X-ray absorption spectroscopic study of mixed valence systems EuCu2Si2, YbCu2Si2 and Sm4Bi3

X-ray absorption spectroscopy technique is employed to determine the valence of the rare earth ions in EuCu₂Si₂, YbCu₂Si₂ and Sm₄Bi₃. In each case, two absorption peaks corresponding to two different valence states of respective rare earth ions have been observed. Low temperature (77 K) study of EuCu₂Si₂ indicates distinct change in the relative intensities of the absorption peaks compared to those registered at room temperature (300 K). It is inferred from the change in the relative intensities that the population of Eu²⁺ in EuCu₂Si₂ decreases at liquid nitrogen temperature compared to Eu³⁺. Conclusions drawn from these results agree well with those reported by others using different experimental techniques. In Sm₄Bi₃, Sm²⁺ and Sm³⁺ are found to occur in the ratio of 3:1.     

Combined Mössbauer and LIII-edge X-ray absorption study of mixed- valent EuPd2Si2 and EuNi2P2

The mean valence of Eu is determined by L_III-edge X-ray absorption (L_III-XA) and ¹⁵¹Eu Mössbauer isomer shift measurementd for the mixed-valent compounds EuPd₂Si₂ and EuNi₂P₂ in the temperature range from 1.7 to 300 K. For EuPd₂Si₂, the behaviour of the satellite line observed in the Mössbauer spectra was investigated in detail. From a comparison of the L_III-Xa and Mössbauer results obtained on identical samples the valence/isomer shift calibration problem as well as possible final-state effects in L_III-XA spectra are discussed.     

Effect of pressure on the electrical resistivity and the thermoelectric power of EuPd2Si2

A continuous valence transition has been found in EuPd₂Si₂ from the measurement of the electrical resistivity and thermoelectric power upto 70 kbar.     

Neutron diffraction study of magnetic ordering in ErMn2Si2, ErMn2Ge2 and ErFe2Si2

Neutron diffraction study of polycrystalline compounds ErMn₂Si₂, ErMn₂Ge₂ and ErFe₂Si₂ was performed in the temperature range between 1.8 and 293 K. All compounds have tetragonal, ThCr₂Si₂-type crystal structure. The antiferromagnetic collinear structure of ErMn₂Si₂ and ErMn₂Ge₂ at both RT and LNT, consists of a sequence + - + - of ferromagnetic layers of Mn atoms. The magnetic moment of an Mn atom (≈2μ_B) is parallel to the c-axist. At low temperatures (LHT and lower), the ferromagnetic ordering within the Er sublattice is observed. The magnetic moment (μ_Er ≈ 9μ_B) is perpendicular to the c-axis. From the temperature dependence of the intensities of the magnetic peaks, the following values for the Curie temperatures were obtained: (10±5) K for ErMn₂Si₂ and (8.5±3) K for ErMn₂Ge₂. For ErFe₂Si₂ a collinear antiferromagnetic structure of the + - - + type was found, the magnetic unit cell consisting of the chemical one, doubled along the c-axis.     

Structural study of the Lu2Si2O7-Sc2Si2O7 system

Different compositions in the Lu₂Si₂O₇-Sc₂Si₂O₇ system have been synthesized following the ceramic method. All XRD patterns are compatible with the thortveitite structure (β-RE₂Si₂O₇ polymorph). Unit cell parameters change linearly with composition, which indicates a complete solid solubility of Sc₂Si₂O₇ in Lu₂Si₂O₇. ²⁹Si MAS NMR spectra show a decrease of the ²⁹Si chemical shift with increasing Sc content. A correlation reported in the literature to predict ²⁹Si chemical shifts in silicates is applied here to obtain the theoretical variation in ²⁹Si chemical shift values in the system Lu₂Si₂O₇-Sc₂Si₂O₇ and the results compare favourably with the values obtained experimentally. The FWHM values of the ²⁹Si MAS NMR curves indicate a random distribution of Lu and Sc in the structure of the intermediate members. Finally, the IR study of the system confirms the solubility of Sc₂Si₂O₇ in Lu₂Si₂O₇, showing the splitting of several modes in the intermediate members and a linear shift of the frequency on going from one end-member to the other.     

Magnetic ordering in NdRh2Si2 and ErRH2Si2

Neutron diffraction and magnetization study of polycrystalline NdRh₂Si₂ and ErRh₂Si₂ was performed in the temperature range from 4.2 to 293 K. Both compounds are of ThCr₂Si₂ type crystal structure and exhibit antiferromagnetic ordering below T_N = 53 K and T_N = 12.8 K respectively. The magnetic structure wave vector is τ = [0, 0, 1].     

Neutron diffraction studies of the magnetic ordering in the rare earth compounds TbNi2Si2, HoCo2Si2 and TbCo2Si2

Neutron diffraction studies and magnetic measurements on the compounds TbNi₂Si₂ (1), HoCo₂Si₂ (2) and TbCo₂Si₂ (3) revealed a collinear antiferromagnetic order below T_N = 10 ± 1 K (1), T_N = 13 ± 1 K (2) and T_N = 30 ± 2 K (3) with the rare earths moments oriented along the c-axis [m₀ = 8.8 ± 0.2 μ_B (1), m₀ = 8.1 ± 0.2 μ_B (2), m₀ = 8.8 ± 0.2 μ_B (3)] and the corresponding wavevector are $\text{k}\text{= [}\text{1}\text{2}\text{1}\text{2}\text{0] (1)}\text{and}\text{k}\text{= [ 0 0 1] (2) (3)}$. The magnetic structure of the compounds HoCo₂Si₂ and TbCo₂Si₂ consists of ferromagnetic layers perpendicular to the c-axis coupled antiferromagnetically (+?+?) while for TbNi₂Si₂ the ordering within (0 0 1) plane is antiferromagnetic and the planes (0 0 1) are indeed decoupled.     

Magnetic structures of PrCO2Si2 and TbCo2Si2 compounds

Neutron diffraction studies of polycrystalline PrCo₂Si₂ and TbCo₂Si₂ compounds were carried out at 4.2 and 293 K. Both samples have collinear antiferromagnetic order below T_N(31(1) and 46(1) K for Pr and Tb compound respectively), with their magnetic moments parallel to the c axis. The ordered magnetic moment values of Pr and Tb at 4.2 K (3.19 and 9.12 μ_B respectively), are close to the saturation value of the free ions. The corresponding magnetic space group P_l4/mnc (Sh⁴¹⁰₁₂₈) is body-anticentered ($\text{k =}\text{111}\text{222}$ refering to P_l cell).     

Neutron diffraction study of RECo2Si2 intermetallics

A neutron diffraction study of polycrystalline RECo₂Si₂ intermetallics (RE = Pr, Nd, Tb, Ho, Er) carried out at liquid helium temperature shows the presence of a collinear antiferromagnetic ordering of +?+? type. Magnetic moment is localized on RE ions only and amounts to the RE³⁺ free ion value. In ErCo₂Si₂ the magnetic moment is normal to the tetragonal unique axis, whereas in the remaining compounds the magnetic moment is aligned along it. Néel points were determined from the temperature dependence of magnetic peak heights.     

金属离子掺杂的Lu2Si2O7的第一性原理研究

焦硅酸镥掺铈(LPS:Ce)具有突出的闪烁性能, 比如高光产额和快衰减, 但晶格中的氧空位会影响其闪烁性能. 本文通过第一性原理方法研究了Li, Na, Mg和Ca在LPS中的稳定性和对氧空位的影响. 结果表明: 在缺氧环境下, 这些离子倾向于占据间隙位, 从而可能抑制氧空位. 分析了杂质离子对LPS电子结构的影响. 关键词： 第一性原理 焦硅酸镥 杂质缺陷     

Neutron diffraction determination of the magnetic structures of NpCo2Si2 and NpCu2Si2

A small polycrystalline ingot sample of NpCo₂Si₂ (weight ≈ 1.5 g) has been studied by neutron diffration between 2 and 160 K on the multi-detector D1B of ILL, Grenoble. At 100 K, the crystal structure is body-centered tetragonal (space group 14/mmm) with a = 3.886 Å and c =9.649 Å. Below T_N = (44 ± 2) K, seven superlattice lines are observed which correspond to a simple tetragonal lattice with lattice constants as above. They are consistent with a type I antiferromagnetic structure of the Np (2a) sublattice, with (001) ferromagnetic sheets coupled antiferromagnetically according to the sequence +-+-. At 6 K, the neptunium moment obtained from the diffracted intensities is: (1.48 ± 0.20)_μuB, and makes an angle 52° ± 15° with the c axis. The cobalt moment is certainly smallet than 0.3_μuB. The Np moment correlates well with the ²³⁷Np hyperfine field deduced from Mos?sbauer spectroscopy; the sublattice magnetization-temoperature curve follows very well the $\text{J=}\text{1}\text{2}$ brillouin curve. The magnetism is therefore probably of lovalized character in this compound. An isomorphous sample of NpCu₂Si₂ (a = 3.990 Å c = 9.920 Å) was shown to be ferromagnetic below (41 ± 2) K, with the Np moment [1.5 ± 0.2)_μuB] aligned along the c axis.     

Superconductivity in CeCu2Si2

Resistivity measurements of CeCu₂Si₂ are carried out under pressures p up to 12 kbars. Unlike polycrystalline samples, no traces of superconductivity have been observed in CeCu₂Si₂ at ambient pressure. When pressure is applied, CeCu₂Si₂ monocrystals become superconducting with anomalously large ratio H_c2(0)/T_c (0) = 34 K0e/K and with the derivative dH_c2/dT(T=T_c) = 140 K0e/K     

X-ray absorption spectroscopic study of a hot pressed MgB2

X-ray near edge absorption spectra (XANES) of boron and oxygen K edge of a hot-pressed MgB₂ (HP2) sample were measured by using synchrotron radiation. The HP2 was produced by annealing a commercial powder of MgB₂ in ambient air under a hydrostatic pressure of 2.0 GPa at 900 °C. No substantial change of the electronic structure in HP2 was observed as indicated in the B K-edge XANES. This sample maintains high superconductivity and enhances the critical current density. The XANES and the XRD combined indicate that both MgO and B₂O₃ in HP2 increase and more B₂O₃ than MgO was produced during the hot-press process. The better connection of the grain in HP2 can be the major cause to increase its critical current density. However, the impurity may also increase the flux pinning and therefore increases the current density.     

Neutron diffraction study of magnetic ordering in PrCu2Si2, PrCu2Ge2, PrFe2Ge2 and NdFe2Ge2

A neutron diffraction study of polycrystalline PrCu₂Si₂ [1], PrCu₂Ge₂ [2], PrFe₂Ge₂ [3] and NdFe₂Ge₂ [4] intermetallics carried out at liquid helium temperature shows the presence of a collinear antiferromagnetic order below T_N = 19 ± 1 K [1], T_N = 16 ± 1 K [2], T_N = 9 ± 1 K [3] and 13 ± 1 K [4]. Magnetic moment, parallel to the c-axis is localized on RE ions only. The magnetic structure of these compounds consists of ferromagnetic layers perpendicular to the c-axis coupled antiferromagnetically with sequence +-+- for PrCu₂Si₂ and PrCu₂Ge₂ and +--+ for PrFe₂Ge₂ and NdFe₂Ge₂. The RE moments amount close to the free ion values for Fe containing compounds but are smaller in those containing Cu suggesting a fairly strong influence of crystal field.     

Valence state of Eu and unit-cell volume anomaly in EuPd2P2

Mössbauer isomer shift and magnetic susceptibility measurements clearly prove the divalent nature of Eu in EuPd₂P₂, a new compound recentlu classified as intermediate valent on grounds of its unit-cell volume anomaly. We explain the relatively small positive deviation in unit-cell volume from the systematic trend in trivalent REPd₂P₂ compounds as a consequence of strong chemical bonding between the divalent Eu ion and the ligands.     

Pressure-induced transition in a heavy fermion YbPd2Si2

We report the results of a room-temperature investigation of the thermoelectric and the dilatometric properties of a heavy fermion system YbPd₂Si₂ (itterbium-palladium-silicon, 1-2-2) at high pressure P up to 22 GPa; YbPd₂Si₂ is a less-studied representative of the RM₂X₂ family (R=Ce, Yb, U; M=transition metal; X=Si, Ge) with the tetragonal ThCr₂Si₂-type structure of the I4/mmm space group. Around P∼6±0.5 GPa, a phase transition in Yb-Pd-Si was registered by the drastic changes in the pressure dependencies of the electrical resistance R, the thermopower (Seebeck effect) S, a temperature difference along a sample ΔT, and a sample's thickness Δx (related to compressibility). Both a nature of the found phase transition and a presumable P-T phase diagram of YbPd₂Si₂ are discussed.     

Optical spectroscopy of Ca3Sc2Si3O12, Ca3Y2Si3O12 and Ca3Lu2Si3O12 doped with Pr

The silicates Ca₃Sc₂Si₃O₁₂, Ca₃Y₂Si₃O₁₂ and Ca₃Lu₂Si₃O₁₂, both undoped and doped with Pr³⁺ ions, have been synthesized by solid-state reaction at high temperature. The luminescence spectroscopy and the excited state dynamics of the materials have been studied upon VUV and X-ray excitation using synchrotron radiation. All doped samples have shown efficient 5d-4f emission upon direct VUV excitation of 5d levels, but only Ca₃Sc₂Si₃O₁₂:Pr³⁺ shows luminescence upon interband VUV or X-ray excitation. The VUV excited emission spectra of Ca₃Y₂Si₃O₁₂:Pr³⁺ and Ca₃Lu₂Si₃O₁₂:Pr³⁺ show features attributed to emission from two distinct sites accommodating the Pr³⁺ dopant. The decay kinetics of the Pr³⁺ 5d-4f emission in Ca₃Sc₂Si₃O₁₂:Pr³⁺ upon VUV excitation across the band gap are characterized by decay times in the range 25-28 ns with no significant rise after the excitation pulse. They appear to be faster upon X-ray irradiation than for VUV excitation. Weak afterglow components are attributed to defect luminescence.     

Magnetic properties of PrRh2Si2: A neutron diffraction study

The magnetic properties of polycrystalline PrRh₂Si₂ sample have been investigated by neutron diffraction measurements. Antiferromagnetic transition with an anomalously high ordering temperature (T_N∼68 K) is clearly observed in magnetic susceptibility, specific heat, electrical resistivity and neutron diffraction measurements. Neutron diffraction study shows that Pr³⁺ ions carry an ordered moment of 2.99(7)μ_B/Pr³⁺ and align along the crystallographic±c-directions for the ions located at the (0,0,0) and positions. The magnetoresistance at 2 K and 10 T is rather large (∼35%).     

The magnetic structure of HoCo2Si2

We have carried out neutron diffraction on a HoCo₂Si₂ powder sample at 4.2 K. The magnetic structure of this compound is collinear antiferromagnetic with the holmium magnetic moments parallel to the c-axis of the crystal. The magnetic moment value of holmium is 9.85 μ_B. The magnetic space group is I4/mm'm' (Sh⁴¹⁰₁₂₈) k = 000 The ordering temperature is t_n = 12(1) K.     

The surface state of URu2Si2

The ‘hidden-order’ (HO) transition of URu₂Si₂ remains a puzzle after 25 years of research. Using high-resolution angle-resolved photoemission spectroscopy (ARPES) we found that a hole-like band around Γ having its band maximum at E = −35 meV, and previously thought to be a bulk band of the system, is indeed a surface state not related to the HO phase transition. Here we present our detailed investigations to assign that state to a surface feature, and discuss on the possible origins of this surface band.