Superconductivity of F-substituted LnOBiS2 (Ln=La,Ce, Pr,Nd, Yb) compounds

Polycrystalline samples of F-substituted LnOBiS₂ (Ln?=?La, Ce, Pr, Nd, Yb) compounds were synthesized by solid-state reaction. The samples were characterized by X-ray diffraction measurements and found to have the ZrCuSiAs crystal structure. Electrical resistivity and magnetic susceptibility measurements were performed on all of the samples and specific heat measurements were made on those with Ln?=?La, Ce, and Yb. All of these compounds exhibit superconductivity in the range 1.9?K–5.4?K, which has not previously been reported for the compounds based on Ce, Pr, and Yb. The YbO_0.5F_0.5BiS₂ compound was also found to exhibit magnetic order at ～2.7?K that apparently coexists with superconductivity below 5.4?K.     

Magnetic properties of R3Co29Si4B10 (R=La, Ce, Pr, Nd, Sm, Gd and Dy) borides

The crystal structure and magnetic properties of quaternary rare-earth intermetallic borides R₃Co₂₉Si₄B₁₀ with R=La, Ce, Pr, Nd, Sm, Gd and Dy have been studied by X-ray powder diffraction and magnetization measurements. All compounds crystallize in a tetragonal crystal structure with the space group P4/nmm. Compounds with R=La, Ce, Pr, Nd and Sm are ferromagnets, while ferrimagnetic behavior is observed for R=Gd and Dy. The Curie temperatures vary between 149 K and 210 K. The Curie temperatures in R₃Co₂₉Si₄B₁₀ (R=Ce, Pr, Nd, Sm, Gd, Dy) compounds are roughly proportional to the de Gennes factors.     

Crystal structure and the magnetic properties of CeTiGe3

The crystal structure of the RTiGe₃ compounds (R=La, Ce and Pr) has been studied by X-ray powder diffraction methods; Rietveld refinement has been carried out on the La homologue. These compounds crystallise in the BaNiO₃ prototype structure, hP10-P6₃/mmc, also called the hexagonal perovskite (a=6.300(1), c=5.915(1) Å for LaTiGe₃). This seems to be the first example in which an intermetallic phase adopts such a structure type which can be considered as derived from the Ni₃Sn type (anti) by a distortion of the lattice and the occupation of the quasi-octahedral 2a site at the origin of the cell (0, 0, 0) by Ti. The composition, also confirmed by microprobe analyses, was found to be strictly 1:1:3 indicating that these are line compounds, forming very likely by a peritectoid reaction. The existence of homologous compounds has been established for the lighter rare earths La, Ce and Pr. Heat capacity and magnetisation data show that CeTiGe₃ orders ferromagnetically with a Curie temperature of nearly 14 K. On the other hand a−ln T variation of the magnetic part of the resistivity below 300 K is consistent with that expected for single impurity Kondo behaviour. CeTiGe₃ is thus an uncommon example of a ferromagnetic dense Kondo lattice.     

A位掺杂对La5/8(PrxCa1-x)3/8MnO3（x=0.25,0.5,0.75）相分离及输运性质的影响

采用固相反应法制备La5/8(PrxCa1-x)3/8MnO3(x=0.25,0.5,0.75)多晶样品,研究其磁性质和电磁输运特性.X射线衍射表明,La5/8(PrxCa1-x)3/8MnO3(x=0.25,0.5,0.75)多晶样品室温的晶体结构呈Pnma空间群的正交结构.磁化强度-电阻(M～T)关系显示,La5/8(PrxCa1-x)3/8MnO3(x=0.25,0.5,0.75)的居里温度TC随Pr掺杂量增加而逐渐降低,三种样品分别为160K、150K、100K.此外,随着Pr3+掺杂量增加,样品晶格畸变程度增大,铁磁相互作用减弱,并且三种成分均形成自旋玻璃态,其自旋冻结温度分别为150K、75K、70K.电阻-温度(ρ～T)关系表明,样品在x=0.25时出现电阻的双峰现象,这是由于样品中铁磁相与反铁磁相相互竞争造成的.结果表明,通过对钙钛矿锰氧化物的A位稀土掺杂,可对其CMR效应进行有效调控.     

Combined Study of Structural,Magnetic and Transport Properties of Eu_(0.5)Ln_(0.5)BiS_2F Superconductor

Superconductivity below 0.3 K and a charge-density-wave-like(CDW-like) anomaly at 280 K were observed in EuBiS_2F recently.Here we report a systematic study of structural and transport properties in Eu_(0.5)Ln_(0.5)BiS_2F(Ln=La,Ce,Pr,Nd,Sm) by electrical resistivity,magnetization,and specific heat measurements.The lattice constants have a significant change upon rare earth substitution for Eu,suggesting an effective doping.As Ln is changed from Sm to La,the superconducting transition temperature T_c increases from 1.55 K to 2.8 K.In contrast to the metallic parent compound,the temperature dependence of electrical resistivity displays semiconductinglike behavior for all the Eu_(0.5)Ln_(0.5)BiS_2F samples.Meanwhile,the CDW-like anomaly observed in EuBiS2F is completely suppressed.Unlike the mixed valence state in the undoped compound,Eu ions in these rareearth-doped samples are mainly divalent.A specific anomaly at 1.3 K resembling that in EuBiS2F suggests the coexistence of superconductivity and spin glass state for Eu_(0.5)La_(0.5)BiS_2F.Coexistence of ferromagnetic order and superconductivity is found below 2.2 K in Eu_(0.5)Ce_(0.5)BiS_2F samples.Our results supplies a rich diagram showing that many interesting properties can be induced in BiS_2-based compounds.     

Der Übergang vom magnetischen zum nichtmagnetischen Ce in flüssigen Legierungen

Under pressure and in several intermetallic compounds Ce exhibits a phase transition from the magnetic to the nonmagnetic state connected with the delocalisation of the 4felectron. We have measured the magnetic susceptibility of liquid La, Ce and Pr and of liquid alloys of Ce with normal metals and transition metals. In liquid alloys with La, Pr, Cu and Sn the Ce keeps its localized magnetic moment over the full range of concentration. In liquid alloys with Ni, Co and Rh, however a continuous transition of Ce into the nonmagnetic state is observed.     

Magnetocrystalline anisotropy in RAu2Ge2 (R = La, Ce and Pr) single crystals

Anisotropic magnetic properties of single crystalline RAu₂Ge₂ (R=La, Ce and Pr) compounds are reported. LaAu₂Ge₂ exhibits a Pauli-paramagnetic behaviour whereas CeAu₂Ge₂ and PrAu₂Ge₂ show an antiferromagnetic ordering with Nèel temperatures T_N = 13.5 and 9 K, respectively. The anisotropic magnetic response of Ce and Pr compounds establishes [0 0 1] as the easy axis of magnetization and a sharp spin-flip type metamagnetic transition is observed in the magnetic isotherms with H // [0 0 1]. The transport and magnetotransport behaviour of these compounds, in particular LaAu₂Ge₂, indicate an anisotropic Fermi surface. The magnetoresistivity of CeAu₂Ge₂ apparently reveals the presence of a residual Kondo interaction. A crystal electric field analysis of the anisotropic susceptibility in conjunction with the experimentally inferred Schottky heat capacity enables us to propose a crystal electric field level scheme for Ce and Pr compounds. For CeAu₂Ge₂ our values are in excellent agreement with the previous reports on neutron diffraction. The heat capacity data in LaAu₂Ge₂ show clearly the existence of Einstein contribution to the heat capacity.     

Magnetic properties of ternary rare-earth compounds of the type R2Fe14B

Ternary tetragonal compounds of the composition R₂Fe₁₄B were observed for R = Y, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, and Lu. The lattice constants and the X-ray density of these compounds were determined. Also determined were the magnetic properties, comprising the temperature dependence of the magnetization in the range 4.2–700 K and the field dependence of the magnetization at 4.2 K in fields up to 20 T. These latter measurements were made in two mutually perpendicular directions, making it possible to determine the anisotropy fields. The magnetocrystalline anisotropy was found to consist of contributions due to the Fe and rare-earth sublattice, respectively.     

High temperature superconductivity in rare-earth (R)-barium copper oxides (RBa2)Cu3O9−σ

The series of rare-earth (R)-barium copper oxides with nominal composition (RBa₂)Cu₃O_9−σ and the prototype compound (YBa₂)Cu₃O_9−σ have been prepared from the R (except Pm), Y, and Cu oxides and Ba carbonate by sintering, followed by arc-melting and annealing in pure oxygen. X-ray diffraction measurements show that, except for R = Ce, Tb, and Lu, the compounds have the perovskite-type structure reported by Cava et al. for high superconducting transition temperature T_c (YBa₂)Cu₃O_9−σ. Electrical resistivity and magnetic susceptibility vs temperature measurements reveal super-conductive onsets above 90 K for all R elements, except La, Ce, Pr, and Tb, for which no superconductivity was observed down to 4.2 K. Light (heavy) rare-earth compounds tend to have relatively little (large) orthorhombic splitting in their X-ray patterns, relatively high (low) normal-state resistivities with negative (positive) temperature coefficients, and broad (sharp) superconductive transitions. The negligible destructive effect of the R magnetic moments on superconductivity indicates that the superconducting electrons are primarily associated with the Cu-O polyhedral clusters and interact only weakly with the R ions, suggesting that the (RBa₂)Cu₃O_9−σ compounds may constitute an interesting new class of “high T_c” magnetic superconductors.     

Abnormal magnetic properties of the Ce24Co11 hexagonal phase

The lighter rare earth-cobalt and thorium-cobalt binary systems were revised on the rare earth or thorium side, by metallographic, electron microprobe and X-ray methods. In agreement with previous works, it is confirmed that, in these systems, the first intermetallic compound corresponds to the following stoichiometry: 3:1 for trivalent La, Pr and Nd; 7:3 for tetravalent Th; 24:11 for Ce. The electronic structure of Ce in the hexagonal (P6₃mc) Ce₂₄Co₁₁ phase was investigated via magnetic susceptibility measurements in the 4.2–1300 K temperature range. The results show that the Curie-Weiss law is not followed, no magnetic order occurs down to 4.2 K and a very small change in the thermal behaviour of the magnetic susceptibility appears above the melting point of the phase (750 K). The abnormally low values of the magnetic susceptibility of Ce₂₄Co₁₁ could be understood by assuming Co is a non-magnetic state and Ce in a temperature dependent mixed valence state.     

Sm-Co-Ti三元系相关系及某些单相化合物的结构与磁性

通过X射线衍射和磁性测量研究了Sm-Co-Ti三元体系富Co区固相线下的相关系,并探索了Co基3:29型化合物存在的可能性,进而研究了某些单相化合物的结构和磁性.实验表明,该体系中存在三个三元化合物SmCo_7-xTi_x,Sm₂Co_17-xTi_x和SmCo_12-xTi_x,其固溶区分别为0.32≤x≤0.54,0≤x≤1.13和1.45≤x≤1.95.按Sm_9.31Co_90-xTi_x(3≤x≤15)成分配料,Sm按其质量的15%,20%,25%三个比例过量加入,在1303—1403K温度范围内退火,均未发现3∶29相.在制备出的SmCo_12-xTi_x,和Sm₂Co_17-xTi_x两个系列化合物中,随着Ti含量的增加,它们的居里温度和饱和磁化强度都单调降低.Sm₂Co_17-xTi_x化合物在居里温度以下表现为单轴各向异性,而SmCo_12-xTi_x化合物表现为面各向异性.SmCo_12-xTi_x和Sm₂Co_17-xTi_x化合物1.5K下的磁晶各向异性场随Ti含量的变化都呈现一个极大值,这可能与Ti原子的择优占位有关 关键词： 稀土过渡族化合物 X射线衍射 相图 磁晶各向异性     

Interconfigurational 5d?→?4f luminescence of Ce(3+) and Pr(3+) in Ca(9)Lu(PO(4))(7)

Ca(9)Lu(PO(4))(7):Ce (3+) and Ca (9)Lu (PO (4))(7):Pr (3+) polycrystalline materials were synthesized by solid state reaction at high temperature. The materials were characterized by powder x-ray diffraction (XRPD). The luminescence spectroscopy and the excited state dynamics of these compounds were investigated upon excitation with UV/VUV synchrotron radiation. Both materials showed efficient and fast 5d-4f emission upon direct VUV excitation into the 5d levels but only Ca(9)Lu(PO(4))(7):Ce (3+) revealed luminescence upon excitation across the bandgap. The decay kinetics of the 5d-4f emission upon VUV intra-center excitation is characterized by a decay time of 29?ns for Ce (3+) and 17 ns for Pr (3+) with no significant build-up after the excitation pulse. For the both compounds, no significant temperature dependence of the 5d-4f emission lifetime was observed within the range 8-300?K.     

A comparative study of magnetic and dielectric behaviors for La(1-x)Bi(x)Mn(1-y)Fe(y)O3 series (with x = 0.5, 0.7 and y = 0.3, 0.7)

We have carried out an extensive investigation into the effect of doping on both the A- and B-sites for the multiferroic La(0.5)Bi(0.5)Mn(0.5)Fe(0.5)O(3) in relation to its physical properties. The temperature dependent magnetization and dielectric response are determined for different percentages of Bi- and Fe-substitutions. For La(0.5)Bi(0.5)Mn(0.7)Fe(0.3)O(3), there is a prominent ferromagnetic transition T(C) around 110 K, whereas the other La(0.5)Bi(0.5)Mn(0.3)Fe(0.7)O(3) and La(0.3)Bi(0.7)Mn(0.3)Fe(0.7)O(3) phases fail to exhibit any clear transition. On the other hand, for the Fe-rich phases, the coercive field increases to 2450 Oe compared to 1720 Oe (for the Mn-rich phase). All the compositions exhibit coexistence of ferromagnetic and antiferromagnetic phases at low temperatures. The temperature dependent dielectric constant of the investigated samples varies from 32,000 to 500 at room temperature and the data has been analyzed using the universal dielectric response model.     

Magnetic and superconducting properties of Tl(Sr1.5R0.5)CaCu2O7−δ compounds

DC magnetic susceptibility and resistivity measurements have been performed on 14 Tl(Sr_1.5R_0.5)CaCu₂O_7−δ compounds with R=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu. All samples except the Ce-doped compound show superconducting phase transition temperature around 80–90 K. The rare-earth atoms behave as local moments above the superconducting transition temperature of these compounds. Mechanism of filling of holes in the CuO₂ plane can be employed to interpret the suppression or enhancement of superconductivity by rare-earth ions in Tl(Sr_1.5R_0.5)CaCu₂O_7−δ.     

EXAFS study of intermetallics of the type RGe2 (R=La,Ce, Pr,Nd, Sm,Gd, Tb,Dy, Ho,Er and Y) Part I: Determination of Ge-Ge distances

A study of theEXAFS associated with theK x-ray absorption discontinuity of germanium in pure germanium and in the rare-earth germanides RGe₂ (where R=La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er and Y) has been carried out. The Ge-Ge distances have been obtained in these compounds. Considering the phase to the RGe₂ system, the bond lengths in these compounds have been determined. The values obtained by us for the RGe₂ compounds (R=La, Ce, Pr, Nd, Sm, Gd, Dy and Y) agree with those obtained earlier by crystallographic methods. The bond lengths for the compounds TbGe₂, HoGe₂ and ErGe₂ are also being reported.     

Frequency–temperature response of Pb(Zr0.65−xCexTi0.35)O3 ferroelectric ceramics: Structural and dielectric studies

A high-temperature solid-state reaction technique was used to prepare polycrystalline samples of Pb(Zr_0.65−xCe_xTi_0.35)O₃ (x=0, 0.05, 0.10, 0.15) (PZCT). X-ray diffraction (XRD) technique and scanning electron microscopy (SEM) were used to study the structural and microstructural properties of the compounds, respectively. The XRD study confirmed the formation of compounds at room temperature. Microstructural analysis of the surface of the compounds exhibits that there is a change in grain size, shape and density on introduction of cerium (Ce) in PZCT. Detailed studies of the dielectric properties reveal that PZCT show: (i) increase in T_c on increasing Ce concentration and (ii) improvement in dielectric constant and ac conductivity.     

Magnetic studies of RCo12B6 compounds (R=Y,Ce, Pr,Nd, Sm,Gd and Dy)

Magnetization of the RCo₁₂B₆ borides (R=Y, Ce, Pr, Nd, Sm, Gd and Dy), which crystallize in a rhombohedral structure of the SrNi₁₂B₆-type, has been measured in the temperature range 4.2–300 K. All compounds were found to order magnetically with Curie temperatures ranging from 154 to 177 K. Saturation moments at 4.2 K were found to be 6.5, 5.4, 8.4, 8.8, 6.8, 2.1 and 5.9μ_B/f.u. for R=Y, Ce, Pr, Nd, Sm, Gd and Dy, respectively. These results imply a ferromagnetic coupling of Co and rare earth moments for light rare earths and an antiferrimagnetic coupling for heavy rare earths in these compounds. A spin-compensation effect is observed in GdCo₁₂B₆ alloys at T_comp=46 and 72 K, respectively. Results suggest that in CeCo₁₂B₆ the Ce ion exists in the quadripositive state. It is clear that RCo₁₂B₆ materials are not of interest for permanent magnet applications.     

ELECTRONIC STRUCTURE AND CRYSTALLINE ELECTRIC FIELD IN Rco5(R= Y,La, Ce,Pr, Nd,Sm, Gd,and Tb)

Self consistent charge and spin polarized local spin-density approximation functional theory calculations based on the discrete variational method have been performed for RCo₅(R=Y, La, Ce, Pr, Nd, Sm, Gd, and Tb) compounds. The partial density of states of the Pr atom in the PrCo₆Co₁₂ cluster is established to be strikingly similar to that of the Ce atom in the CeCo₆Co₁₂ cluster, supporting the suggestion that the Pr atom is valence fluctuating. The radii ＜r_4f＞ and ＜r₄f²＞ of the 4f electrons of the R atom from La to Tb, except Ce, show the lanthanide contraction. The crystalline electric field (CEF) parameter A⁰₂ at the R site is calculated using a real charge distribution ρ(R) in the cluster, except for Pr and Nd, and is in agreement with that evalu ated based on the single-ion model. This result shows that the CEF parameter A⁰₂ is mainly determined by the near electronic structure. There exists a hybridization in a certain degree between the light rare-earth R-4f and Co-3d orbitals in some single-electron-molecular-orbitals, which are n ear the Fermi energy level and occupied by electrons. For light rare-earths the R-4f electrons in R Co₆Co₁₂(R=Y, La, Ce, Pr, Nd, and Sm) clu sters are not localized entirely and a small amount of the R-4f electrons have itinerant properties.     

Magnetic susceptibility and electrical resistivity of some Th2Zn17-type rare-earth zinc phases

We report measurements of the magnetic susceptibility and electrical resistivity of the iostructural compounds RE₂Zn₁₇ (RE=La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu). The composition dependence of the lattice parameter and effective moment indicate that all the RE ions are trivalent except Yb which is divalent. Magnetic order is observed in compounds where RE=Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho and Er. A second transition is seen for RE=Pr, Ho, Sm and Tb. Superzone boundary effects are observed in the electrical resistivity of these four alloys as well as in Er₂Zn₁₇. Resistivity measurements reveal concentrated Kondo behavior (or 4f instability) of Ce in Ce₂Zn₁₇.     

On the nature of the dhcp to fcc transition under pressure in Pr and Pr-Th alloys

The results of electrical resistance (R), thermoelectric power (TEP) and X-ray diffraction measurements on praseodymium (Pr) and its alloys with thorium under pressure are reported. The maximum inR vsP curve exhibited by Pr persists only in the dhcp phase of PrTh alloy. X-ray measurements confirmed that in the alloys also the maximum inR vsP curve is due to the dhcp → fcc transition. Thus the behaviour of Pr and Pr-Th alloys is different from that of La and its alloys with Ce and Th where the maximum in theR vsP curve is electronic in origin and is exhibited by the dhcp, fcc and dist fcc phases.