Structural and magnetic properties of Zn1−xCoxO (0<x⩽0.30) nanoparticles

We present a systematic investigation on the structural and magnetic properties of Zn_1−xCo_xO nanoparticles synthesized by an auto-combustion method. The single-phase Zn_1−xCo_xO crystallize in the wurtzite-type structure with a homogeneity range as large as x≈0.30, which enables the observation of some anomalies. The lattice parameter a and the unit cell volume V increase with the Co content, and anomalies are discernable around x=0.15 on the a−x and V−x curves. The magnetization data show no evidence of ferromagnetic (FM) ordering in our samples down to T=5 K, and the magnetization at 5 K and 5 T exhibits a maximum around x=0.125. Based on the detailed analysis of the magnetization data and the donor impurity band exchange model, the anomalies on composition dependence of both the lattice parameters and magnetization can be associated with an occurrence of cation percolation around the threshold x_p (≈1.5/Z=0.125 for three-dimensional lattice with coordination number Z=12). Within the framework of the donor impurity band exchange model, the absence of FM in the well-characterized Zn_1−xCo_xO can be attributed to insufficient donor electron concentration.     

Structural and magnetic properties of SmCo7−xMox alloys

Phase structure and magnetic properties of the as-cast and as-milled/annealed SmCo_7−xMo_x (x=0, 0.1, 0.2, 0.3, 0.4) alloys have been systematically studied. It is found that all the as-cast series alloys are composed of the CaCu₅-type and Th₂Zn₁₇-type phases. Saturation magnetization of the samples decreases with the Mo content increasing. Intrinsic coercivities (_iH_c) of no more than 0.06 T are observed in these as-cast samples, due to their rather coarse grain microstructures with an average grain size of 50 μm. The as-milled/annealed SmCo_7−xMo_x powders crystallize in the disordered TbCu₇-type (1:7) structure with very fine nanograins, and a minor Co₃Mo phase appears in the samples with x=0.1-0.4. High _iH_c (?0.95 T) are achieved in these samples, with a maximum of 1.26 T located at x=0.2, which can be primarily attributed to strong pinning of the domain wall motion at the nanograin boundaries. The temperature coefficient (β) of the _iH_c is about −0.22%/°C in the temperature range of 25-400 °C for the as-milled/annealed samples.     

Defects-driven appearance of half-metallic ferrimagnetism in Co-Mn-based Heusler alloys

Half-metallic ferromagnetic full-Heusler alloys containing Co and Mn, having the formula Co₂MnZ where Z is a sp element, are among the most studied Heusler alloys due to their stable ferromagnetism and the high Curie temperatures which they present. Using state-of-the-art electronic structure calculations we show that when Mn atoms migrate to sites occupied in the perfect alloys by Co, these Mn atoms have spin moments antiparallel to the other transition metal atoms. The ferrimagnetic compounds, which result from this procedure, keep the half-metallic character of the parent compounds and the large exchange-splitting of the Mn impurities atoms only marginally affects the width of the gap in the minority-spin band. The case of [Co_1−xMn_x]₂MnSi is of particular interest since Mn₃Si is known to crystallize in the Heusler L2₁ lattice structure of Co₂MnZ compounds. Robust half-metallic ferrimagnets are highly desirable for realistic applications since they lead to smaller energy losses due to the lower external magnetic fields created with respect to their ferromagnetic counterparts.     

A study of Sm-substituted SrM magnets sintered using hydrothermally synthesised powders

Anisotropic SrM magnets with Sm substitution, which is observed to have the largest beneficial effect both on the coercivity and on the inhibition of grain growth at high temperature among the other elements such as La, Nd and Pr, were investigated. The average grain size of the samples decreases with increasing Sm/Sr ratio. All the magnets with Sm additions exhibit a bigger coercivity and remanence than those of the SrM magnet without Sm and the coercivity of the magnets increases with increasing Sm/Sr ratio. EDX quantitative analysis suggests that the solubility of Sm³⁺ in the SrM-type structure is very small and that the Sm³⁺ preferably goes into SrFeO_3−x, which is probably located around the SrM grain boundaries. The coercivity mechanism of the magnets is nucleation controlled. The formation and the distribution of the SrFeO_3−x phase around the SrM grain boundraies probably provides the inhibition of SrM grain growth, the reduction of the reverse domain nucleation at the grain surface and the isolation of the SrM grains. All these factors would contribute to the improvements of the coercivity of the magnets with Sm additions.     

Spin-glass-like phase behaviour in CeNi2−xCuxSn2

We report the results of our investigation in CeNi_2−xCu_xSn₂ (x=0, 0.4, 1.0, 1.6 and 2.0), a new pseudoternary series with CaBe₂Ge₂-type tetragonal structure. Substitution of Cu for Ni leads to a linear increase in the constants a, c and the unit cell volume v. As probed by the low temperature dependence of ac susceptibility χ_ac(T), the T_f temperature, which corresponds to the freezing temperature of the spin-glass clusters, is annihilated above 2.0 K significantly for the samples with x≥1.6. This observation proves conclusively that the Ni-rich samples in the series CeNi_2−xCu_xSn₂ have the advantage of forming the spin-glass-like state.     

The influence of hydrogen annealing on magnetism of Co-doped TiO2 films prepared by sol–gel method

Co-doped TiO₂ (Co_xTi_1−xO₂, 0.05?x?0.2) films have been prepared on Si (0 0 1) substrates by sol–gel method. When heat treated in air, Co_xTi_1−xO₂ films are non-ferromagnetic at room temperature. However, after further annealed in a flowing hydrogen atmosphere, Co_xTi_1−xO₂ films show room-temperature ferromagnetism (RTFM). Measurements of magnetization (M) vs. temperature (T), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) fail to detect Co clusters in the hydrogenated Co_0.1Ti_0.9O₂ films, suggesting that RTFM in the hydrogenated Co_0.1Ti_0.9O₂ films may be intrinsic. But, metal Co appears in the hydrogenated Co_0.2Ti_0.8O₂ films, showing that RTFM in the hydrogenated Co_0.2Ti_0.8O₂ films is as least partly due to metal Co. These results indicate that hydrogen annealing can produce room-temperature ferromagnetism in Co_xTi_1−xO₂ films, but it should be carefully designed to avoid the formation of metal Co in the hydrogenated Co_xTi_1−xO₂ films.     

Structure and magnetic properties of SmCoxTi0.4-1:7 ribbons

SmCo_xTi_0.4 (x=6.6, 7.1, 7.6, 8.1) ribbons have been prepared by melt spinning at a wheel speed of 42 m/s, followed by annealing at 750 °C for 2 h. Both as-spun and as-annealed ribbons possess the disordered TbCu7-type (1:7) phase even when the Sm/(Co,Ti) atomic ratio deviates from 1/7. The c/a ratio increases with increasing Co concentration x, but the unit cell volume decreases. The Curie temperatures show above 700 °C, increasing from 707 °C for x=6.6 to 782 °C for x=8.1. The saturation magnetizations increase almost linearly with increasing Co content. The observed magnetic hardening is believed to arise from the high magnetocrystalline anisotropy of the 1:7 phase and the fine nanograin structure. The intrinsic coercivity of 9797 Oe has been obtained in the melt-spun SmCo_7.1Ti_0.4 ribbons.     

The role of oxygen vacancies in magnetism of CoxTi1−xO2−δ films on Si(001) prepared by sol-gel method

Co_xTi_1−xO_2−δ films have been prepared on Si(001) substrates by sol-gel method. When heat treated in air, Co_xTi_1−xO_2−δ films are non-ferromagnetic at room temperature. However, after further vacuum annealing or hydrogenation, Co_xTi_1−xO_2−δ films show room-temperature ferromagnetism (RTFM). When the vacuum annealed Co_xTi_1−xO_2−δ films are reheated in air, the magnetic moments of the films strongly reduce. After these films are vacuum annealed once again, the magnetic moments are greatly enhanced, confirming the role of vacuum annealing in ferromagnetism of Co_xTi_1−xO_2−δ films. The x-ray diffraction (XRD), x-ray photoelectron spectroscopy (XPS) and measurements of magnetization (M) vs temperature (T) fail to detect Co clusters in the vacuum annealed and the hydrogenated Co_xTi_1−xO_2−δ films. Oxygen vacancies are formed in Co_xTi_1−xO_2−δ films after vacuum annealing and hydrogenation, determined by XRD and XPS measurements. These results indicate that oxygen vacancies created by vacuum annealing and hydrogenation play an important role in the generation of RTFM in Co_xTi_1−xO_2−δ films.     

Research on La–Co-substituted strontium ferrite magnets for high intrinsic coercive force

M-type strontium ferrites with substitution of Sr²⁺ by rare-earth La³⁺, and a little amount of Fe³⁺ by Co²⁺ according to the formula Sr_1−xLa_xFe_12−xCo_xO₁₉, are prepared by the ceramic process. Effects of the substituted amount of La³⁺ and Co²⁺ on structure and magnetic properties of Sr_1−xLa_xFe_12−xCo_xO₁₉ compounds have systematically been investigated by X-ray diffraction (XRD), vibrating sample magnetometer (VSM) and B–H hysteresis curve measurements. In our results, the suitable amount of La³⁺–Co²⁺ substitution may remarkably increase saturation magnetization. Intrinsic coercive force (H_cj) of Sr ferrite magnets is evidently increased without significant decrease in residual flux density (B_r) by La³⁺–Co²⁺ substitution.     

Transmission electron microscopy study of large field induced anisotropy (Co1−xFex)89Zr7B4 nanocomposite ribbons with dilute Fe-contents

Electron microscopy was employed to investigate the structure of magnetic field crystallized (Co_1−xFe_x)₈₉Zr₇B₄ alloys with only dilute Fe-contents (x=0, 0.025, 0.05, and 0.10). The x=0.025 and 0.05 alloys exhibit very large field induced anisotropies and multiple nanocrystalline phases (BCC, FCC, and HCP) surrounded by an intergranular amorphous phase. Correlation between the volume fraction crystallized and the measured value of H_K suggests that the large K_U values are associated with the crystalline phases that form. Multiple crystalline phases are present for the highest K_U alloys and so the presence of FCC and/or HCP-type nanocrystals may be responsible for these observations. High-resolution transmission electron microscopy (HRTEM) illustrates a number of microstructural features including (1) high densities of stacking faults in many of the FCC and, in particular, the HCP-type nanocrystals, (2) infrequent BCC/FCC orientation relationships, and (3) nanocrystals with disordered or long period stacking sequences of close-packed planes. High densities of planar faults are suggested as a potential source of K_U for the FCC and HCP-type nanocrystals, but the origin of the large values of K_U found in dilute Fe-containing, Co-rich “nanocomposite” alloys is an area where further work is needed.     

Metastable ferromagnetic phases with predictable Tcs in La2MnCo1−xNixO6

Metastable ferromagnetic phases, for different compositions in La₂MnCo_1−xNi_xO₆, are obtained for samples synthesized by a low-temperature method and annealed in air at different temperatures in the range 200-1350 °C. The T_cs of the ferromagnetic phases vary linearly between those of the phases of the end members. T_cs of the different phases of La₂MnCo_1−xNi_xO₆ can be predicted based on the T_cs and spin states of Mn, Co and Ni in the different phases of the end members, La₂MnCoO₆ and La₂MnNiO₆.     

Hard magnetic properties of ErCo7−xCux [0.3⩽x⩽1] system

We report the observation of excellent hard magnetic properties on purely single phase ErCo_7−xCu_x compounds with x=0.3, 0.5, 0.8 and 1. Cu substitution leads to a decrease in the saturation magnetization, but enhances the uniaxial anisotropy in this system. The large anisotropy field (∼100 kOe) is attributed to the Er and the Co sublattices. Domain wall pinning effect seems to play a crucial role in determining the temperature and field dependences of magnetization in these compounds. The hard magnetic properties obtained at room temperature (RT) are comparable to the best results obtained in other RCo₇ based materials.     

Phase boundary between uniaxial and planar ferromagnets in layered perovskite manganite La2−2xSr1+2xMn2O7 (0.313⩽x⩽0.350)

We have examined magnetizations as a function of temperature and magnetic field in layered perovskite manganites La_2−2xSr_1+2xMn₂O₇ single crystals (x=0.313, 0.315, 0.318, 0.320 and 0.350) in order to determine the phase boundary between two ferromagnets (one is an uniaxial ferromagnet whose easy axis is parallel to the c-axis and the other is a planar ferromagnet whose easy axis is within the ab-plane) and following results are obtained: (i) all the present manganites exhibit magnetic transitions from a ferromagnet to a paramagnet at 76, 107, 116, 120 and 125 K for x=0.313, 0.315, 0.318, 0.320 and 0.350, respectively; (ii) for x=0.318, 0.320 and 0.350, the magnetic structure is a planar ferromagnet below Curie temperature; (iii) for x=0.313 and 0.315, the magnetic structure changes from an uniaxial to a planar ferromagnet at 66 and 85 K, respectively. From the results described above we have constructed the magnetic phase diagram of layered perovskite manganite La_2−2xSr_1+2xMn₂O₇ (0.313?x?0.350).     

Structure and magnetic phase diagram of mixed rare-earth Nd1−xTbxFe10.5Mo1.5 compounds

The structural and magnetic properties of Nd_1−xTb_xFe_10.5Mo_1.5 (x=0$x=0$, 0.2, 0.4, 0.6, 0.8, 1.0) compounds have been investigated by means of X-ray diffraction and magnetic measurements. All the investigated compounds crystallize in the tetragonal ThMn₁₂-type structure with I4/mmm space group. The lattice parameters a, c and the unit-cell volume V decrease with increasing x. The Curie temperatures T_C are almost independent x. There exists a unique spin-reorientation transition for the end compositions of Nd_1−xTb_xFe_10.5Mo_1.5 compounds with x=0$x=0$ and x=1$x=1$, while two spin-reorientation transitions are observed for x=0.2–0.8$x=0.2–0.8$. The room-temperature magnetocrystalline anisotropy of Nd_1−xTb_xFe_10.5Mo_1.5 compounds changes from uniaxial to planar with increasing x content. Based on magnetic measurements, a magnetic phase diagram of Nd_1−xTb_xFe_10.5Mo_1.5 compounds is constructed. By minimizing the magnetocrystalline anisotropy energy, a theoretical magnetic phase diagram for the Nd_1−xTb_xFe_10.5Mo_1.5 system is derived, showing a reasonable agreement with the observations.     

Properties of exchange interaction in Yb3Fe5O12 under extreme conditions

In Yb₃Fe₅O₁₂, the exchange effective field can be expressed as H_eff=−λ·M_Fe=−λχ_eff·H_e=−γ·H_e where γ is named as the exchange field parameter and H_e is the external magnetic field. Then, in this paper, by the discussions on the characteristics of the exchange field parameter γ, the properties of exchange interaction in ytterbium iron garnet (Yb₃Fe₅O₁₂) are analyzed under extreme conditions (high magnetic fields and low temperatures). Our theory suggests that the exchange field parameter γ is the function of the temperatures under different external magnetic fields, and γ=a+b·T+c·T², where the coefficients a, b, c are associated with the external magnetic fields and the magnetized directions. Thus, the temperature-dependence, field-dependence and anisotropic characteristics of the exchange interaction in Yb₃Fe₅O₁₂ are revealed. Also, excellent fits to the available experiments are obtained.     

Giant intrinsic magnetic hardness in RFe5−x Ni x (R=rare earth,x=4 to 5)

Giant low temperature intrinsic magnetic hardness is observed in structurally homogeneous CaCu₅ type compounds RFe_5−x Ni _x . In SmFe_5−x Ni _x , this magnetic hardness peaks approximately at a composition SmFe_0.2Ni_4.8, with an extrapolated coercive force of 230 kOe at absolute zero. The transition metal sublattice is not anisotropic. Thus, the rare earth alone creates giant coercivity. Only compounds withc-axis preference exhibit substantial magnetic hardness (Sm, Er, Tm). Partial substitution of a tetravalent rare earth to produce crystal field anisotropy fluctuations apparently increases coercivity somewhat in the axis-preference compound SmFeNi₄, but has no effect in the plane-preferred compound TbFeNi₄.     

Controlled Cu content of electrodeposited CoCu nanowires through pulse features and investigations of microstructures and magnetic properties

CoCu alloy nanowire arrays embedded in anodic alumina template were fabricated by ac pulse electrodeposition. Different off-times between pulses in an electrolyte with constant concentration of Co⁺² and Cu⁺² and acidity of 4 were employed. The effect of deposition parameters on the alloy contents, microstructures and magnetic properties of Co_xCu_1−x nanowires were studied. It is shown that Co content decreased by increasing the off-time between pulses in a wide range (x = 0.53-0.07). These results are in consistence with saturation magnetization, which was reduced with increase in the off-time between pulses. It was also found that by optimizing the off-times, it is possible to fabricate CoCu nanowires with mixed phase of hcp Co, fcc Cu and fcc CoCu crystal phase.     

Magnetotransport properties of (La0.7Pb0.3MnO3)1−xAgx composites

Magnetic and transport properties of (La_0.7Pb_0.3MnO₃)_1−xAg_x composites are explored in this study. Ferromagnetism is gradually attenuated due to the magnetic dilution with increase of Ag content percentage. Clearly irreversible behavior in the zero-field cooling and field cooling curves at a low field caused by the competition between the magnetization and magnetic domain orientation processes has been observed as x increases. Saturation magnetization decreases as x increases, while ferromagnetic transition temperature remains around 346 K for all composites. The resistivity decreases significantly for (La_0.7Pb_0.3MnO₃)_1−xAg_x composites. It is suggested that introduction of Ag into the niche of grain boundaries forms artificial conducting network and improves the carriers to transport. However, enhancement of magnetoresistance has been observed for the system.     

Synthesis and magnetic characterization of cobalt-substituted ferrite (CoxFe3−xO4) nanoparticles

Cobalt-substituted ferrite nanoparticles were synthesized with a narrow size distribution using reverse micelles formed in the system water/AOT/isooctane. Fe:Co ratios of 3:1, 4:1, and 5:1 were used in the synthesis, obtaining cobalt-substituted ferrites (Co_xFe_3−xO₄) and some indication of γ-Fe₃O₄ when 4:1 and 5:1 Fe:Co ratios were used. Inductively coupled plasma mass spectroscopy (ICP-MS) verified the presence of cobalt in all samples. Fourier transform infrared (FTIR) showed bands at ∼560 and ∼400 cm⁻¹, characteristic of the metal–oxygen bond in ferrites. Transmission electron microscopy showed that the number median diameter of the particles was ∼3 nm with a geometric deviation of ∼0.2. X-ray diffraction (XRD) confirmed the inverse spinel structure typical of ferrites with a lattice parameter of a=8.388 Å for Co_0.61Fe_0.39O₄, which is near that of CoFe₂O₄ (a=8.394 Å). Magnetic properties were determined using a superconducting quantum interference device (SQUID). Coercivities higher than 8 kOe were observed at 5 K, whereas at 300 K the particles showed superparamagnetic behavior. The anisotropy constant was determined based on the Debye model for a magnetic dipole in an oscillating field and an expression relating χ′ and the temperature of the in-phase susceptibility peak. Anisotropy constant values in the order of ∼10⁶ erg/cm³ were determined using the Debye model, whereas anisotropy constants in the order of ∼10⁷ erg/cm³ were calculated assuming Ωτ=1 at the temperature peak of the in-phase component of the susceptibility curve as commonly done in the literature. Our analysis demonstrates that the assumption Ωτ=1 at the temperature peak of χ′ is rigorously incorrect.     

Electronic structure and ferromagnetism of polycrystalline Zn1−xCoxO (0≤x≤0.15)

The electronic structure of polycrystalline ferromagnetic Zn_1−xCo_xO (0.05≤x≤0.15) and the oxidation state of Co in it, have been investigated. The Co-doped polycrystalline samples are synthesized by a combustion method and are ferromagnetic at room temperature. XPS and optical absorption studies show evidence for Co²⁺ ions in the tetrahedral symmetry, indicating substitution of Co²⁺ in the ZnO lattice. However, powder XRD and electron diffraction data show the presence of Co metal in the samples. This give evidence to the fact that some Co²⁺ ion are incorporated in the ZnO lattice which gives changes in the electronic structure whereas ferromagnetism comes from the Co metal impurities present in the samples.