Spin-glass-like behaviour and magnetic order in Mn[Cr0.5Ga1.5]S4 spinels

Magnetization and susceptibility were investigated as a function of temperature and magnetic field in polycrystalline Mn[Cr_0.5Ga_1.5]S₄ spinel. The dc susceptibility measurements at 919 Oe showed a disordered ferrimagnetic behaviour with a Curie-Weiss temperature θ_CW=−55 K and an effective magnetic moment of 5.96 μ_B close to the spin-only value of 6.52 μ_B for Cr³⁺ and Mn²⁺ ions in the 3d³ and 3d⁵ configurations, respectively. The magnetization measured at 100 Oe revealed the multiple magnetic transitions with a sharp maximum at the Néel temperature T_N=3.9 K, a minimum at the Yafet-Kittel temperature T_YK=5 K, a broad maximum at the freezing temperature T_f=7.9 K, and an inflection point at the Curie temperature T_C=48 K indicating a transition to paramagnetic phase. A large splitting between the zero-field-cooled (ZFC) and field-cooled (FC) magnetizations at a temperature smaller than T_C suggests the presence of spin-glass-like behaviour. This behaviour is considered in a framework of competing interactions between the antiferromagnetic ordering of the A(Mn) sublattice and the ferromagnetic ordering of the B(Cr) sublattice.     

Understanding the magnetic ground state of rare-earth intermetallic compound Ce4Sb3: Magnetization and neutron diffraction studies

Magnetization and neutron diffraction studies have been performed on Ce₄Sb₃ compound (cubic Th₃P₄-type, space group I4¯3d, no. 220). Magnetization of Ce₄Sb₃ reveals a ferromagnetic transition at ∼5 K, the temperature below which the zero-field-cooled and field-cooled magnetization bifurcate in low applied fields. However, a saturation magnetization (M_S) value of only ∼0.93μ_B/Ce³⁺ is observed at 1.8 K, suggesting possible presence of crystal field effects and a paramagnetic/antiferromagnetic Ce³⁺ moment. Magnetocaloric effect in this compound has been computed using the magnetization vs. field data obtained in the vicinity of the magnetic transition, and a maximum magnetic entropy change, −ΔS_M, of ∼8.9 J/kg/K is obtained at 5 K for a field change of 5 T. Inverse magnetocaloric effect occurs at ∼2 K in 5 T indicating the presence of antiferromagnetic component. This has been further confirmed by the neutron diffraction study that evidences commensurate antiferromagnetic ordering at 2 K in zero magnetic field. A magnetic moment of ∼1.24μ_B/Ce³⁺ is obtained at 2 K and the magnetic moments are directed along Z-axis.     

Structural and magnetic properties of ferromagnetic In1−xMnxAs1−yPy layers

The structural and magnetic properties of epitaxial In_1−xMn_xAs_1−yP_y quaternary layers with Mn content ranging from 0.01 to 0.04 and phosphorous content ranging from 0.11 to 0.21 were studied. X-ray diffraction indicated that the films were two phase consisting of an InMnAsP solid solution and hexagonal MnAs nanoprecipitates. Addition of phosphorus promoted precipitate formation. Films were ferromagnetic showing hysteretic behavior in the field dependence of magnetization at 5 and 298 K. From field-cooled magnetization measurements ferromagnetic transitions were observed at 280 and 325 K. The zero field-cooled magnetization versus temperature measurements showed irreversibility for T<300 K that was attributed to the presence of MnAs nanoprecipitates. The calculated coercivity using the Neel model was 1380 G compared to the experimental value of 380 G at 5 K. The difference was attributed to a strong inter-cluster exchange that stabilizes the ferromagnetic state.     

Magnetic properties of nanoscale crystalline maghemite obtained by a new synthetic route

In this work we describe the synthesis and characterization of maghemite nanoparticles obtained by a new synthetic route. The material was synthesized using triethylamine as a coprecipitation agent in the presence of the organic ligand N,N′-bis(3,5-di-tert-butyl-catechol)-2,4-diaminotoluene (LCH₃). Mössbauer spectrum at 4 K shows typical hyperfine parameters of maghemite and Transmission Electron Microscopy images reveal that the nanoparticles have a mean diameter of 3.9 nm and a narrow size distribution. AC magnetic susceptibility in zero field presents an Arrhenius behavior with unreasonable relaxation parameters due to the strong influence of dipolar interaction. In contrast when the measurements are performed in a 1 kOe field, the effect of dipolar interactions becomes negligible and the obtained parameters are in good agreement with the static magnetic properties. The dynamic energy barrier obtained from the AC susceptibility results is larger than the expected from the average size observed by HRTEM results, evidencing the strong influence of the surface contribution to the anisotropy.     

Some aspects of antiferromagnetic ordering in LiMnP0.85V0.15O4: Neutron diffraction and DC-magnetization studies

V-substituted LiMnPO₄ has been synthesized by the solid state reaction route. Combined Rietveld refinement of neutron and X-ray data revealed that all vanadium ions are located in the same positions as the phosphorus ions. The magnetic structure of LiMnP_0.85V_0.15O₄ was found to be the same as that described for undoped antiferromagnetic LiMnPO₄ (T_N=34.5 K). DC-magnetization measurements were carried out to study the peculiarities of magnetic ordering in LiMnP_0.85V_0.15O₄. An irreversible behavior of DC magnetization was found at magnetic fields less than ∼2 kOe. It was demonstrated that an increase in the magnitude of the applied field leads to a reduction of the discrepancy between zero-field-cooled and field-cooled processes. These effects were explained by the movement of domain walls and by transition of the system to a monodomain state. The anomaly in the magnetization vs field dependence attributed presumably to the spin-flop transition was observed at ∼40 kOe. The existence of magnetic inhomogeneity in the paramagnetic phase of LiMnP_0.85V_0.15O₄ was proved by the analysis of the χ?T product. It was concluded that the observed changes in χ?T are indicative of a competition between ferromagnetic and antiferromagnetic correlations at temperatures slightly exceeding T_N.     

Magnetic properties of compounds in the system CaBaCo4−x−yZnxAlyO7 (x=0,1,2, y=0,1)

The magnetic properties of four compounds in the series CaBaCo_4−x−yZn_xAl_yO₇ (x=0,1,2, y=0,1) were investigated. Using AC-susceptibility and DC-magnetometry, magnetic transitions (T_fs) were found for all four compositions in the range 50-3 K. The data from the AC measurements proved to be frequency dependent: T_f increases with higher frequencies. An energy-loss in the magnetic coupling, indicated as contributions in the imaginary part of the magnetic susceptibility (χ″), was seen for every compound and its maximum appeared just below the maximum χ′. Modelling the data with Arrhenius-, Vogel-Fulcher-, and the power-law made it possible to relate the four compounds to spin-glass materials. The Casimir-du Pré relation was used to extract average relaxation times at T_f. The DC magnetisations clearly show differences between field-cooled and zero-field-cooled measurements. None of the compounds exhibit any metamagnetic properties up to 8 T. A new method is presented to calculate the saturation fields using DC data. Relaxation measurements on three compounds indicate that the systems relax very fast, in contrast to spin-glasses. Aging does not affect the fast relaxations. The compounds are interpreted as disordered anti-ferromagnets with spin-glass features.     

Hydrogen absorption and field-dependent diamagnetism of SmNiAl

Hydrogen absorption properties of SmNiAl were systematically investigated between room temperature and 673 K over the pressure range from 0 to 10 MPa. It absorbs hydrogen without clear plateaus, forms hydride SmNiAlH_x (x=0.75–2.04) without structural change below 623 K and decomposes into SmH₂ and NiAl at higher temperatures. Then, the magnetic curves, the field-cooled (FC) and the zero-field-cooled (ZFC) susceptibilities of SmNiAl and its hydride were investigated. SmNiAl behaves as paramagnetic above 65 K, but has three antiferromagnetic transitions at lower temperatures. Hydrogenation enhances its magnetism, but weakens the interaction between magnetic moments. In the FC process, hydrogenation especially induces an anomalous diamagnetism. Mechanisms for the hydrogen absorption, structural change and magnetism were discussed.     

A re-evaluation of the heat capacity of cerium zirconate (Ce2Zr2O7)

The heat capacity of cerium zirconate pyrochlore, Ce₂Zr₂O₇, was measured from 0.4 to 305 K by hybrid adiabatic relaxation method for various magnetic field strengths. Magnetisation measurements were performed on the sample also. The results revealed a low-temperature anomaly that showed Schottky-type characteristics with increasing magnetic field strength. The estimated entropy due to the magnetic ordering of the two Ce³⁺ moments is 1.37R, close to the theoretical value for a doublet ground state (1.39R). The enthalpy increments relative to 298.15 K were measured by drop calorimetry from 531 to 1556 K. The obtained results significantly differ from those reported in the literature; the origin of the discrepancy is due to the probable oxidation of the pyrochlore structure into fluorite.     

Metamagnetic transition and magnetocaloric effect in antiferromagnetic TbPdAl compound

Magnetic properties and the magnetocaloric effect of the compound TbPdAl are investigated. The compound exhibits a weak antiferromagnetic (AFM) coupling, and undergoes two successive AFM transitions at T_N=43 K and T_t=22 K. A field-induced metamagnetic transition from AFM to ferromagnetic (FM) state is observed below T_N, and a small magnetic field can destroy the AFM structure of TbPdAl, inducing an FM-like state. The maximal value of magnetic entropy change is −11.4 J/kg K with a refrigerant capacity of 350 J/kg around T_N for a field change of 0-5 T. Good magnetocaloric properties of TbPdAl result from the high saturation magnetization caused by the field-induced AFM-FM transition.     

Magnetism of ferriprotoporphyrin IX monomers and dimers

The SQUID and the ⁵⁷Fe Mössbauer spectroscopy studies of the magnetic properties of monomeric and dimeric forms of iron porphyrin were performed between 2 and 305 K. The effective magnetic relaxation rate of the Fe atoms in iron porphyrin monomers exhibits complex temperature dependence, resulting from the competing spin-spin and spin-lattice relaxation processes. The dimerization of iron porphyrin dramatically speeds up the magnetic relaxation. The Fe-Fe antiferromagnetic exchange coupling constant in Fe-O-Fe dimer is J≈−110 cm⁻¹. The complementary application of SQUID and the Mössbauer spectroscopy is proposed as a new precise quantitative analytical methodology for monitoring of the aggregation process of iron porphyrin.     

Magnetic Properties of Nanoparticles Useful for SQUID Relaxometry in Biomedical Applications

We use dynamic susceptometry measurements to extract semiempirical temperature-dependent, 255-400 K, magnetic parameters that determine the behavior of single-core nanoparticles useful for SQUID relaxometry in biomedical applications. Volume susceptibility measurements were made in 5 K degree steps at nine frequencies in the 0.1-1000 Hz range, with a 0.2 mT amplitude probe field. The saturation magnetization (M_s) and anisotropy energy density (K) derived from the fitting of theoretical susceptibility to the measurements both increase with decreasing temperature; good agreement between the parameter values derived separately from the real and imaginary components is obtained. Characterization of the Néel relaxation time indicates that the conventional prefactor, 0.1 ns, is an upper limit, strongly correlated with the anisotropy energy density. This prefactor decreases substantially for lower temperatures as K increases. We find, using the values of the parameters determined from the real part of the susceptibility measurements at 300 K, that SQUID relaxometry measurements of relaxation and excitation curves on the same sample are well described.     

Effects of high-temperature annealing on magnetic properties of V-doped GaN thin films grown by MOCVD

Metal organic chemical vapor deposition (MOCVD) has been used to grow vanadium-doped GaN (GaN:V) on c-sapphire substrate using VCl₄ as the V source. The as-grown GaN:V exhibited a saturated magnetic moment (M_s) of 0.28 emu/cm³ at room temperature. Upon high-temperature annealing treatment at 1100 °C for 7 min under N₂ ambient, the M_s of the GaN:V increased by 39.28% to 0.39 emu/cm³. We found that rapid thermal annealing leads to a remarkable increase in surface roughness of the V-doped GaN as well as the electron concentration. The annealing also leads to a significant increase in the Curie temperature (T_C), we have identified Curie temperatures about 350 K concluded from the difference between the field-cooled and zero-field-cooled magnetizations. Structure characterization by x-ray diffraction indicated that the ferromagnetic properties are not a result of secondary magnetic phases.     

Magnetic entropy change in GdCo13−xSix intermetallic compounds

The magnetic entropy change in GdCo_13−xSi_x (x=3.8, 4, 4.1, and 4.2) intermetallic compounds has been investigated by means of magnetic measurements in the vicinity of their Curie temperature. It was found that the magnetic ordering temperatures decrease from 60 K at x=3.8 to 28 K for x=4.2. The magnetic entropy change is calculated from isothermal magnetization versus magnetic field at various temperatures using the Maxwell relation. As a result, the maximum magnetic entropy changes of the investigated compounds, at their Curie temperatures, decrease from 11.5 J/kg K for x=4.2 to 6.86 J/kg K for x=3.8 in a field change of 0-3 T, whereas it decreases from 5.13 J/kg K for x=4.2 to 2.60 J/kg K for x=3.8 in a field change of 0-1 T. Moreover, the maximum value of the magnetic entropy change obtained at a higher field for GdCo_13−xSi_x with x=4 (23.75 J/kg K at 5 T) is comparable to that of various types of compounds with a cubic NaZn₁₃-type structure. Finally, the maximum of the magnetic entropy change is found to decrease with increasing Si content.     

Exchange bias and magnetothermal properties in Fe@Mn nanocomposites

We have studied the Exchange Bias (EB) effect in nanocomposite films consisting of Fe nanoparticles (mean size ∼1.9 nm) embedded in an antiferromagnetic Mn matrix. They were produced by co-deposition through a gas aggregation cluster source and molecular beam epitaxy and have different Fe volume filling fractions (2.2% and 24.8%). The exchange field, higher in the sample with higher Fe concentration (at T=5 K, H_ex∼460 Oe for 24.8% and ∼310 Oe for 2.2% ), in both the samples decreases with increasing T, finally disappearing at T∼40 K. The EB properties have been studied in conjunction with results on the thermal dependence of the magnetic coercivity, zero-field-cooled and field-cooled magnetization and thermoremanence. The different Fe content strongly affects the magnetothermal properties, featuring superparamagnetic relaxation in the diluted sample and a reentrant ferromagnet-type transition in the concentrated one. Hence, the EB properties of the two samples have been discussed in consideration of such peculiarities of the magnetic behavior and highlighting the role of the Mn matrix.     

Magnetic properties of RPd5Al2 (R=Y, Ce, Pr, Nd, Sm, Gd)

Polycrystalline samples of a new rare-earth series RPd₅Al₂ crystallizing in the tetragonal ZrNi₂Al₅-type structure have been prepared. Their physical properties by electrical resistivity ρ, magnetic susceptibility χ, magnetization M and specific heat C_p measurements are reported. The ingots are composed of elongated grains preferentially aligned in the c direction; therefore, measurements were conducted parallel and perpendicular to the grains. Antiferromagnetic ordering appears in R=Ce, Nd, Gd, and Sm at low temperatures. CePd₅Al₂ has two AFM transitions at 4.1 and 2.9 K and ρ(T) indicates a Kondo metal behavior with large anisotropy. In PrPd₅Al₂ no magnetic transition was observed down to 0.4 K. The C_p(T) shows a broad peak around 13 K due to the CEF effect, suggesting a non-magnetic singlet ground state. In NdPd₅Al₂, χ(T) shows anisotropy and the C_p(T) shows a sharp peak at 1.2 K. The magnetic entropy at 3 K is very close to Rln2, indicating a Kramers doublet ground state. In SmPd₅Al₂, C_p(T) shows a magnetic transition at 1.7 K. C_p(T) for GdPd₅Al₂ shows a peak at 6 K, followed by a broad anomaly around 3 K. Within this series, T_N's for CePd₅Al₂ and NdPd₅Al₂ clearly deviate from the relation predicted by de Gennes scaling, which is ascribed to the CEF effect.     

Magnetic properties for the Mn2GeTe4 compound

Measurements of magnetic susceptibility χ, in the temperature range from 2 to 300 K, and of magnetization M vs. applied magnetic field B, up to 5 T, at various temperatures were made on polycrystalline samples of the Mn₂GeTe₄ compound. It was found that Mn₂GeTe₄ has a Néel temperature T_N of about 135 K, shows mainly antiferromagnetic behavior with a very weak superimposed ferromagnetic component that is attributed to spin canting. Also, the magnetic results suggest that a possible spin-glass transition takes place at T_f≈45 K. The spin-glass order parameter q(T), determined from the susceptibility data, was found to be in agreement with the prediction of conventional spin-glass theory. The M vs. B results indicated that bound magnetic polarons (BMPs) occur in the compound, and that the effects from BMPs disappear at approximately 80 K. The M vs. B curves were well fitted by a Langevin type of equation, and the variation of the fitting parameters determined as a function of temperature. Using a simple spherical model, the radius of the BMP in the material was found to be about 27 Å; this value is similar to the effective Bohr radius for an acceptor in the II-IV-V₂ and I-III-VI₂ ternary semiconductor compounds.     

A magnetic study of the ThCr2Si2-type RPd2Ge2 (R=Pr, Nd) compounds. Magnetic structure of PrPd2Ge2 from powder neutron diffraction

The magnetic properties of the PrPd₂Ge₂ and NdPd₂Ge₂ compounds have been investigated by magnetic measurements, specific heat measurements and neutron diffraction experiments. The PrPd₂Ge₂ compound orders antiferromagnetically below T_N=5.0(2) with an original modulated magnetic structure characterized by a magnetic cell three times larger than the chemical one by tripling of the c parameter. The palladium atom is non magnetic and the Pr moments are parallel to the c-axis with a value of ≈2.0 μ_B at 2 K. The specific heat measurements clearly detect a low temperature transition for the NdPd₂Ge₂ compound, interpreted as a Nd sublattice antiferromagnetic ordering below 1.3(2) K.     

Heat capacity of CeIrSi3 under pressure

We measured the heat capacity of CeIrSi₃ (100 mK<T<6 K) under high pressure up to P=1.38 GPa. The measurements have been used a quasiadiabatic method utilizing a CuBe piston-cylinder pressure cell in a dilution refrigerator. At 0 GPa, a sharp anomaly which indicates the antiferromagnetically transition is observed at T_N=5 K. T_N decreases monotonically with increasing pressure up to P=1.38 GPa. The magnetic entropy is released below T_N only 19% of R ln 2 at 0 GPa. And the magnetic entropy decreases with increasing pressure up to 1.38 GPa, 64% compared to that at 0 GPa.     

Antiferromagnetic order and spin glass behavior in Dy2CuIn3

The magnetic properties of the intermetallic compound Dy₂CuIn₃ have been investigated. Ac and dc-susceptibility measurements indicate an onset of antiferromagnetic ordering at T_N=19.5 K and an additional frequency dependent transition at T_ds∼9 K. Neutron diffraction studies confirm the ordered transition at 19.5±1 K. The magnetic unit cell can be described by the propagation vector k=(0.25,0.25,0) with the magnetic moment μ=2.63(4)μ_B/Dy³⁺ parallel to the c-axis. Nevertheless, neutron diffraction reveals no additional magnetic phase transition around or below 9 K, which suggests that, at lower temperatures, a spin glass state may be formed in coexistence with the antiferromagnetic mode as a result of frustration and the antagonism between ferromagnetic and antiferromagnetic exchange interactions.     

Polyol synthesis and magnetic study of Mn3O4 nanocrystals of tunable size

Nanosized manganese oxide particles were prepared by the so-called polyol process. The average diameter of the particles was controlled by the growth time. X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photon spectroscopy (XPS) show that the particles are well crystallized, pure, stoichiometric Mn₃O₄ single crystals of uniform size ranging from about 5 to 12 nm. The variation of their dc-magnetization, M, as a function of the magnetic field, H, and temperature, T, clearly corresponds to ferromagnetic ordering at low temperature, with a Curie temperature slightly higher than 40 K. The evidence for superparamagnetism in these particles, due to their very small size, has been discussed in the light of their M(H) and M(T) for zero-field-cooled (ZFC) and field-cooled (FC) plots.