure and the space group and the mean grain size increases from 8 to 30 nm with the increase of annealing temperature. The magnetic properties of Co_0.8Fe_2.2O₄ thin films are highly dependent on annealing temperature. The sample annealed at 800 °C possesses high saturation magnetization, moderate coercivity and squareness ratio, making it a promising application candidate in high-density record and magneto-optical materials.     

Preparation and characterizations of SiO2-coated nanoparticles of Mn0.4Zn0.6Fe2O4

Core/shell nanoparticles consisting of a magnetic core of zinc-substituted manganese ferrite (Mn_0.4Zn_0.6Fe₂O₄) and a shell of silica (SiO₂) are prepared by a sol-gel method using tetraethyl orthosilicate (TEOS) as a precursor material for silica and salts of iron, manganese and zinc as the precursor of the ferrite. Three weight percentages of the shell materials of SiO₂ are used to prepare the coated nanoparticles. The X-ray diffractograms (XRD) of the coated and uncoated magnetic nanoparticles confirmed that the magnetic nanoparticles are in their mixed spinel phase in an amorphous matrix of silica. Particles sizes of the samples annealed at different temperatures are estimated from the width of the (3 1 1) line of the XRD pattern using the Debye-Sherrer equation. The information regarding the crystallographic structure together with the particles sizes extracted from the high-resolution transmission electron microscopy (HRTEM) of a few selected samples are in agreement with those obtained from the XRD. HRTEM observations revealed that particles are coated with silica. The calculated thickness is in agreement with that obtained from the HRTEM pictures. Hysteresis loops observed in the temperature range 300 down to 5 K and Mössbauer spectra at room temperature indicate superparamagnetic relaxation of the nanoparticles.     

Magnetic-field-induced transition from metastable spin glass to possible antiferromagnetic-ferromagnetic phase separation in Cd0.5Cu0.5Cr2O4

Using ac susceptibility, dc magnetization and heat-capacity measurements, we have investigated the magnetic properties of Cd_0.5Cu_0.5Cr₂O₄. Cd_0.5Cu_0.5Cr₂O₄ has an extraordinary magnetic phase including a metastable spin-glass (SG) phase at zero field, a possible phase separation scenario of AFM/FM above ∼0.5 T field, and at intermediate fields, an apparent pseudo reentrant spin-glass (RSG) plateau is observed. These phenomena are closely correlated with the pinning effect of the Cu²⁺ sublattice on the frustrated lattice.     

PLD of Fe3O4 thin films: Influence of background gas on surface morphology and magnetic properties

Ablation of Fe₃O₄ targets has been performed using a pulsed UV laser (KrF, λ = 248 nm, 30 ns pulse duration) onto Si(100) substrates, in reactive atmospheres of O₂ and/or Ar, with different oxygen partial pressures. The as-deposited films were characterised by atomic force microscopy (AFM), X-ray diffraction (XRD), conversion electron Mössbauer spectroscopy (CEMS) and extraction magnetometry, in order to optimise the deposition conditions in the low temperature range. The results show that a background mixture of oxygen and argon improves the Fe:O ratio in the films as long as the oxygen partial pressure is maintained in the 10⁻² Pa range. Thin films of almost stoichiometric single phase polycrystalline magnetite, Fe_2.99O₄, have been obtained at 483 K and working pressure of 7.8 × 10⁻² Pa, with a high-field magnetization of ∼490 emu/cm³ and Verwey transition temperature of 112 K, close to the values reported in the literature for bulk magnetite.     

Synthesis and magnetic properties of CoFe2O4 ferrite nanoparticles

CoFe₂O₄ ferrite nanoparticles were prepared by a modified chemical coprecipitation route. Structural and magnetic properties were systematically investigated. X-ray diffraction results showed that the sample was in single phase with the space group . The results of field-emission scanning electronic microscopy showed that the grains appeared spherical with diameters ranging from 20 to 30 nm. The composition determined by energy-dispersive spectroscopy was stoichiometry of CoFe₂O₄. The Curie temperature in the process of increasing temperature was slightly higher than that in the process of decreasing temperature. This can be understood by the fact that heating changed Co²⁺ ion redistribution in tetrahedral and in octahedral sites. The coercivity of the synthesized CoFe₂O₄ samples was lower than the theoretical values, which could be explained by the mono-domain structure and a transformation from ferrimagnetic to superparamagnetic state.     

Electronic structure of dimerized spinel ZnV2O4

Electronic structure calculations were performed for ZnV₂O₄, a material close to a metal-insulator transition. Structural optimization leads to the formation of V-V dimers along the off-plane chains. A strong spin-lattice coupling is expected close to the transition to itinerancy. No orbital ordering is observed in such a structure, and the experimentally found magnetic structure is naturally explained.     

Temperature-dependent Mössbauer and dielectric studies of Mg0.95Mn0.05Fe1.0Ti1.0O4

The effect of tetravalent Ti⁺⁴ substitution in Mg_0.95Mn_0.05Fe₂O₄ on its magnetic and electrical properties has been studied using X-ray diffraction, Mössbauer spectroscopy, isothermal dc magnetization and dielectric measurements. X-ray diffraction studies have shown the structural transformation from cubic to tetragonal with the Ti⁺⁴ substitution. The Mössbauer spectra of Mg_0.95Mn_0.05Fe_1.0Ti_1.0O₄ recorded in the temperature range 20-300 K shows the presence of the magnetic as well as quadrupole interactions. The isothermal hysteresis loop infers that the system exhibits a ferrimagnetic ordering at room temperature. The Zero-field-cooled (ZFC) and field-cooled (FC) magnetization studies support ferrimagnetic ordering of Mg_0.95Mn_0.05Fe_1.0Ti_1.0O₄ at room temperature. Signatures of ferroelectric transition have been observed in the temperature range 200-300 K from dielectric measurements. The observed magnetic and dielectric behaviour indicate that this material exhibits multiferroic behaviour.     

Fabrication and magnetic properties of Fe3O4 nanowire arrays in different diameters

Fe₃O₄ nanowire arrays with different diameters of D=50, 100, 150 and 200 nm were prepared in anodic aluminum oxide (AAO) templates by an electrodeposition method followed by heat-treating processes. A vibrating sample magnetometer (VSM) and a Quantum Design SQUID MPMS magnetometer were used to investigate the magnetic properties. At room temperature the nanowire arrays change from superparamagnetism to ferromagnetism as the diameter increases from 50 to 200 nm. The zero-field-cooled (ZFC) and field-cooled (FC) magnetization measurements show that the blocking temperature T_B increases with the diameter of nanowire. The ZFC curves of D=50 nm nanowire arrays under different applied fields (H) were measured and a power relationship between T_B and H were found. The temperature dependence of coercivity below T_B was also investigated. Mössbauer spectra and micromagnetic simulation were used to study the micro-magnetic structure of nanowire arrays and the static distribution of magnetic moments of D=200 nm nanowire arrays was investigated. The unique magnetic behaviors were interpreted by the competition of the demagnetization energy of quasi-one-dimensional nanostructures and the magnetocrystalline anisotropy energy of particles in nanowires.     

Yafet-Kittel-type magnetic ordering in Ni0.35Zn0.65Fe2O4 ferrite detected by magnetosensitive microwave absorption measurements

Magnetosensitive microwave absorption measurements of polycrystalline ferrite Ni_0.35Zn_0.65Fe₂O₄ was carried out at 9.4 GHz (X-band) as a function of temperature. Temperature dependence of the total linewidth (ΔH_pp) deduced from the resonance spectra showed the passage through the Curie point (T_c~430 K). Additionally, the plot ΔH_pp vs. T also indicated the existence of another magnetic phase transition at ~240 K, which can be associated with a Yafet-Kittel-type canting of the magnetic moments. Low-field microwave absorption (LFMA) and the magnetically modulated microwave absorption spectroscopy (MAMMAS) were used to give a further knowledge on this material. For low temperature, these techniques give evidence of a Yafet-Kittel-type canting of the magnetic moments.     

Mössbauer studies on the superparamagnetic behavior of CoFe2O4 with a few nanometers

CoFe₂O₄ nanoparticles with a cubic spinel structure are prepared by a high-temperature thermal decomposition method. The average particle sizes are 4.6  and 5.7 nm for CoFe₂O₄ made with two kinds of solvents by TEM. Mössbauer spectra of 4.6 nm particles displayed a superparamagnetic behavior as demonstrated by a single line with zero hyperfine fields, but that of 5.7 nm particles did not at room temperature. It is considered that anisotropy energy was still more superior to thermal energy because of particle size of 5.7 nm CoFe₂O₄. Furthermore, Mössbauer spectra exhibited the typical spectrum shapes of the CoFe₂O₄ at 4.2 K. The spectrum at 4.2 K was fitted using two magnetic components of hyperfine fields _Hhf=540.4,512.6$H_{\mathrm{hf}}=540.4,512.6$ kOe and isomer shifts δ=0.40,0.30$\delta =0.40,0.30$ mm/s for 4.6 nm and _Hhf=542.7,512.8$H_{\mathrm{hf}}=542.7,512.8$ kOe and δ=0.41,0.29$\delta =0.41,0.29$ mm/s for 5.7 nm corresponding to Fe³⁺ ions at site A and site B, respectively.     

The role of iron in the formation of the magnetic structure and related properties of La0.8Sr0.2Co1−xFexO3 (x=0.15, 0.2, 0.3)

La_0.8Sr_0.2Co_1−xFe_xO₃ (x=0.15, 0.2, 0.3) samples were studied by means of AC magnetic susceptibility, magnetization, magnetoresistance and ⁵⁷Fe Mössbauer spectrometry. Iron was found to take on a high spin 3d^5−α electronic state in each of the samples, where α refers to a partly delocalized 3d electron. The compounds were found to exhibit a spin-cluster glass transition with a common transition temperature of ∼53 K. The spin-cluster glass transition is visualized in the ⁵⁷Fe Mössbauer spectra as the slowing down of magnetic relaxation below ∼70 K, thereby showing that iron takes part in the formation of the glassy magnetic phase. The paramagnetic-like phase found at higher temperatures is identified below T_c≈195 K as being composed of weakly interacting, magnetically ordered nanosized clusters of magnetic ions in part with a magnetic moment oriented opposite to the net magnetic moment of the cluster. For each of the samples a considerable low-temperature negative magnetoresistance was found, whose magnitude in the studied range decreases with increasing iron concentration. The observed results obtained on the present compounds are qualitatively explained assuming that the absolute strengths of magnetic exchange interactions are subject to the relation ∣J_Co–Co∣<∣J_Fe–Co∣<∣J_Fe–Fe∣.     

Spin-canting and transverse relaxation in maghemite nanoparticles and in tin-doped maghemite

The magnetic properties of maghemite nanoparticles and tin-doped maghemite have been studied by ⁵⁷Fe and ¹¹⁹Sn Mössbauer spectroscopy at temperatures from 6 to 300 K with and without applied magnetic fields. The low-temperature ⁵⁷Fe spectra of both samples, obtained in a field of 4 T, can be described in terms of A-site and B-site components with perfect ferrimagnetic order and a strongly canted component, which seems to have its main contribution from B-site ions. At higher temperatures, the components with strong canting are influenced by transverse relaxation, which results in significant line broadening, a reduction of the magnetic hyperfine splitting and a reduction in the relative areas of lines 2 and 5. The ¹¹⁹Sn spectra show a very broad distribution of magnetic hyperfine fields at low temperatures. When the sample was exposed to applied magnetic fields the distribution became narrower. The spectra show that the direction of the hyperfine field of a large fraction of the tin ions in maghemite is antiparallel to the applied field, but a minor fraction of the tin ions have canted hyperfine fields.     

Synthesis and magnetic properties of spinel CoFe2O4 nanowire arrays

Spinel CoFe₂O₄ nanowire arrays were synthesized in nanopores of anodic aluminum oxide (AAO) template using aqueous solution of cobalt and iron nitrates as precursor. The precursor was filled into the nanopores by vacuum impregnation. After heat treatment, it transformed to spinel CoFe₂O₄ nanowires. The structure, morphology and magnetic properties of the sample were studied by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and vibrating sample magnetometer (VSM). The results indicate that the nanowire arrays are compact. And the individual nanowires have a high aspect ratio, which are about 80 nm in diameter and 10 μm in length. The nanowires are polycrystalline spinel phase. Magnetic measurements indicate that the nanowire arrays are nearly magnetic isotropic. The reason is briefly discussed. Moreover, the temperature dependence of the coercive force of the nanowire arrays was studied.     

The effect of B2O3 addition to the microstructure and magnetic properties of Ni0.4Zn0.6Fe2O4 ferrite

The effects of 0.01 and 0.1 mol B₂O₃ addition to the microstructure and magnetic properties of a Ni–Zn ferrite composition expressed by a molecular formula of Ni_0.4Zn_0.6Fe₂O₄ were investigated. The toroid-shaped samples prepared by pressing the milled raw materials used in the preparation of the composition were sintered in the range of 1000–1300 °C. The addition of 0.01 mol B₂O₃ increased the grain growth and densification giving rise to reduced intergranular and intragranular porosity due to liquid-phase sintering. The sintered toroid sample at 1300 °C gave the optimum magnetic properties of B_r=170 mT, H_c=0.025 kA/m and a high initial permeability value of μ_i=4000. The increment of the B₂O₃ content to 0.1 mol resulted in a pronounced grain growth and also gave rise to large porosity due to the evaporation of B₂O₃ at higher sintering temperatures. Hence, it resulted in an air-gap effect in the hysteresis curves of these samples.     

Cluster spin glass ordering in diluted spinel Zn0.5Co0.5FeCrO4

The disordered spinel system, Zn_0.5Co_0.5FeCrO₄ has been investigated using the low field magnetization and ac susceptibility measurements. From the present results it appears that this system orders into a cluster spin glass state with the magnetic moments of the ferrimagnetic clusters randomly frozen. Compared to the Ni and Co zinc ferrites with the same magnetic dilution, introduction of Cr into the B sites appears to increase the frustration and disorder dramatically. The predicted phase diagrams for the ordering in diluted magnetic spinels do not describe the magnetic behaviour of this system, presumably due to the disorder in the B sublattice in addition to the dilution in the A sublattice.     

Structure and magnetism in Ho1−xSrxCoO3−δ

We have magnetically and structurally characterized the Ho_1−xSr_xCoO_3−δ family of materials where 0.67≤x≤0.95. The solid solution range and evolution of the structure as a function of x is established and correlated with the broad range of magnetic behavior observed. The structure is shown to be tetragonal I4/mmm although is possibly cubic when x=0.95. For 0.67≤x≤0.9 the material shows antiferromagnetic long range order and ferromagnetic clusters. At x=0.95 the magnetic transition is at 120 K and the imaginary susceptibility becomes non-zero and the temperature of the cusp in the ac susceptibility shows a frequency dependence indicative of glassiness.     

Ferromagnetic-to-antiferromagnetic transition in (Hf1−xTix)Fe2 intermetallic compounds induced by geometrical frustration of the Fe(2a) sites

The ferromagnetic-to-antiferromagnetic transition in the hexagonal (Hf_1−xTi_x)Fe₂ (0?x?1) intermetallic compounds has been investigated by ⁵⁷Fe Mössbauer spectroscopy. At 10 K, the transition occurs within rather narrow concentration limits, around x=0.55–0.65. We found that the key factor governing the unexpected quick change of the magnetic structure is the magnetic frustration of the Fe(2a) sites. The magnetic frustration is caused by the noncollinearity of the Fe(6h) magnetic sublattice. The noncollinearity arises from the rotation of the magnetic moments due to the competition between the ferromagnetic exchange interactions and the antiferromagnetic Fe(6h)–Ti–Fe(6h) interaction. In the compounds with x=0.4–0.6, the temperature transitions to the antiferromagnetic state are observed. As an example, the Hf_0.4Ti_0.6Fe₂ compound is completely antiferromagnetic above 200 K.