Analysis of the structure and magnetic properties of an interface in multilayered (Fe/Si) N nanostructures with the surface-sensitive XMCD method

The structural and magnetic properties of (Fe/Si) _N nanostructures obtained by successive deposition on the SiO₂/Si(100) surface at a temperature of the substrate of 300 K have been studied. The thicknesses of all Fe and Si layers have been determined by transmission electron microscopy measurements. The magnetic properties have been studied by the X-ray magnetic circular dichroism (XMCD) method near the Fe L _{3, 2} absorption edges. The orbital (m _l ) and spin (m _S ) contributions to the total magnetic moment of iron have been separated. The thicknesses of magnetic and nonmagnetic iron silicide on the Si/Fe and Fe/Si interfaces have been determined with the surface sensitivity of the XMCD method and the model of the interface between the nonmagnetic and weakened magnetic phases.     

Valence states of iron ions in nanostructured yttrium iron garnet Y3Fe5O12 studied by means of soft X-ray absorption spectroscopy

Nanostructured samples of yttrium iron garnet Y₃Fe₅O₁₂ obtained by plastic deformation method (high-pressure torsion) were studied with help of soft X-ray absorption spectroscopy using Fe 2p and O 1s spectra. Experimental spectra were compared with crystal field multiplet calculations for Fe ions. Some amount of Fe²⁺ ions in nanostructured Y₃Fe₅O₁₂ was found. The concentration of Fe²⁺ ions was found to be increased with the increase of the degree of plastic deformation.     

利用X射线磁性圆二色吸收谱计算3d过渡族磁性原子的轨道和自旋磁矩

在4个方面研究了实验数据的预处理和应用加和定则中的问题.1)外磁场对样品电流法测量的吸收谱强度的影响.发现外磁场H<200×10^-4T时，信号强度正比于H^-β；当H>200×10^-4T时，尽管外磁场继续增加，但信号强度基本保持不变.2)不同方向的电磁铁剩磁会导致吸收谱的分离.这种分离与入射光的偏振态和样品的磁性无关，可以通过乘以一个常数很好地消除这种分离.3)通过XPSPEAK 4.1对实验数据拟合，写出了吸收谱的解析函数.利用解析函数的积分值，建立一种相对“客观"的标准，判断在一定的实验条件下，不同的数值积分方法的准确性.4)以误差函数作为吸收谱的背景函数，建立了一套完整的X射线磁性圆二色的数据处理方法.最后用Bode积分法计算出20nm厚Co膜的轨道和自旋磁矩分别为0.141μ_B和1.314μ_B. 关键词： X射线磁性圆二色 加和定则 台阶函数 吸收谱拟合     

Application of X-ray absorption spectroscopy to the investigation of charge states of iron ions in iron borate nanoceramics

The method of X-ray absorption spectroscopy has been used for the investigation of charge states of iron ions in iron borate nanoceramics prepared by shear deformation under pressure. The experimental Fe 2p X-ray absorption spectra have been presented in comparison with the calculation of atomic multiplets of iron ions taking into account the charge transfer from the 2p orbitals of oxygen to the 3d orbitals of iron and the crystal-field splitting of the 3d orbitals of iron. Our results indicate that, in addition to iron ions in the ground charge state Fe³⁺, nanostructured FeBO₃ contains a few percent of Fe²⁺ ions. It has been found that an increase in the degree of plastic deformation (the rotation angle of the anvils) leads to a decrease in the size of crystallites and to an increase in the concentration of Fe²⁺ ions without the formation of new phases. The results of this work agree with the magnetic and optical measurements and confirm high defectness of FeBO₃ nanoceramics.     

Inner shell electron energy loss spectra of the methyl amines and ammonia

Electron energy loss Spectroscopy has been used to obtain the inner shell excitation spectra of the methyl amines CH₃NH₂, (CH₃)₂NH and (CH₃)₃N for both the N 1s and C 1s regions. A spectrum of the N 1s region of NH₃ is also presented at higher resolution than previously published data. The C ls spectra are all very similar and the discrete portions may be assigned to Rydberg transitions. However, features attributable to a σ^* shape resonance are observed just above the N 1s and C ls ionization edges. The NH₃ spectrum is ascribed to Rydberg transitions. The N 1s spectra of the methyl amines, however, become increasingly dominated by a σ* resonance in the continuum with increased methylation. The features in the inner-shell spectra are compared with the reported valence-shell optical absorption spectra and support the Rydberg assignment. The inner-shell spectra of (CH₃)₃N and NH₃ are also compared with previously published inner shell electron energy loss spectra of NF₃ and the third row phosphorus analogues PF₃,P(CH₃)₃andPH₃.     

On the magnetic properties of Y(FexCo1-x)2 compounds

The composition dependence of the mean magnetic moment of cobalt atoms in Y(Fe_xCo_1-x)₂ compounds is analysed in the local environment model. Cobalt has a magnetic moment of 1.56 μ_B if there are at least two Fe atoms as nearest neighbours. The maximum in the composition dependence of the transition metal moments is due to the magnetic contributions of iron atoms only. The thermal variation of reciprocal susceptibility obeys a Curie-Weiss behaviour, in addition to the Pauli paramagnetic term. Finally, the influence of the variable magnetic interactions on the transition metal moments is discussed.     

The magnetic moments of (vg 9/2)-levels in odd Zn isotopes

^69m,71mZn have been implanted with an isotope separator on-line into a cold iron host matrix. Nuclear magnetic resonance of the low-temperature oriented isotopes has been observed. The resonance frequencies for zero external magnetic field are v_L(^69mZnFe@#@) =36.814(35) MHz andv _L (^71mZnFe)=33.47(19) MHz. From these the magnetic moments of the 9/2⁺ iosmeric states have been derived as μ(^69mZn)=(?)1.138(18) n.m. andμ(^71mZn)=(?)1.035(18) n.m. The experimentally known magnetic moments of (vg _9/2)-levels in odd zinc isotopes are compared to theoretical estimates.     

Depth-selective conversion-electron Mössbauer spectroscopy of the surface of Ba-M hexaferrite single crystals

The magnetic properties of a 50-to 2-nm-thick surface layer in hexagonal ferrite BaFe₁₂O₁₉ single crystals are investigated for the first time. Measurements are made on a conversion-electron Mössbauer spectrometer constructed on the basis of a unique ultrahigh-vacuum magnetostatic electron analyzer of the “orange” type. An analysis of the experimental Mössbauer spectra obtained from the surface layer of BaFe₁₂O₁₉ 50-to 2-nm-thick single crystals reveals that (1) the spectral line widths are close to the natural widths of Mössbauer lines and neither changes nor a set of the values of effective magnetic fields, as well as a paramagnetic state of iron ions, could appear due to a defect such as the “surface,” and (2) the experimental spectra are best described only under the assumption that the surface of a hexaferrite BaFe₁₂O₁₉ single crystal contains a 2-nm-thick layer, in which the magnetic moments of iron ions are deflected through ～20° from the crystallographic C axis along which the magnetic moments of ions located in the bulk of the crystal are oriented.     

Ground state of BaCoS2 as a set of energy-degenerate orbital-ordered configurations of Co2+ ions

The linear muffin-tin orbital method in the local density approximation (LDA + U) explicitly considering Coulomb correlations has been applied to calculate the electronic structure, magnetic moments, and parameters of the Heisenberg exchange interaction for cobalt ions in BaCoS₂. Five solutions close in total energy with various orbital ordering of Co²⁺ ions and almost identical spin magnetic moments μ = 2.32μ_B of the Co²⁺ ion 3d-shell have been found. The BaCoS₂ ground state can be considered as a set of energy-degenerate orbital-ordered configurations of Co²⁺ ions in the high-spin state.     

EPR and magnetic susceptibility studies of iron ions in ZnO-Fe2O3-SiO2-CaO-P2O5-Na2O glasses

Room temperature electron paramagnetic resonance (EPR) spectra and temperature dependent magnetic susceptibility data have been obtained on bulk x(ZnO,Fe₂O₃)(65−x)SiO₂20(CaO, P₂O₅)15Na₂O (6≤x≤21 mole%) glasses prepared by melt quenching method. EPR spectra of the glasses revealed absorptions centered at g≈2.1 and 4.3. The variations of the intensity and line width of these absorption lines with composition have been interpreted in terms of the variation in the concentration of the Fe²⁺ and Fe³⁺ ions in the glass and the interaction between the iron ions. EPR and magnetic susceptibility data of the glasses reveal that both Fe²⁺ and Fe³⁺ ions are present in the glasses, with their relative concentration being dependent on the glass composition. The studies reveal superexchange type interactions in these glasses, which are strongly dependent on their iron content.     

Crystal structure and electronic states of Co and Gd ions in a Gd<Subscript>0.4</Subscript>Sr<Subscript>0.6</Subscript>CoO<Subscript>2.85</Subscript> single crystal

X-ray diffraction and X-ray absorption near edge structure (XANES) spectra have been measured at the Со K-edge and Gd L ₃-edge in GdCoO₃ and Gd_0.4Sr_0.6CoO_2.85 cobaltites. The effect of Sr substitution on the crystal structure and electronic and magnetic states of Co³⁺ ions in a Gd_0.4Sr_0.6CoO_2.85 single crystal has been analyzed. The XANES measurements at the Co K-edge have not showed a noticeable shift of the absorption edge with an increase in the concentration of Sr. This indicates that the effective valence of cobalt does not change. An increase in the intensity of absorption at the Gd L ₃-edge is due to an increase in the degree of hybridization of the Gd(5d) and O(2p) states. The effect of hole doping on the magnetic properties results in the appearance of the ferromagnetic component and in a significant increase in the magnetic moment.     

Spin crossover in the magnetic phase transition in YBa2(Cu1−x Fex)3O7±δ superconductors

All iron ions in the Cu1 and Cu2 local lattice sites of the YBa₂(Cu_0.9 ⁵⁷Fe_0.1)₃O_7.01 superconductor with T _c=31 K experienced magnetic ordering below T _m=22 K. Therefore, at T < T _m, magnetic ordering coexisted with superconductivity. According to the Mössbauer spectroscopy data, iron ions in Cu2 (Fe2) sites were in the low-spin state at T < T _m(S= 3/2 or 1/2), whereas an equal number of iron ions in Cu1 (Fe1) sites were in the high-spin Fe³⁺ state (S=5/2). The magnetic transition near T _m changed iron ion spin states-low-spin ions turned into high-spin ions, and vice versa. This preserved the spin balance between iron ions in the Cu1 and Cu2 layers. Control measurements on other samples of the YBa₂(Cu_{1? x} Fe_x)₃O_7±δ series substantiated these conclusions.     

Coexistence of long range magnetic order and intervalent state of Eu in EuCu2(Si x Ge1 − x )2: Evidence from neutron diffraction and spectroscopic studies

Experimental results of the X-ray absorption spectroscopy, Mössbauer spectroscopy (isomer shift) and neutron diffraction are presented for the series of EuCu₂(Si _x Ge_{1 ? x} )₂ polycrystalline samples (0 < x < 0.75). Homogeneous intermediate valence state is established for Eu ions as well as long range magnetically ordered state at the temperatures below 10–15 K. Observation of the ordered magnetic moments at Eu site gives rise to the experimental statement for the coexistence of valence fluctuations and long range magnetic order takes place in the wide range of Ge concentrations for this substance.     

EPR and magnetic properties of MgO-CaO-SiO2-P2O5-CaF2-Fe2O3 glass-ceramics

Glass-ceramics have been derived from 4.5MgO(45−x)CaO34SiO₂16P₂O₅0.5CaF₂xFe₂O₃ (x=5, 10, 15, 20 wt%) glasses by heat treatment. Room temperature electron paramagnetic resonance (EPR) spectra and temperature-dependent magnetic susceptibility (χ) of the glass-ceramics have been obtained. The EPR absorption line centered at g≈4.3 disappeared at higher concentrations of iron oxide. The intensity and line width of the EPR absorption line centered at g≈2.1 increased as the iron oxide concentration was increased. Temperature-dependent magnetization of samples with low iron oxide content revealed ferrimagnetic as well as paramagnetic contributions. Information about the structural changes involving iron ions, their valence state and the type of magnetic interactions between the Fe ions as a function of composition was obtained using EPR and χ studies.     

Superhyperfine structure in the EPR spectra and optical spectra of impurity f ions in dielectric crystals: A review

The results of observation and simulation of the superhyperfine (ligand hyperfine) structure (SHFS) of the electron paramagnetic resonance (EPR) spectra of rare-earth and uranium impurity ions in dielectric crystals have been systematized. The resolved SHFS of the EPR spectra of doped cubic crystals (with the fluorite and perovskite structures) has been observed for orientations of a constant magnetic field along the crystallographic axes. Most attention has been paid to tetragonal double fluorides LiRF₄ (R = Y, Lu, Tm), in which the SHFS of the EPR spectra has also been found for intermediate orientations of the magnetic field. For the LiYF₄: Nd³⁺ single crystal, the splitting of optical spectral lines due to the interaction of Nd³⁺ ions with nuclear magnetic moments of the nearest neighbor fluorine ions has been observed for the first time. The Van Vleck paramagnet LiTmF₄: U³⁺ is characterized by the SHFS with clearly distinguishable components due to the interaction of uranium ions both with nuclei of the fluorine ions and with enhanced magnetic moments of the thulium nuclei. The SHFS envelopes of the EPR spectra of Yb³⁺, Ce³⁺, Nd³⁺, and U³⁺ ions in LiYF₄ and LiLuF₄ crystals are well reproduced by numerical calculations based on the microscopic model using only three fitting parameters: the width of transitions between the electron-nuclear sublevels of the complex containing the paramagnetic ion and nuclei of the ligands and two constants of covalent bonding of the f electrons with 2s and 2p electrons of the nearest neighbor fluorine ions.     

Investigations of the magnetic structure of the surface and volume of aluminum-substituted Sr-M type hexaferrites

The magnetic structure of the surface layer of single crystals of hexagonal ferrites of the type Sr-M (SrFe₁₂O₁₉) in which some iron ions are replaced by diamagnetic Al ions is investigated, in direct comparison with the magnetic structure in the bulk of the sample, by the method of simultaneous gamma, x-ray, and electron Mössbauer spectroscopy. It is found that under conditions of diamagnetic dilution of the magnetic lattice of hexagonal ferrites of the type Sr-M by Al ions, a layer ~200 nm thick in which the orientation of the magnetic moments is not collinear with the direction of the moments in the bulk of the sample is observed on the surface of SrFe_10.2Al_1.8O₁₉ crystals. Thus a “transitional” surface layer has been observed on macroscopic ferromagnetic crystals.     

Neutron scattering length of terbium structure refinement and magnetic moments of terbium iron garnet

The neutron scattering length of terbium was redetermined from powder data on terbium iron garnet (TbIG) and TbO₂ by the profile analysis technique. The mean value obtained is b (Tb) = 0.735(10) x 10^?12cm. Furthermore the positional and thermal parameters of TbIG have been refined from single crystal X-ray and neutron powder data. The results from both experiments agree well. The X-ray data from a sphere of diameter φ = 282μm were collected by MoKα radiation. The refinement was carried out including an extinction parameter which was also applied to correct for anomalous transmission. The powder data were treated by the profile analysis technique where the structural parameters and the magnetic moments were refined simultaneously. Two slightly different form factor curves were applied for Fe³⁺ in the crystallographic sites. The magnetic moments for the iron ions were found to be μ = 3.69(10)μ_B for the octahedral and 3.65(10)μ_B for the tetrahedral site at room temperature. The moment for terbium is μ = 1.15(09)μ_B and the whole magnetisation for one formula unit is 0.12(0.40)μ_B. The observed moments of Fe³⁺ are considerably reduced as compared to the free ion spin only value which was calculated from a Brillouin function for $\text{S =}\text{5}\text{2}$ to be 4.34μ_Bat 300 K.     

Study on magnetic properties of nanocrystalline La-, Nd-, or Gd-substituted Ni–Mn ferrite at low temperatures

The effects of rare-earth ions with different radii and magnetic moments on the magnetic properties of Ni–Mn ferrite are investigated. X-ray diffraction pattern has shown the presence of cubic structure of spinel ferrite for all samples. The values of M_s and H_c are decreasing with increasing of testing temperatures for all samples. The H_c value of Ni_0.7Mn_0.3La_0.1Fe_1.9O₄ reaches 1082 Oe at 2 K. Mössbauer spectra tested at 273 K indicate the presence of superparamagnetism for samples calcined at 873 K.     

Mn3<Emphasis Type="Italic">s</Emphasis> X-ray photoelectron spectra of polynuclear trimethylacetate complexes of manganese

The Mn3s X-ray photoelectron spectra of manganese at oms in mono-, bi-, tri-, and hexanuclear trimethylacetate Mn complexes and Mn^IICl₂, Mn^IIIOOH, Mn^IVO₂. ionic compounds were measured. The 3s spectra of the manganese atoms in Mn^II, Mn^III, and Mn^IV valent states were calculated within the isolatedion approximation. The relationship between the characteristics of the Mn3s spectra and the magnetic moments of the manganese ions in the complexes is discussed.     

X-ray-line plasma satellites of ions in solid target plasmas produced by picosecond laser pulse

The X-ray lines of ions in a solid target interacting with picosecond laser pulses of moderate intensity (2×10¹⁷ W/cm²) were measured on the “Neodim” laser facility. X-ray Ly _α emission spectra of hydrogen-like fluorine ions were observed. Satellite lines were also observed, evidencing the presence of intense plasma oscillations. The positions and separation between the satellites allow their assignment to the intense electrostatic oscillations with an amplitude larger than 10⁸ V/cm and a frequency of about 7× 10¹⁴ s^?1 that is noticeably lower than the laser frequency ω_las～1.8×10¹⁵ s^?1. It is suggested that these oscillations may be due to strong plasma turbulence caused by the development of plasma oscillations of the Bernstein-mode type under the action of a strong magnetic field generated in plasma. The experimental results are compared with the calculated spectra of multicharged ions.