Structural and magnetic properties of sol-gel Co2xNi0.5−x Zn0.5−xFe2O4 thin films

Nanocrystalline Co_2xNi_0.5−xZn_0.5−xFe₂O₄ (x=0−0.5) thin films have been synthesized with various grain sizes by a sol-gel method on polycrystalline silicon substrates. The morphology as well as magnetic and microwave absorption properties of the films calcined at 1073 K were studied using X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, and vibrating sample magnetometry. All films were uniform without microcracks. The Co content in the Co-Ni-Zn films resulted in a grain size ranging from 15 to 32 nm while it ranged from 33 to 49 nm in the corresponding powders. Saturation and remnant magnetization increased with increase in grain size, while coercivity demonstrated a drop due to multidomain behavior of crystallites for a given value of x. Saturation magnetization increased and remnant magnetization had a maximum as a function of grain size independent of x. In turn, coercivity increased with x independent of grain size. Complex permittivity of the Co-Ni-Zn ferrite films was measured in the frequency range 2-15 GHz. The highest hysteretic heating rate in the temperature range 315-355 K was observed in CoFe₂O₄. The maximum absorption band shifted from 13 to 11 GHz as cobalt content increased from x=0.1 to 0.2.     

Reentrant spin glass behavior and large initial permeability of Co0.5−xMnxZn0.5Fe2O4

A series of polycrystalline ferrites having nominal chemical composition Co_0.50−xMn_xZn_0.5Fe₂O₄ (0<x<0.4) have been synthesized by the solid-state reaction technique. The XRD analysis confirms single phase cubic spinel structure for all compositions. Lattice constant increases from 0.84195 to 0.84429 nm with the increasing Mn content and obeys Vegard's law. The average grain size increases by increasing both Mn content and sintering temperatures. Room temperature saturation magnetization increases for x=0.1 and decreases for increasing Mn content. The coercivity decreases with increasing Mn content due to the decrease of anisotropy constant. A reentrant spin glass behavior of these samples is observed from the zero field cooled magnetization measurements. The real part of the initial permeability increases by increasing both Mn content and sintering temperatures. This is due to the homogeneous grain growth and densification of the ferrites. The highest initial permeability 137 is observed for x=0.4 sintered at 1573 K on the other hand, the highest relative quality factor (2522) is obtained for the sample Co_0.2Mn_0.3Zn_0.5Fe₂O₄ sintered at 1523 K. The Mn substituted Co_0.50−xMn_xZn_0.5Fe₂O₄ ferrites showed improved magnetic properties.     

Structural and magnetic characteristics of Co1−xNix/2Srx/2Fe2O4 nanoparticles

Co_1−xNi_x/2Sr_x/2Fe₂O₄ (x=0–0.5 in steps of 0.1) ferrite nanoparticles have been synthesized at room temperature, without calcination, using a reverse micelle process. The site preference was determined by Mössbauer spectroscopy at 300 K. The hyperfine parameters were obtained, for the whole series of solid solutions. For the X≤0.20 samples, the spectra were fitted with two discrete sextets and for the X>0.20 samples, a magnetic hyperfine field distribution and a doublet were also imposed in the fit procedure. Hysteresis loops were measured using a superconducting quantum interference device magnetometer at 2 K and 300 K. The results indicate that the relative decrease in saturation magnetization of nanoparticles compared to the submicron particles could be attributed to a surface spin termination and disorder. Magnetic dynamics of the nanoparticles was studied by the measurement of ac magnetic susceptibility versus temperature at different frequencies and it is found that the results are well described by the Vogel–Fulcher model.     

Room temperature ferromagnetism behavior of Sn1−xMnxO2 powders

In this paper, we have investigated Mn-doped SnO₂ powder samples prepared by solid-state reaction method. X-ray diffraction showed a single phase polycrystalline rutile structure. The atomic content of Mn ranged from ∼0.8 to 5 at%. Room temperature M-H loops showed a ferromagnetic behavior for all samples. The ferromagnetic Sn_0.987Mn_0.013O₂ showed a coercivity H_c=545 Oe, which is among the highest reported for dilute magnetic semiconductors. The magnetic moment per Mn atom was estimated to be about 2.54 μ_B of the Sn_0.9921Mn_0.0079O₂ sample. The average magnetic moment per Mn atom sharply decreases with increasing Mn content, while the effective fraction of the Mn ions contributing to the magnetization decreases. The magnetic properties of the Sn_1−xMn_xO₂ are discussed based on the competition between the antiferromagnetic superexchange coupling and the F-center exchange coupling mechanism, in which both oxygen vacancies and magnetic ions are involved.     

Magnetocaloric effect in high Ni content Ni52Mn48−xInx alloys under low field change

Ni-rich Heusler alloys Ni₅₂Mn_48−xIn_x (x=15.5, 16 and 16.5) were prepared by the arc melting method. X-ray diffraction analysis revealed that the martensite has orthorhombic structure (S.G. Pmm2) at room temperature. The only alloy with x=15.5 has structural transmission from martensite to austenite without any magnetic transmission. The temperature dependence and the field dependence of the magnetization measurement indicated that the magnetization increased with the decreasing of the concerntration of Mn. The lesser the Mn atoms located in the In atom sites, the weaker the total AFM interaction in the system. Giant entropy changes ΔS_M(T, H) were found in Ni₅₂Mn_48−xIn_x alloys with the maximum ΔS_M value of 22.3 J kg K for the sample with x=16.5 at 270 K under the magnetic field change of 1.5 T.     

Structural and magnetic properties of Mg(In2−xMnx)O4 system

We synthesized the Mn-doped Mg(In_2−xMn_x)O₄ oxides with 0.03?x?0.55 using a solid-state reaction method. The X-ray diffraction patterns of the samples were in a good agreement with that of a distorted orthorhombic spinel phase. Their lattice parameters and unit-cell volumes decrease with x due to the substitution of the smaller Mn³⁺ ions to the larger In³⁺ ions. The undoped MgIn₂O₄ oxide presents diamagnetic signals for 5 K?T?300 K. The M(H) at T=300 K reveals a fairly negative-sloped linear relationship. Neither magnetic hysteresis nor saturation behavior was observed in this parent sample. For the Mn-doped samples, however, positive magnetization were observed between 5 and 300 K even if the x value is as low as 0.03. The mass susceptibility enhances with Mn content and it reaches the highest value of 1.4×10⁻³ emu/g Oe (at T=300 K) at x=0.45. Furthermore, the Mn-doped oxides with x=0.06 and 0.2, respectively, exhibit nonlinear magnetization curves and small hysteretic loops in low magnetic fields. Susceptibilities of the Mn-doped samples are much higher than those of MnO₂, Mn₂O₃ oxides, and Mn metals. These results show that the oxides have potential to be magnetic semiconductors.     

Mn1−xFexIn2Se4: a new layered semiconductor system

Mn_1−xFe_xIn₂Se₄ compounds (x=0.1; x=0.7) were grown by the chemical vapor transport method. X-ray diffraction analysis data show that these compositions crystallize as different polytypes that belong to the hexagonal structure. The crystal symmetry of the sample with x=0.1 belongs to the space group Rm and for the sample with x=0.7 the space group is P6₃mc.The magnetic behavior of both samples has been investigated in the temperature range between 5 and 300 K. Spin-glass-like behavior below the freezing temperature T_f=9 K has been found for the sample with x=0.7. The sample with Fe content x=0.1 behaves as a paramagnet down to the lowest experimental measured temperature. High-temperature susceptibility data follow the Curie-Weiss law with a negative paramagnetic temperature indicating predominant antiferromagnetic interactions.Optical studies reveal that both samples (x=0.1; 0.7) are direct band gap semiconductors. The temperature dependence of the energy gap fits Varshni relation quite well.     

Synthesis, structural and magnetic study of polycrystalline LaNi1−xMnxO3 films

Polycrystalline double perovskite LaNi_1−xMn_xO₃ (x=0.3, 0.4, 0.5 and 0.7, which is defined as Mn03, Mn04, Mn05 and Mn07, respectively) thin films are successfully deposited on Si (1 0 0) substrates via chemical solution deposition method. Their structural and magnetic properties are measured. All the thin films are of single phase. Raman spectra indicate that relative intensity of Mn05 is stronger than that of others that can be attributed to the higher degree of B-site ordering. The low temperature magnetic moment of Mn05 is about 500 emu/cm³, which is obviously larger than that of Mn03 and Mn07 because of the long-range ordering of Mn and Ni ions in Mn05.     

Effect of Fe substitution on magnetocaloric effect in La0.7Sr0.3Mn1−xFexO3 (0.05≤x≤0.20)

We have studied the effect of Fe substitution on magnetic and magnetocaloric properties in La_0.7Sr_0.3Mn_1−xFe_xO₃ (x=0.05, 0.07, 0.10, 0.15, and 0.20) over a wide temperature range (T=10-400 K). It is shown that substitution by Fe gradually decreases the ferromagnetic Curie temperature (T_C) and saturation magnetization up to x=0.15 but a dramatic change occurs for x=0.2. The x=0.2 sample can be considered as a phase separated compound in which both short-range ordered ferromagnetic and antiferromagnetic phases coexist. The magnetic entropy change (−ΔS_m) was estimated from isothermal magnetization curves and it decreases with increase of Fe content from 4.4 J kg⁻¹ K⁻¹ at 343 K (x=0.05) to 1.3 J kg⁻¹ K⁻¹ at 105 K (x=0.2), under ΔH=5 T. The La_0.7Sr_0.3Mn_0.93Fe_0.07O₃ sample shows negligible hysteresis loss, operating temperature range over 60 K around room temperature with refrigerant capacity of 225 J kg⁻¹, and magnetic entropy of 4 J kg⁻¹ K⁻¹ which will be an interesting compound for application in room temperature refrigeration.     

Magnetic properties of the Ce2Fe17−xMnx helical magnets up to high magnetic fields

Magnetic properties of the Ce₂Fe_17−xMn_x, x=0–2, alloys in magnetic fields up to 40 T are reported. The compounds with x=0.5–1 are helical antiferromagnets and those with 1<x?2 are helical ferromagnets or helical antiferromagnets at low and high T, respectively. Mn ions in the system carry average magnetic moment of 3.0±0.2 μ_B that couple antiparallelly to the Fe moments. Easy-plane magnetic anisotropy in the Ce₂Fe_17−xMn_x compounds weakens upon substitution of Mn for Fe. The absolute value of the first anisotropy constant in the Ce₂Fe_17−xMn_x helical ferromagnets decreases slower with increasing temperature than that calculated from the third power of the spontaneous magnetization. Noticeable magnetic hysteresis in the Ce₂Fe_17−xMn_x, x=0.5–2, helical magnets over the whole range of magnetic fields reflects mainly irreversible deformation of the helical magnetic structure during the magnetization of the compounds. A contribution from short-range order (SRO) magnetic clusters to the magnetic hysteresis of the helical magnets has been also estimated.     

Structure, magneto-structural transitions and magnetocaloric properties in Ni50−xMn37+xIn13 melt spun ribbons

Melt spun Ni_50−xMn_37+xIn₁₃ (2≤x≤5) ribbons were investigated for the structure, microstructure, magneto-structural transitions and inverse magnetocaloric effect (IMCE) associated with the first-order martensitic phase transition. The influence of excess Mn in Ni site (or Ni/Mn content) on the martensite transition and the associated magnetic and magnetocaloric properties are discussed. It was found that with the increase in Mn content, the martensitic transition shifted from 325 to 240 K as x is varied from 2 to 4, and the austenite phase was stabilized at room temperature. The x=5 ribbon did not show the martensitic transition. For the x=3 ribbon, the structural and magnetic transitions are close together unlike in the x=4 ribbon in which they are far (∼60 K) apart. The zero field cooled and field cooled curves support the presence of exchange bias blocking temperature due to antiferromagnetic interactions in the ribbons. A large change in the magnetization between the martensite and austenite phases was observed for a small variation in the Ni/Mn content, which resulted in large IMCE. A large positive magnetic entropy change (ΔS_M) of 32 J/kg K at room temperature (∼ 300 K) for a field change of 5 T with a net refrigeration capacity of 64 J/kg was obtained in the Ni₄₇Mn₄₀In₁₃ ribbon.     

Synthesis and characterization of Sr(ZnZr)x Fe12−2xO19-PANI composites

Strontium zinc zirconium hexaferrites/polyaniline (Sr(ZnZr)_xFe_12−2xO₁₉-PANI, x=0, 0.5, 1.0) composites were synthesized by oxidative chemical polymerization of aniline in the presence of ammonium peroxydisulfate (APS). The structure and morphology of the product was characterized by FTIR, TGA and SEM. The particle size of the core material was found to be about 250-500 nm. After coating with polyaniline, the particle size of Sr(ZnZr)_0.5Fe₁₁O₁₉-PANI composites grew upto 0.5-1.0 μm. XRD of the ferrites indicated that the structure of the core materials is hexagonal, with lattice constants around 5.886-5.885 Å. It was found that the saturation magnetization (M_S) and coercivity (H_C) for Sr(ZnZr)_xFe_12−2xO₁₉-PANI composites decreased after polyaniline coating. The composite under applied magnetic field, exhibited ferromagnetic hysteretic loops with high saturation magnetization (M_S=18.9-3.8 emu/g) and coercivity (H_C=3850.0-583.91 Oe).     

Effect of Co or Mn addition on the soft magnetic properties of amorphous Fe89−xZr11Bx (x=5, 10) alloy ribbons

The temperature and field dependent magnetic properties of melt-spun amorphous Fe_89−x−yZr₁₁B_x(Co,Mn)_y (x=5, 10 and 0≤y≤10) alloys in the temperature range 5-1200 K are reported. The Curie temperature and saturation magnetization at room temperature increase (decrease) almost linearly with Co (Mn) addition. With increasing Co concentration, the room temperature coercivity increases at the rate of 2.26 (0.28) A/m per at% for the x=5 (10) samples. The high-field magnetic susceptibility and local magnetic anisotropy decrease (increases) rapidly with increasing Co (Mn) concentration. The thermomagnetic curves show a marked increase in magnetization above 850 K corresponding to the crystallization of α-FeCo (α-Fe) phase in samples containing Co (Mn). The Curie temperature of the crystalline phase increases (remains same) with increasing Co (Mn) concentration with the formation of α-FeCo (α-Fe). Addition of Co up to 10 at% in Fe-Zr-B improves the room temperature saturation magnetization from 0.56 to 1.2 T, and Curie temperature from 315 to 476 K. Also, the coercivity increases with Co addition from 1.27 to 23.88 A/m for x=5 and from 7.64 to 10.35 A/m for x=10 alloy. The non-collinear spin structures that characterize Fe rich Fe-Zr-B amorphous alloys have been used to describe the observed results.     

Photocatalytic O2 evolution performances of Cd1+xIn2−2xSnxO4 (x=0.1, 0.3, 0.5, 0.7, 1.0) conducting oxides

The conducting oxides solid solutions of Cd_1+xIn_2−2xSn_xO₄ (x=0.1, 0.3, 0.5, 0.7, 1.0) were prepared via a solid state reaction method. The band gaps were estimated to be 2.4 eV for x=1.0, 2.5 eV for x=0.7, 2.6 eV for x=0.5, 2.7 eV for x=0.3 and 2.8 eV for x=0.1. Oxygen could be evolved over Cd₂SnO₄ under the irradiation of Xe-lamp or even visible light (λ>420 nm), while the others could only work in the UV-light range. Raman showed the cation distribution in Cd₂SnO₄ is ordered, while that in the others is disordered. The cations distribution was proposed to be the cause of the difference in photocatalytic O₂-evolution activities.     

Observation of mixed-phase behavior in the Mn-doped cobaltite La0.7Sr0.3Co1−xMnxO3 (x=0-0.5)

Studies on La_0.7Sr_0.3Co_1−xMn_xO₃ (x=0-0.5) compounds evidence that the interaction between Mn and Co ions in this system is antiferromagnetic super-exchange and not ferromagnetic (FM) double-exchange (DE). As a result, antiferromagnetism and magnetic glassiness develop steadily with increasing Mn content and the system becomes a spin glass at x∼0.1. Analyses of high-field magnetization data indicate that the system consists of two major phases: a metallic FM phase which magnetically saturates in rather low field, and an insulating non-FM phase which has a linear dependence of magnetization on magnetic field. In the low doping regime, the fraction of the non-FM component expands with temperature at the expense of the FM phase and becomes maximal at T_C. Ferromagnetism reappears in highly doped (x≥0.2) compounds due to the presence of DE interaction between the Mn ions. The small volume fraction of the FM phase derived from the M(H) data in high-field region supports the coexistence of insulating and FM behaviors in the highly doped samples.     

Magnetic properties and magnetic structures of Sr3−xCaxRu2O7

We have measured magnetization curves and powder neutron diffraction of double-layered Ruddlesden-Popper type ruthenate Sr_3−xCa_xRu₂O₇ (x=1.5, 2.0 and 3.0). The field dependence of the magnetization revealed that the transition field of metamagnetic transition along the b-axis shifted to lower fields and that the transition became broad with increasing Sr content. The slope of the magnetization curve also increased with increasing Sr content below the metamagnetic transition. These results indicate that an itinerant component is partly introduced by the Sr substitution. From the magnetic reflection, on cooling below T_N, an additional reflection was observed at (0 0 1) for each x, and the amplitude increased with decreasing temperature. The observed diffraction patterns are very similar to those of Ca₃Ru₂O₇. We conclude that the magnetic structure of the antiferromagnetic ordered phase is basically the same structure with that of Ca₃Ru₂O₇.     

Ferromagnetism in amorphous Ge1−xMnx grown by low temperature vapor deposition

Magnetic properties of amorphous Ge_1−xMn_x thin films were investigated. The thin films were grown at 373 K on (100) Si wafers by using a thermal evaporator. Growth rate was ∼35 nm/min and average film thickness was around 500 nm. The electrical resistivities of Ge_1−xMn_x thin films are 5.0×10⁻⁴∼100 Ω cm at room temperature and decrease with increasing Mn concentration. Low temperature magnetization characteristics and magnetic hysteresis loops measured at various temperatures show that the amorphous Ge_1−xMn_x thin films are ferromagnetic but the ferromagnetic magnetizations are changing gradually into paramagnetic as increasing temperature. Curie temperature and saturation magnetization vary with Mn concentration. Curie temperature of the deposited films is 80-160 K, and saturation magnetization is 35-100 emu/cc at 5 K. Hall effect measurement at room temperature shows the amorphous Ge_1−xMn_x thin films have p-type carrier and hole densities are in the range from 7×10¹⁷ to 2×10²² cm⁻³.     

Synthesis of aqueous ferrofluids of ZnxFe3−xO4 nanoparticles by citric acid assisted hydrothermal-reduction route for magnetic hyperthermia applications

Superparamagnetic and monodispersed aqueous ferrofluids of Zn substituted magnetite nanoparticles (Zn_xFe_3−xO₄, x=0, 0.25, 0.3, 0.37 and 0.4) were synthesized via hydrothermal-reduction route in the presence of citric acid, which is a facile, low energy and environmental friendly method. The synthesized nanoparticles were characterized by X ray diffraction (XRD) analysis, Fourier transform infrared (FTIR) spectroscopy, scanning and transmission electron microscopy (SEM and TEM) and the dynamic light scattering (DLS) method. The results showed that a certain amount of citric acid was required to obtain single phase Zn substituted magnetite nanoparticles. Citric acid acted as a modulator and reducing agent in the formation of spinel structure and controlled nanoparticle size and crystallinity. Mean particle sizes of the prepared nanoparticles were around 10 nm. The results that are obtained from XRD, magnetic and power loss measurements showed that the crystallinity, saturation magnetization (M_S) and loss power of the synthesized ferrofluids were all influenced by the substitution of Zn in the structure of magnetite. The Zn substituted magnetite nanoparticles obtained by this route showed a good stability in aqueous medium (pH 7) and hydrodynamic sizes below 100 nm and polydispersity indexes below 0.2. The calculated intrinsic loss power (ILP) for the sample x=0.3 (e.g. 2.36 nH m²/kg) was comparable to ILP of commercial ferrofluids with similar hydrodynamic sizes.     

Analysis of magnetic field dependent mobility in ferromagnetic Ga1−xMnxAs layers

The magneto-transport properties of ferromagnetic Ga_1−xMn_xAs epilayers with Mn mole fractions in the range of x≈2.2-4.4% were investigated through Hall effect measurements. The magnetic field-dependent Hall mobility for a metallic sample with x≈2.2% in the temperature range of T=0-300 K was analyzed by magnetic field-dependent mobility model including an activation energy of Mn acceptor level. This model provides outstanding fits to the measured data up to T=300 K. It was found that the acceptor levels with activation energies of 112 meV at B=0 Oe decreased to 99 meV at B=5 kOe in the ferromagnetic region. The decrease in acceptor activation energy was due to the spin splitting of the Mn acceptor level in the ferromagnetic region, and was responsible for increase in carrier concentration.     

Magnetic, electric, and optical functionalities of (PLZT)x(BiFeO3)1−x ferroelectric-ferromagnetic thin films

We have prepared a series of (PLZT)_x(BiFeO₃)_1−x transparent thin films with thickness of 300 nm by a thermal pyrolysis method. Only films with x≦0.10 formed a single phase of perovskite structure. The film where x=0.10 exhibited both ferromagnetic and ferroelectric properties at room temperature with spontaneous magnetization and coercive magnetic fields of 0.0027μ_B and 5500 G, respectively. The remanent electric polarization and coercive electric field for the film where x=0.10 were 3.0 μC/cm² and 24 kV/cm, respectively. Additionally, films with 0.02≦x≦0.10 showed both magneto-optical effects and the second harmonic generation of transmitted light.