Neutron diffraction studies of Tb2Rh3Si5 compound

In this work neutron diffraction studies of Tb₂Rh₃Si₅ compound are reported. The compound crystallizes in the monoclinic crystal structure of Lu₂Co₃Si₅-type. At 1.5 K an antiferromagnetic ordering with a propagation vector k=(1/2;1/2;1/2) was observed. The Tb magnetic moments of 9.8(2) μ_B form a non-collinear magnetic structure. In the vicinity of Néel temperature of 8 K a change of the magnetic ordering is evidenced. The change seems to be connected with phase transition from commensurate to incommensurate sine-wave modulation of the Tb magnetic moments.     

Possible anisotropy gap in La1.35Sr1.65Mn2O7 and La1.5Sr0.5NiO4 detected through specific heat and magnetization measurements

Magnetization and specific heat measurements, as a function of temperature, were performed on single crystals of La_1.35Sr_1.65Mn₂O₇ and La_1.5Sr_0.5NiO₄, under different applied magnetic fields (H). The specific heat in La_1.35Sr_1.65Mn₂O₇ was decreased for H=9 T parallel to the crystal c axis, compared with H=0, possibly due to a suppression of spin-wave excitations (magnons) in that ferromagnetic bilayer structure. On the other hand, the applied magnetic field had no effect in the specific heat of the antiferromagnetic La_1.5Sr_0.5NiO₄. For H=9 T and below the temperature of 4 K the specific heat data, for each crystal, was well fitted by an exponential decay law. This allowed the calculation of energy gaps around 1 meV for both compounds, in close agreement with Δ=2μ_BH for an expected energy gap in the magnon spectrum. Detailed magnetization measurements showed monotonic variations below 4 K and a steep increase close to 2 K. Both magnetization and specific heat measurements suggest the existence of an anisotropy gap in the energy spectrum of La_1.35Sr_1.65Mn₂O₇ and La_1.5Sr_0.5NiO₄.     

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).     

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.     

Valence fluctuation in Ce2Co3Ge5 and crystal field effect in Pr2Co3Ge5

Polycrystalline samples of ternary rare-earth germanides R₂Co₃Ge₅ (R=La, Ce and Pr) have been prepared and investigated by means of magnetic susceptibility, isothermal magnetization, electrical resistivity and specific heat measurements. All these compounds crystallize in orthorhombic U₂Co₃Si₅ structure (space group Ibam). No evidence of magnetic or superconducting transition is observed in any of these compounds down to 2 K. The unit cell volume of Ce₂Co₃Ge₅ deviates from the expected lanthanide contraction, indicating non trivalent state of Ce ions in this compound. The reduced value of effective moment (μ_eff≈0.95 μ_B) compared to that expected for trivalent Ce ions further supports valence-fluctuating nature of Ce in Ce₂Co₃Ge₅. The observed temperature dependence of magnetic susceptibility is consistent with the ionic interconfiguration fluctuation (ICF) model. Although no sharp anomaly due to a phase transition is seen, a broad Schottky-type anomaly is observed in the magnetic part of specific heat of Pr₂Co₃Ge₅. An analysis of C_mag data suggests a singlet ground state in Pr₂Co₃Ge₅ separated from the singlet first excited state by 22 K and a doublet second excited state at 73 K.     

Crystal and magnetic structure of Ho2NiGe6

The crystal and magnetic structure of Ho₂NiGe₆ was studied by powder neutron diffraction. The paramagnetic neutron diffraction data confirmed the Ce₂CuGe₆-type crystal structure reported earlier for this compound. Below the Néel temperature equal to 11 K the Ho magnetic moments form a uniaxial antiferromagnetic ordering. The Ho magnetic moments equal to 8.16(7)μ_B at 1.5 K are parallel to the b-axis. The data are compared with those published for HoNi_0.46(6)Ge₂.     

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.     

Antiferromagnetic phase transition in garnet-type AgCa2Co2V3O12 and AgCa2Ni2V3O12

Antiferromagnetic phase transition in two vanadium garnets AgCa₂Co₂V₃O₁₂ and AgCa₂Ni₂V₃O₁₂ has been found and investigated extensively. The heat capacity exhibits sharp peak due to the antiferromagnetic order with the Néel temperature T_N=6.39 K for AgCa₂Co₂V₃O₁₂ and 7.21 K for AgCa₂Ni₂V₃O₁₂, respectively. The magnetic susceptibilities exhibit broad maximum, and these T_N correspond to the inflection points of the magnetic susceptibility χ a little lower than T(χ_max). The magnetic entropy changes from zero to 20 K per mol Co²⁺ and Ni²⁺ ions are 5.31 J K⁻¹ mol-Co²⁺-ion⁻¹ and 6.85 J K⁻¹ mol-Ni²⁺-ion⁻¹, indicating S=1/2 for Co²⁺ ion and S=1 for Ni²⁺ ion. The magnetic susceptibility of AgCa₂Ni₂V₃O₁₂ shows the Curie-Weiss behavior between 20 and 350 K with the effective magnetic moment μ_eff=3.23 μ_B Ni²⁺-ion⁻¹ and the Weiss constant θ=−16.4 K (antiferromagnetic sign). Nevertheless, the simple Curie-Weiss law cannot be applicable for AgCa₂Co₂V₃O₁₂. The complex temperature dependence of magnetic susceptibility has been interpreted within the framework of Tanabe-Sugano energy diagram, which is analyzed on the basis of crystalline electric field. The ground state is the spin doublet state ²E(t₂⁶e) and the first excited state is spin quartet state ⁴T₁(t₂⁵e²) which locates extremely close to the ground state. The low spin state S=1/2 for Co²⁺ ion is verified experimentally at least below 20 K which is in agreement with the result of the heat capacity.     

Magnetic structure of the Mn5Si3-type Er5Ge3 compound

The Er₅Ge₃ compound (Mn₅Si₃-type, hP16, P6₃/mcm) at 4 K shows magnetic ordering of the antiferromagnetic type. Its magnetic structure consists of sine modulated collinear magnetic moments of Er that are parallel to the c axis (with a propagation vector k=[0 0 ±0.3]). This corresponds to the magnetic unit cell (a a 10c), the values of the magnetic moment of the Er atoms being, as a general formula, M_z≈M₀ cos [2π(Z–1/4)(1–kZ)], with M₀=9.2(2) μ_B at 4 K.     

Magnetic ordering in CeMnCuSi2

Temperature and field-dependent magnetization measurements on polycrystalline CeMnCuSi₂ reveal that the Mn moments in this compound exhibit ordering with a ferromagnetic (FM) component ordered instead of the previously reported purely antiferromagnetic (AFM) ordering. The FM ordering temperature, T_c, is about 120 K and almost unchanged with external fields up to 50 kOe. Furthermore, an AFM component (such as in a canted spin structure) is observed to be present in this phase, and its orientation is modified rapidly by the external magnetic field. The Ce L₃-edge X-ray absorption result shows that the Ce ions in this compound are nearly trivalent, very similar to that in the heavy fermion system CeCu₂Si₂. Large thermomagnetic irreversibility is observed between the zero-field-cooled (ZFC) and field-cooled (FC) M(T) curves below T_c indicating strong magnetocrystalline anisotropy in the ordered phase. At 5 K, a metamagnetic-type transition is observed to occur at a critical field of about 8 kOe, and this critical field decreases with increasing temperature. The FM ordering of the Mn moments in CeMnCuSi₂ is consistent with the value of the intralayer Mn–Mn distance R^a_Mn–Mn=2.890 Å, which is greater than the critical value 2.865 Å for FM ordering. Finally, a magnetic phase diagram is constructed for CeMnCuSi₂.     

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.     

Magneto-structural correlations in Pr0.15Gd0.85Mn2Ge2

Magneto-structural correlations in Pr_0.15Gd_0.85Mn₂Ge₂ have been studied by synchrotron diffraction in the temperature range between 11 and 300 K. This compound crystallizes in the ThCr₂Si₂-type structure (space group ). The unit cell parameters a and c were determined by Rietveld refinements as a function of temperature. Anomalies in the temperature dependence of the unit cell parameters a and c, the c/a ratio and the unit cell volume V at about 240 and 140 K, which is close to the magnetic phase transition temperatures, indicate a pronounced magneto-structural correlation. Spontaneous volume change and linear magnetostrictions are derived as a function of temperature.     

Magnetic and crystallographic study of Tb0.75Y0.25Co3B2

Tb_0.75Y_0.25Co₃B₂ was studied as a function of temperature by neutron powder diffraction, ac susceptibility and SQUID magnetization measurements. The solid solution, which is of hexagonal symmetry and is paramagnetic at 300 K, undergoes a magnetic Co–Co ordering transition at ∼150 K, and a second magnetic Tb–Tb ordering transition at ∼17 K. The latter induces a spin-reorientation transition, in which the magnetic axis rotates from the c-axis toward the basal plane. The component of the magnetic axis, which is perpendicular to c, leads to a crystal symmetry reduction from hexagonal to monoclinic. The observed magnitude of the magnetic moment of the Tb ion is 1.5 μ_B, unusually small relative to the free ion and parent compound (TbCo₃B₂) values. These magnetic and crystal properties are discussed and compared with what was previously published for the parent compound.     

Magnetic structure of geometrically frustrated compound Co2Cl(OH)3 determined by proton NMR

The magnetic structure of a geometrically frustrated system Co₂Cl(OH)₃ is determined by comparing the observed proton NMR spectrum with numerical calculations based on various magnetic models. The best fit is obtained with a model that the magnetic moments of Co²⁺ ions in the triangular plane are parallel to the principal axis of local crystal field and those of Co²⁺ ions in the kagome lattice plane are randomly disordered in the a-b plane, which nearly bisects the angle between the principal axis of the local field and a line pointing towards the body center of the tetrahedron. The coexistence of the ferromagnetic order in the triangular plane and the random disorder in the kagome plane is consistent with the results of measurements by Zheng et al. However, the magnetic moments of Co²⁺ ions are not directed towards the body center of the tetrahedron as characteristic in the “spin ice” magnetic structure. Furthermore, the Co²⁺ ions in the triangular plane have a smaller magnitude of magnetic moment than those in the kagome plane. Thus, our result suggests that the transition metal compound Co₂Cl(OH)₃ is different from the “spin ice” in magnetic structure, although it is similar to rare-earth pyrochlores in crystal structure.     

Two magnetic phase transitions in quasi-one-dimensional system SrCo2V2O8

Magnetic properties of SrCo₂V ₂O₈ single crystal are investigated by means of ac magnetic susceptibility, dc magnetization and heat capacity measurements. The results show that SrCo₂V ₂O₈ possesses two canted antiferromagnetic transitions at ∼5 and ∼3 K, which is different from isostructural BaCo₂V ₂O₈ with only one antiferromagnetic transition at ∼5 K. We suggest that such different magnetic properties are mainly due to their different structural symmetry.     

Magnetic ordering above room temperature in the sigma-phase of Fe66V34

Magnetic properties of four sigma-phase Fe_100−xV_x samples with 34.4?x?55.1 were investigated by Mössbauer spectroscopy and magnetic measurements in the temperature interval 4.2-300 K. Four magnetic quantities, viz. hyperfine field, Curie temperature, magnetic moment and susceptibility, were determined. The sample containing 34.4 at% V was revealed to exhibit the largest values found up to now for the sigma-phase for average hyperfine field, 〈B〉=12.1 T, average magnetic moment per Fe atom, 〈μ〉=0.89 μ_B, and Curie temperature, T_C=315.3 K. The quantities were shown to be strongly correlated with each other. In particular, T_C is linearly correlated with 〈μ〉 with a slope of 406.5 K/μ_B, as well as 〈B〉 is so correlated with 〈μ〉, yielding 14.3 T/μ_B for the hyperfine coupling constant.     

The large anisotropy of the magnetic and transport properties in the Ba5Co5ClO13 single crystal

In this Letter, the single crystals of Ba₅Co₅ClO₁₃ were grown by the flux method successfully. Their structure, magnetic and transport properties were studied. A large anisotropy of the magnetic and transport properties has been detected in this compound. Below the TN∼108 K, the magnetic susceptibility exhibits an antiferromagnetic peak in χc and an upturn transition in χab. We suggest that this behavior is consistent with the competition of the ferromagnetic (FM) intra-blocks coupling and antiferromagnetic (AFM) inter-blocks coupling in this compound. The temperature dependence of the resistivity displays a hump in ρab and a kink in ρc around TN, suggesting the strong coupling between the transport and magnetic properties. Above and below the transition, the transport properties in ab plane follow the three-dimensional (3D) variable range hopping (VRH) mechanism.     

Magnetic and transport properties of Pr2Pd3Si5

We have investigated the magnetic and transport properties of a new ternary intermetallic compound Pr₂Pd₃Si₅ which forms in U₂Co₃Si₅-type orthorhombic structure (space group Ibam). At low field (0.01 T) magnetic susceptibility exhibits an abrupt increase below 7 K and peaks at 5 K, revealing a magnetic phase transition. The onset of magnetic order is also confirmed by well defined anomalies in the specific heat and electrical resistivity data. Apart from the sharp λ-type anomaly, magnetic part of specific heat also shows a broad Schottky-type hump due to crystal field effect. Magnetoresistance data as a function of temperature exhibits a pronounced peak in paramagnetic state which could be interpreted in terms of crystal field effect and short-range ferromagnetic correlations.     

Magnetic phase diagrams of Ho1−xDyxNi2B2C

We performed the magnetization measurement on Ho_1−xDy_xNi₂B₂C single crystals (x=0.1, 0.2, 0.3, 0.4, and 0.6) with magnetic field applied perpendicular and parallel to the c-axis. But only for the magnetic field perpendicular to the c-axis, the increase of Dy³⁺ concentration affects the magnetically ordered states of HoNi₂B₂C compound and makes the phase diagram more complicated. The antiferromagnetic ordering state attributed to Dy³⁺ sublattice starts to appear from a case of x=0.2 and finally the magnetic phase diagram becomes analogous to that of DyNi₂B₂C as x is increased which is consistent with the neutron scattering result.     

Dopant distribution, oxygen stoichiometry and magnetism of nanoscale Sn0.99Co0.01O2

In recent work, we have shown that chemically synthesized Sn_1−xCo_xO₂ nanoscale powders with x≤0.01 are ferromagnetic at room temperature when prepared by annealing the reaction precipitate in the narrow temperature window of 350-600 ^°C. Combined high resolution x-ray photoelectron spectroscopy (on as-prepared and Ar⁺ ion sputtered samples), x-ray diffraction and magnetometry measurements showed that the Co distribution is more uniform throughout the individual Sn_0.99Co_0.01O₂ particles when prepared at lower annealing temperatures of 350-600 ^°C and this uniform dopant distribution is essential to produce stable high temperature ferromagnetism. However, surface segregation of the dopant atoms in samples annealed at >600 ^°C destroys the room-temperature ferromagnetic behavior and reduces the Curie temperature to <300 K.