Paramagnetic and spin-glass properties of pyrochlore-like oxides Ln2Mn2/3Mo4/3O7 (Ln=Sm, Gd, Tb, or Y)

The magnetic properties of complex oxides Ln ₂Mn_2/3Mo_4/3O₇ (Ln=Sm, Gd, Tb, or Y) with a pyrochlore-type structure are studied in the temperature range 2–300 K. For all compounds in the paramagnetic state, the temperature dependence of the magnetic susceptibility is described by a generalized Curie-Weiss law with a temperature-independent component of ∼10⁻⁶ cm³/g and with a Weiss constant Θ<0 and |Θ|<16 K. At low temperatures (T<10–12 K), the compounds have spin-glass properties; they exhibit magnetic and temperature hysteresis and the typical dependences of the imaginary and real parts of the dynamic magnetic susceptibility on temperature and the frequency of an ac magnetic field in a wide range of magnetization relaxation times. The data obtained suggest that d electrons are responsible for the formation of frustrated exchange interactions in the compounds and that 4f electrons in the compounds with Sm or Tb provide strong magnetic-anisotropy effects. __________ Translated from Fizika Tverdogo Tela, Vol. 46, No. 2, 2004, pp. 287–295. Original Russian Text Copyright ? 2004 by Korolev, Bazuev.     

Magnetic Properties of Iron Clusters in Silver

Time differential perturbed γ-γ angular correlation technique was used to measure the magnetic hyperfine field (MHF) at Tb sites in the intermetallic compound Tb₃In₅ using the ¹⁴⁰La → ¹⁴⁰Ce nuclear probe. The measurements were carried out in the temperature range of 8 to 295 K. Two different temperature dependent magnetic frequencies were observed below 30 K, which were assigned as ¹⁴⁰Ce substituting the two inequivalent Tb sites in the orthorhombic structure of Tb₃In₅. The temperature dependence of MHF also shows a possible deviation from an expected Brillouin-like behavior for temperatures below 18 K. A Néel transition at 27 K was observed from magnetization measurements in the samples. The magnetization as a function of the applied magnetic field was measured at two temperatures, 5 and 40 K, and the results show antiferromagnetic and a typical paramagnetic behavior, respectively. In both cases it was not observed saturation under high magnetic field.     

Magnetic moment measurements of picosecond states: New results and open problems

The temperature dependence of the precession of the angular correlation of decay gamma rays from swift¹⁵⁰Sm (2 ₁ ⁺ ) ions traversing a gadolinium foil has been found to be proportional to the foil magnetization, supporting the assertion that the transient hyperfine magnetic field acting on these ions is proportional to the magnetization of the hosts (iron or gadolinium). Similar experiments on¹⁹⁴Pt (2 ₁ ⁺ ) ions traversing iron and gadolinium foils are consistent with both the magnetic moment obtained from Rutgers experiments on iron and with a hyperfine field at Pt ions larger for gadolinium than for iron foils, in agreement with the Chalk River parametrization for heavy nuclei traversing gadolinium foils. Finally, the magnetic moments of the 2 ₁ ⁺ states in^144–150Nd,^145,150Sm and¹⁵²Gd have been measured. These data support the evidence of shell closure atZ=64 forN≤88 andZ=50 forN>90.     

Magnetic behaviour of Tb impurities in Gd andY single crystals: a nuclear orientation study

The low temperature nuclear orientation of¹⁶⁰Tb impurities in Gd andY single crystals has been studied in the temperature range 7–40 mK andin the external magnetic field range 0–7.3 T applied alonga-, b- andc-crystal axes. In the case of Tb in Gd we found a considerable noncollinearity of the Tb magnetic moment with respect to the magnetic external field direction even for highB _ext. In the case of Tb in Y the results cannot be described by a simple model, taking into account the simultaneous influence of the crystal andexternal magnetic fields. Some new proposals for interpretation of the experimental dat are given.     

Antiferromagnetic resonance and dielectric properties of rare-earth ferroborates in the submillimeter frequency range

The magnetoresonance and dielectric properties of a number of crystals of a new family of multiferroics, namely, rare-earth ferroborates RFe₃(BO₃)₄ (R = Y, Eu, Pr, Tb, Tb_0.25Er_0.75), are studied in the sub-millimeter frequency range (ν = 3–20 cm⁻¹). Ferroborates with R = Y, Tb, and Eu exhibit permittivity jumps at temperatures of 375, 198, and 58 K, respectively, which are caused by the R32 → P3₁21 phase transition. Antiferromagnetic resonance (AFMR) modes in the subsystem of Fe³⁺ ions are detected in the range of anti-ferromagnetic ordering (T < T _N = 30–40 K) in all ferroborates that have either an easy-plane (Y, Eu) or easy-axis (Pr, Tb, Tb_0.25Er_0.75) magnetic structure. The AFMR frequencies are found to depend strongly on the magnetic anisotropy of a rare-earth ion and its exchange interaction with the Fe subsystem, which determine the type of magnetic structure and the sign and magnitude of an effective anisotropy constant. The basic parameters of the magnetic interactions in these ferroborates are found, and the magnetoelectric contribution to AFMR is analyzed.     

Magnetic and quadrupole interaction studies at 111Cd in GdMn2 and TbMn2

The temperature dependence of the electric quadrupole interaction and the magnetic hyperfine field at ¹¹¹Cd probe sites in RMn₂ (R=Gd, Tb) has been studied by TDPAC method. In the paramagnetic region the quadrupole interaction frequency ν_Q in both compounds varies linearly with temperature. Below the Neel temperature, we find an abrupt decrease in the magnitude of ν_Q which is consistent with an expansion of the unit cell. As an important feature, the data near T_N shows the coexistence of localized and itinerant magnetism of Mn atoms. This revised version was published online in August 2006 with corrections to the Cover Date.     

Hyperfine field of156Gd in TbFe2, TbFe3, TbCo2 and TbCo3 compounds

Time integral γ-γ angular correlation measurements have been made on¹⁵⁶Gd in Tb-3d metal compounds, TbFe₂, TbFe₃, TbCo₂ and TbCo₃, using two Ge(Li) detetctors. From the observation of a linear relation between magnetic hyperfine fields at Gd and Tb nuclei in corresponding compounds, it is inferred that crystalfield induced variations of the Tb moment are negligible. The experimental results are discussed in terms of the conduction electron polarization caused by the magnetic moment of 3d metals.     

Hydrothermally prepared oxide-ion and Mixed Conductors based on CeO2

The structure, thermal expansion coefficients, electrical and electrochemical properties of Ce_1−xM_xO_2−δ (M=Bi, La, Pr, Eu, Tb; x=0–0.30) solid solutions, prepared hydrothermally for the first time, are surveyed. For all cation substitution a solubility limit depending on the cation size was found. The uniformly small particle size (10–50 nm) of the hydrothermally prepared materials allows sintering of the samples into highly dense ceramic pellets at 1300–1400 °C, a significantly lower temperature, compared to that at 1600–1650 °C required for samples prepared by solid state techniques. X-ray absorption near edge spectroscopy (XANES) was used for the identification of Tb³⁺/Tb⁴⁺ or Pr³⁺/Pr⁴⁺ ions. The maximum of total conductivity in all solid solutions was found for x ∼ 0.15–0.25 with electronic contribution to the total conductivity ∼ 50 % for Tb/Pr substitution and close to zero in all other cases. The conductivity becomes more ionic with decreasing Tb/Pr substitution. The thermal expansion coefficients, determined from high-temperature X-ray diffraction data, are 11.7×10⁻⁶ K⁻¹ for CeO₂ and slowly decrease for Tb and increase for all other cases with increasing substitution. Paper presented at the 7th Euroconference on Ionics, Calcatoggio, Corsica, France, Oct. 1–7, 2000.     

Fluorescent Property of the Gd<Superscript>3+</Superscript>-Doped Terbium Complexes and Crystal Structure of [Tb(TPTZ)(H<Subscript>2</Subscript>O)<Subscript>6</Subscript>]Cl<Subscript>3</Subscript>·3H<Subscript>2</Subscript>O

The complex of Tb(TPTZ)Cl₃·3H₂O was synthesized by adding the ethyl alcohol solution of TbCl₃ (1 mmol) to the solution of 2,4,6-tris-(2-pyridyl)-s-triazine(TPTZ,1 mmol) with constant stirring. The solution which had been filtered was kept at the room temperature for 4 weeks, and then a kind of transparent crystal was formed. Besides, nine kinds of solid complexes in the different molar proportion of terbium to gadolinium had been synthesized by adopting the similar method mentioned above. It was inferred from the elemental analysis and rare earth complexometry that the composition of these complexes is (Tb_xGd_y)(TPTZ)Cl₃·3H₂O (x : y = 0.9 : 0.1, 0.8 : 0.2, 0.7 : 0.3, 0.6 : 0.4, 0.5 : 0.5, 0.4 : 0.6, 0.3 : 0.7, 0.2 : 0.8, 0.1 : 0.9). The absorption spectra and photoluminescence of the complexes were determined in dimethylsulfoxide (DMF), which showed that the excitation of the complexes is mostly ligand based. The triplet state energy level of TPTZ was measured, indicating that the lowest excitation state energy level of Tb(III) and the triplet state energy level of TPTZ match well each other. The fluorescent data indicated that the fluorescent emission intensity of Tb³⁺ ions would be enhanced in the complexes after terbium was doped with Gd³⁺ ion. When x : y was 0.5 : 0.5, the fluorescent emission intensity was the largest. The result obtained by testing the X-ray diffraction of the monocrystal revealed that the molecular formula of the mono-crystal complex is [Tb(TPTZ)(H₂O)₆]Cl₃·3H₂O. The number of metal ion coordinates is nine, and the tridentate TPTZ and six water molecules are bonded with terbium respectively. Besides, it also revealed that the monocrystal belongs to the monoclinic system, and space group Cc with the following unit cell parameters is a = 1.4785 (3) nm, b = 1.0547 (2) nm, c = 1.7385 (4) nm, β = 94.42 (3)°, V = 2.7028 (9) nm³ and Z = 4.     

The 2<Superscript>1/3</Superscript> rule for magnetic susceptibility of gadolinium

The dependences of the magnetization M and the magnetic susceptibility χ = ∂M/∂H of pure gadolinium (the concentration of foreign impurities is lower than 0.1 wt %) on the temperature T and the magnetic field H have been measured using a Quantum Design MPMS-5XL SQUID magnetometer. In this material, inhomogeneities of the atomic structure should not lead to a nonuniform distribution of the magnetic characteristics (including the Curie temperature T _C) over the volume of the sample. The obtained dependences of M and χ have been used to investigate the possibility of suppressing magnetic inhomogeneities of other types by magnetic fields with a strength of up to 50 kOe. It has been assumed that these inhomogeneities are suppressed when the specific relationship, namely, the 2^1/3 rule is fulfilled. The rule relates the portions of the dependence χ(T, H) which at the temperature T = T _C and at the maximum in the curve χ(T) (T = T _m ) depend on H in accordance with the H ^2/3 law. It has been shown that the portions separated from the experimental curves χ(T _C, H) and χ(T _m , H) obey the 2^1/3 rule.     

Improvement to the exchange field acting upon Tb ions in TbIG

The spin fluctuations of the magnetic ions play an important role on the magnetic properties of the crystals and lead to a new mechanism for the Curie-Weiss susceptibility. The exchange field H_exch acting on the rare-earth ions in Tb:YIG is improved based on the temperature dependence of the spin fluctuations, which is expressed as H_exch=n₀(1+γT+βT⁻²)M_YIG. By means of the improved exchange field, the magnetic and magneto-optical properties of Tb³⁺ ions in Tb:YIG are calculated. The calculated results are in good agreement with the measured data in the temperature range from 40 to 300 K.     

Magnetic twisted state of Fe/Tb multilayers

The information of the Fe and Tb magnetic moments in [Fe(12 nm)/Tb(15 nm)]₂₅ multilayer was got separately with X-ray magnetic circular dichroism (XMCD) measurements at various temperature. The Tb magnetic moments become to twist with increasing the applied magnetic field, as follows. (1) When the applied field H is less than the coercive force H_C, Fe and Tb magnetic moments align anti-parallel, Fe moments being parallel to the magnetic field. This would be due to the ordinary exchange coupling between Fe and Tb magnetic moments. (2) H>H_C, a twisted magnetic structure appears when the sample temperature is low, particularly lower than 150 K. This magnetic phase could come from the competition among the exchange coupling, the Zeeman energy and the anisotropic energy.     

Syntheses and Fluorescence Properties of Two Novel Lanthanide (III) Perchlorate Complexes with Bis(benzylsulfinyl)methane

A novel ligand with double sulfinyl groups, bis(benzylsulfinyl)methane, was synthesized by a new method and its two lanthanide (III) complexes were synthesized and characterized by element analysis, molar conductivity, coordination titration analysis, IR, TG-DSC, ¹HNMR and UV spectra. The results indicated that the composition of these complexes was REL_2.5(ClO₄)₃·3H₂O (RE = Tb (III), Dy (III), L = C₆H₅CH₂SOCH₂SOCH₂C₆H₅). The FT-IR results revealed that the perchlorate group was bonded with the lanthanide ion by the oxygen atoms, and the coordination was bidentate. The fluorescent spectra illustrated that both the Tb (III) and Dy (III) complexes displayed characteristic fluorescence in solid state, especially for the Tb (III) complex, the peak of ⁵D₄ → ⁷ F₅ of the Tb (III) ion in 544 nm was stronger than that of others. It indicated that the Tb (III) complex could emit purer green fluorescence. By analysis fluorescence and phosphorescence spectra, it was found that the ligand had the advantage to absorb energy and transfer it to the Tb (III) and Dy (III) ions. The phosphorescence spectra and fluorescence lifetimes of the complexes were also measured.     

Spin and temperature dependence of the magnetic hyperfine field of Cd in the rare earth-aluminum Lavesphase compounds RAl2

Perturbed angular correlation spectroscopy has been used to investigate the combined magnetic and electric hyperfine interaction of the probe nucleus ¹¹¹Cd in ferromagnetically ordered rare earth (R)-dialuminides RAl₂ as a function of temperature for the rare earth constituents R=Pr, Nd, Sm, Eu, Tb, Dy, Ho and Er. In compounds with two magnetically non-equivalent Al sites (R=Sm, Tb, Ho, Er), the magnetic hyperfine field was found to be strongly anisotropic. This anisotropy is much greater than the anisotropic dipolar fields, suggesting a contribution of the anisotropic 4f-electron density to magnetic hyperfine field at the closed-shell probe nucleus. The spin dependence of the magnetic hyperfine field reflects a decrease of the effective exchange parameter of the indirect coupling with increasing R atomic number. For the compounds with the R constituents R=Pr, Nd, Tb, Dy and Ho the parameters B₄, B₆ of the interaction of the crystal field interaction have been determined from the temperature dependence of the magnetic hyperfine field. The ¹¹¹Cd PAC spectrum of EuAl₂ at 9 K confirms the antiferromagnetic structure of this compound.     

Magnetization studies of TbFeO3

The spontaneous magnetization and principal magnetic susceptibilities of TbFeO₃ were measured from 4.2 to 300 K. The weak ferromagnetic moment is along the c crystallographic axis in the entire temperature range. The field dependence of the magnetization at 4.2 K was also studied. The magnetic behavior is interpreted in terms of an interaction between the ordered Fe³⁺ spin system and the electrons occupying the lowest lying “accidental” doublet of the Tb³⁺ ions. The FeTb interaction and the Tb³⁺ Van Vl eck susceptibility along the c axis play significant roles in determining the magnetic configuration of the Fe³⁺ spin system. No indication was found that the TbTb interaction plays a significant role in the magnetic behavior of TbFeO₃ at temperature above 4.2 K.     

Nanocrystalline GdAlO3: XPS,EPR and magnetic susceptibility studies

Nanocrystalline gadolinium monoaluminate (GdAlO₃) has been synthesized by sol–gel method after sintering the precursor gel at 950°C. The microstructural features have been proved by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and energy-dispersive X-ray analysis (EDX). The XRD pattern confirms the formation of single-phase GdAlO₃ while EDX shows that this nanomaterial is stoichiometric; the average size of the nanoparticles is 40 nm. X-ray photoelectron spectroscopy (XPS) has been used to study the chemical composition and bonding in the as-prepared samples. The binding energies of core-level electrons in Gd, Al and O in GdAlO₃ nanopowder have been found slightly shifted compared to the corresponding values of the same elements. The electron paramagnetic resonance (EPR) spectra at 9.23 GHz (X-band) and different temperatures indicate the existence of magnetically concentrated solid containing Gd³⁺ ions. Nèel temperature, T _N =3.993 K, effective Bohr magneton number, μ _eff=8.18, and constant of magnetic exchange interaction, J _ex=−0.069 cm⁻¹, have been determined from DC magnetic susceptibilities measured in the range 2–300 K.     

Influence of gadolinium concentration on the EMR spectrum of Gd in zircon

Electron magnetic resonance (EMR) spectra of gadolinium-doped zircon (ZrSiO₄) powders have been studied at room temperature for gadolinium concentrations between 0.20 and 1.0 mol%. The results suggest that Gd³⁺ ions occupy substitutional sites in the zircon lattice, that the electron magnetic resonance linewidth increases with increasing gadolinium concentration and that the range of the exchange interaction between Gd³⁺ ions is about 1.17 nm, larger than that of the same ion in other host lattices, such as ceria (CeO₂), strontium oxide (SrO) and calcium oxide (CaO). The fact that the electron magnetic resonance linewidth of the Gd³⁺ ion in polycrystalline zircon increases, regularly and predictably, with Gd concentration, shows that the Gd³⁺ ion can be used as a probe to study, rapidly and non-destructively, the crystallinity and degradation of ZrSiO₄.     

Nuclear orientation study of160Tb impurity in yttrium single crystal

The low temperature nuclear orientation of¹⁶⁰Tb impurity in yttrium single crystal has been studied in the temperature range 5–60 mK and in the external magnetic field up to 9 T applied along a- or c-crystal axes. The experimental results are interpreted as a consequence of the interaction of Tb³⁺ ion with crystal field produced by the yttrium neighbours. A possible influence of technology used is also discussed.     

Magnetic and crystalline properties of GdxLa1−x FeSi compounds

The magnetic and crystalline properties of the polycrystalline compounds Gd_xLa_1−x FeSi (x=0, 0.1, 0.3, 0.45, 0.55, 0.65, 0.8, 1) and single crystal GdFeSi are studied. All the compounds have the CeFeSi tetragonal structure. The temperature dependences of the magnetization and initial susceptibility show that ferromagnetic behavior is characteristic of these compounds; the exception is the Pauli paramagnetic LaFeSi. Substitution of gadolinium by the nonmagnetic lanthanum leads to a sharp drop in the Curie temperature T _c, and to a reduction in the saturation magnetic moment μ ₀, effective magnetic moment μ _eff, and paramagnetic Curie temperature Θ_p. Measurements on single crystal GdFeSi imply that the easy magnetization axis of this compound is the c axis and the anisotropy field is H _a∼4 kOe. No magnetic moment was observed on the iron ion in any of these compounds. Fiz. Tverd. Tela (St. Petersburg) 39, 325–329 (February 1997)