Magnetic properties of Fe2P-type R6CoTe2 compounds (R=Gd-Er)

The magnetic structure of the Fe₂P-type R₆CoTe₂ phases (R=Gd-Er, space group P6¯2m) has been investigated through magnetization measurement and neutron powder diffraction. All phases demonstrate high-temperature ferromagnetic and low-temperature transitions: T_C=220 K and T_CN=180 K for Gd₆CoTe₂, T_C=174 K and T_CN=52 K for Tb₆CoTe₂, T_C=125 K and T_CN=26 K for Dy₆CoTe₂, T_CN=60 K and T_N=22 K for Ho₆CoTe₂ and T_CN∼30 K and T_N∼14 K for Er₆CoTe₂.Between 174 and 52 K Tb₆CoTe₂ has a collinear magnetic structure with K₀=[0, 0, 0] and with magnetic moments along the c-axis, whereas below 52 K it adopts a non-collinear ferromagnetic one.Below 60 K the magnetic structure of Ho₆CoTe₂ is that of a non-collinear ferromagnet. The holmium magnetic components with a K₀=[0, 0, 0] wave vector are aligned ferromagneticaly along the c-axis, whereas the magnetic component with a K₁=[1/2, 1/2, 0] wave vector are arranged in the ab plane. The low-temperature magnetic transition at ∼22 K coincides with the reorientation of the Ho magnetic component with the K₀ vector from the collinear to the non-collinear state.Below 30 K Er₆CoTe₂ shows an amplitude-modulate magnetic structure with a collinear arrangement of magnetic components with K₀=[0, 0, 0] and K₁=[1/2, 1/2, 0]. The low-temperature magnetic transition at ∼14 K corresponds to the variation in the magnitudes of the M_Er^K0 and M_Er^K1 magnetic components.In these phases, no local moment was detected on the cobalt site.The magnetic entropy of Gd₆CoTe₂ increases from ΔS_mag=−4.5 J/kg K at 220 K up to ΔS_mag=−6.5 J/kg K at 180 K for the field change Δμ₀H=0-5 T.     

Magnetic properties of DyCo5 and TbCo5 intermetallics from the electronic structure calculations

LSDA and LSDA+U calculations, with spin-orbit coupling (SOC) included, were performed for DyCo₅ and TbCo₅ intermetallic compounds. In the case of magnetic moments, LSDA-SOC calculations give results in good agreement with the experimental data. However, LSDA has shown to be unable to predict relative stabilities of ferromagnetic and ferrimagnetic configurations of the 4f and 3d spin sublattices giving the wrong result that the ferromagnetic configuration is more stable. LSDA+U method cures this problem and gives correct result. Additionally, within the accuracy of available experimental data, the corresponding effective exchange fields are in reasonable agreement with experiment.     

Magnetic properties of RE2MnGe6 (RE = La,Ce) and YMn0.3Ge2 germanides

The magnetic data of RE₂MnGe₆ (RE = La, Ce) and YMn_0.3Ge₂ are reported. La₂MnGe₆ and Ce₂MnGe₆ crystallize in the orthorhombic Ce₂CuGe₆ structure type, space group Amm2 (No. 38). The non-stoichiometric YMn_0.3Ge₂ compound crystallizes with the orthorhombic CeNiSi₂-type structure (space group Cmcm (No. 36)). The studied RE₂MnGe₆ (RE = La, Ce) intermetallics are characterized by ferromagnetic properties with Curie temperatures 177 (La) and 150 K (Ce), respectively. For YMn_0.3Ge₂ the low-field magnetic measurements indicate the antiferromagnetic property below 395 K with the small ferromagnetic component. The values of the magnetic moments in the ordered state indicate the ferromagnetic ordering in La₂MnGe₆ and complex magnetic order with the ferromagnetic component in YMn_0.3Ge₂ and Ce₂MnGe₆. The hysteresis loop and values of the coercivity field indicate that these compounds are soft magnetic materials.     

Magnetic and thermodynamic properties of NdT2Ge2 (T=Pd, Ag) compounds

Physical properties of NdPd₂Ge₂ and NdAg₂Ge₂, crystallizing with the tetragonal ThCr₂Si₂-type crystal structure, were investigated by means of magnetic, calorimetric, electrical transport as well as by neutron diffraction measurements. The specific heat studies and neutron diffraction measurements were performed down to 0.30 K and 0.47 K, respectively. Both compounds exhibit antiferromagnetic ordering below T_N equal to 1.5 K for NdPd₂Ge₂ and 1.8 K for NdAg₂Ge₂. Neutron diffraction data for the latter germanide indicate antiferromagnetic collinear structure described by the propagation vector k=(0.5, 0, 0.5). The Nd magnetic moments equal to 2.24(5) μ_B at 0.47 K are aligned along the a-axis and have the +− sequence within the crystal unit cell. For NdPd₂Ge₂ only very small Bragg peaks of magnetic origin were observed in the neutron diffraction patterns measured below T_N, thus hampering determination of the magnetic structure. Both compounds exhibit metallic-like electrical conduction. From the specific heat data the crystal electric field (CEF) levels schemes were determined. Difference between the overall CEF splitting in the two compounds is correlated with their structural parameters.     

Magnetocaloric effect in the ternary DyCo3B2 compound

A large magnetocaloric (MCE) effect has been observed for the ternary compound DyCo₃B₂. This material shows the magnetic ordering below T_C = 22 K for H = 0 T. MCE has been determined based on the isothermal magnetization curves measurements and the isomagnetic heat capacity dependence on temperature. The maximum magnetic entropy change −ΔS_M = 17.5 J kg⁻¹K⁻¹ and the adiabatic temperature change ΔT_ad = 14 K have been observed in the neighborhood of the magnetic phase transition at the magnetic field change of 9 T. The analysis of the magnetic contribution to the specific heat indicates on the important role of the crystal electric field and the anisotropy for the properties of the DyCo₃B₂ compound.     

Magnetic structure of pyrochlore-type Er2Ru2O7

Powder neutron diffraction measurements were carried out for the ruthenium pyrochlore oxide Er₂Ru₂O₇. The magnetic structure for this compound at 3.0 K has been solved using Rietveld analysis. The observed magnetic reflections suggest that the magnetic transitions are regarded as those to a long-range ordered state. It seems that the magnetic order of the Ru⁴⁺ and Er³⁺ magnetic moments occurs at 90 and 10 K, respectively.     

Metamagnetic transition in the 75 K antiferromagnet Gd4Co2Mg3

Gd₄Co₂Mg₃ (Nd₄Co₂Mg₃ type; space group P2/m; a=754.0(4), b=374.1(1), c=822.5(3) pm and β=109.65(4)° as unit cell parameters) was synthesized from the elements by induction melting in a sealed tantalum tube. Its investigation by electrical resistivity, magnetization and specific heat measurements reveals an antiferromagnetic ordering at T_N=75(1) K. Moreover, this ternary compound presents a metamagnetic transition at low critical magnetic field (H_cr=0.93(2) T at 6 K) and exhibits a magnetic moment of 6.3(1) μ_B per Gd-atom at 6 K and H=4.6 T. Due to this transition the compound shows a moderate magnetocaloric effect; at 77 K the maximum of the magnetic entropy change is ΔS_M=−10.3(2) J/kg K for a field change of 0-4.6 T. This effect is compared to that reported previously for compounds exhibiting a magnetic transition in the same temperature range.     

Sm2NiSn4: The intermediate structure type between ZrSi2 and CeNiSi2

A new rare earth nickel stannide, Sm₂NiSn₄, has been prepared by reacting the pure elements at high temperature in welded tantalum tubes. Its crystal structure was established by single crystal X-ray diffraction studies. Sm₂NiSn₄ crystallizes in the orthorhombic space group Pnma (No. 62) with cell parameters of a=16.878(2) Å, b=4.4490(7) Å, c=8.915(1) Å, and Z=4. Its structure can be viewed as the intermediate type between ZrSi₂ and CeNiSi₂. Sm₂NiSn₄ features two-dimensional (2D) corrugated [NiSn₄]⁶⁻ layers in which the 1D Sn zigzag chains and the 2D Sn square sheets are bridged by Ni atoms. The Sm³⁺ cations are located at the interlayer space. Results of both resistivity measurements and extended-Hückel tight-binding band structure calculations indicate that Sm₂NiSn₄ is metallic.     

Crystal growth, structures, and optical properties of the cubic double perovskites Ba2MgWO6 and Ba2ZnWO6

Single crystals of the tungstates Ba₂MgWO₆ and Ba₂ZnWO₆ have been grown for the first time. The crystals were prepared with molten potassium carbonate acting as a flux. According to the single-crystal X-ray diffraction structure determination, the compounds crystallize in space group Fm3¯m of the cubic system with a double perovskite structure, A₂BB′O₆. These structural findings were confirmed with neutron diffraction on polycrystalline samples synthesized by a high-temperature solid-state route. Both sets of diffraction data reveal that the M²⁺ and W⁶⁺ cations are fully ordered on the B and B′ sites. Ba₂MgWO₆ and Ba₂ZnWO₆ exhibit room-temperature luminescence with green and yellow emissions, respectively.     

Structural and magnetic properties of Zn1−xSbxCr2−x/3Se4 (x=0.11, 0.16 and 0.20) single crystals

Single crystals of Zn_1−xSb_xCr_2−x/3Se₄ based on the ZnCr₂Se₄ spinel, which is known to exhibit interesting magnetic and electronic transport properties, have been prepared by solid state reaction from the appropriate selenides. Three compounds of different Sb content (x=0.11, 0.16, and 0.20) were studied by X-ray diffraction, X-ray photoelectron scattering technique and macroscopic magnetic measurements with the aim to determine (i) stability of the cubic symmetry and (ii) influence of the Sb admixture on the magnetic properties. The results show that the Sb³⁺ and Zn²⁺ ions share the tetrahedral sites in the spinel structure, while the Cr³⁺ions carrying magnetic moments, are located in the octahedral sites. The X-ray photoelectron spectroscopy (XPS) data indicate that in this series of compounds the chromium ions have a 3d³ electronic configuration. The three samples studied order antiferromagnetically at low temperatures, with the magnetic characteristics being hardly altered with respect to those reported for the parent ZnCr₂Se₄ compound.     

The effects of doping ferromagnetic spinel CdCr2Se4 with Sb ions

Semiconducting spinel CdCr₂Se₄ orders ferromagnetically below T_C=130 K. A series of single-crystals of CdCr₂Se₄ doped with Sb³⁺ ions has been synthesized in order to study an effect of the substitution on the cation distribution and the magnetic properties. The compounds of Cd_ySb_xCr_zSe₄ have been investigated by means of X-ray diffraction, magnetization measurements and electron spin resonance spectroscopy. Two selected samples of the composition (Cd_1−xSb_x)[Cr₂]Se₄ with x=0.13 and 0.44 retained cubic symmetry with space group . The unit cell parameter appeared to be sensitive to the concentration of Sb³⁺ admixture: it increases with x, despite a close similarity in the ionic radii of Cd²⁺ and Sb³⁺ in tetrahedral coordination. Upon partial substitution of Cd²⁺ by Sb³ no obvious change in the Curie temperature was observed, however, the effective magnetic moment slightly increased, what may result from the appearance of Cr²⁺ ions. The characteristic feature of the system studied is an extended range of short-range magnetic order, in which the magnetic properties in the paramagnetic state are governed by the formation of ferromagnetic clusters, as indicated by both the bulk magnetometric and spectroscopic data.     

Exchange interactions in R2Fe17−xGax (R=Y, Sm, Gd, Tb, Ho and Tm) compounds

We calculated the molecular field coefficients, n_FeFe and n_RFe (R=Sm, Gd, Tb, Ho and Tm), for R₂Fe_17−xGa_x and the values of n_FeFe and n_SmFe for R₂Fe_17−xT_x (T=Al and Si) using the experimental values of the Curie temperature. The values of n_FeFe increase in spite of the decrease of μ_Fe for 0?x?5. The values of n_SmFe have large values when the magnetic anisotropy is axial. For 6?x?8, the values of n_FeFe, n_HoFe and n_TmFe increase largely, which is related to the change of the easy magnetization direction. For Y₂Fe_17−xT_x (T=Ga and Al), the values of n_FeFe have a maximum value with increasing those of μ_Fe. With increasing V⁻¹, the values of n_FeFe have a maximum value around the same value of V⁻¹ for Y₂Fe_17−xT_x (T=Ga and Al). For Y₂Fe_17−xSi_x, the values of n_FeFe increase with increasing V⁻¹.     

Magnetic and transport properties of RCr0.3Ge2 (R=Tb, Dy, Ho and Er) compounds

The magnetic and transport properties of ternary rare-earth chromium germanides RCr_0.3Ge₂ (R=Y and Tb-Er) have been determined. X-ray and neutron diffraction studies indicate that these compounds have the CeNiSi₂-type structure (space group Cmcm) [1]. Magnetic measurements reveal the antiferromagnetic ordering below T_N equal to 18.5 K (R=Tb), 11.8 K (Dy), 5.8 K (Ho) and 3.4 K (Er). From the neutron diffraction data the magnetic structures have been determined. For TbCr_0.3Ge₂ and DyCr_0.3Ge₂ at low temperatures the magnetic ordering can be described by two vectors k₁=(,0,0) and k₂=(,0,), and k₁′=(,0,0) and k₂′=(,0,), respectively. In HoCr_0.3Ge₂ and ErCr_0.3Ge₂ the ordering can be described by one propagation vector equal to (,,0) and (0,0,0.4187(2)), respectively. In DyCr_0.3Ge₂ some change in the magnetic ordering is observed at T_t=5.1 K. In temperature range from T_t to T_N the magnetic ordering is given by one propagation vector k=(,0,0). YCr_0.3Ge₂ is a Pauli paramagnet down to 1.72 K which suggests that in the entire RCr_0.3Ge₂ series the Cr atoms do not carry magnetic moments. All compounds studied exhibit metallic character of the electrical conductivity. The temperature dependencies of the lattice parameters reveal strong magnetostriction effect at the respective Nèel temperatures.     

High temperature crystal structures and superionic properties of SrCl2, SrBr2, BaCl2 and BaBr2

The structural properties of the binary alkaline-earth halides SrCl₂, SrBr₂, BaCl₂ and BaBr₂ have been investigated from ambient temperature up to close to their melting points, using the neutron powder diffraction technique. Fluorite-structured SrCl₂ undergoes a gradual transition to a superionic phase at 900–1100 K, characterised by an increasing concentration of anion Frenkel defects. At a temperature of 920(3) K, the tetragonal phase of SrBr₂ undergoes a first-order transition to a cubic fluorite phase. This high temperature phase shows the presence of extensive disorder within the anion sublattice, which differs from that found in superionic SrCl₂. BaCl₂ and BaBr₂ both adopt the cotunnite crystal structure under ambient conditions. BaCl₂ undergoes a first-order structural transition at 917(5) K to a disordered fluorite-structured phase. The relationship between the (disordered) crystal structures and the ionic conductivity behaviour is discussed and the influence of the size of the mobile anion on the superionic behaviour is explored.     

Neutron powder diffraction, and solid-state deuterium NMR analyses of Yb2RuD6 and spectroscopic vibrational analysis of Yb2RuD6 and Yb2RuH6

The crystal structure of Yb₂RuD₆ has been determined by neutron powder diffraction and the results were consistent with the Fm3m (#225) space group, a=7.2352(18) Å, with the atoms arranged according to the well-known K₂PtCl₆ structure. No structural phase transition was observed in going from room temperature to 4 K. Raman spectra were not available due to fluorescence, but all fundamental bands and combination bands were assigned from FTIR and PAIR spectra only following previous studies for other alkaline earth and europium ruthenium ternary metal hydrides and deuterides. The deuterium nuclear quadrupole coupling constant, 40.9 kHz, leads to an ionic character of the Ru-D bond of 82%.     

Synthesis, structure, and magnetism of Tb4PdGa12 and Tb4PtGa12

Single crystals of Tb₄MGa₁₂ (M=Pd, Pt) have been synthesized. The isostructural compounds crystallize in the cubic space group , with Z=2 and lattice parameters: a=8.5940(5) and 8.5850(3) Å for Tb₄PdGa₁₂ and Tb₄PtGa₁₂, respectively. The crystal structure consists of corner-sharing MGa₆ octahedra and TbGa₃ cuboctahedra. Magnetic measurements suggest that Tb₄PdGa₁₂ is an antiferromagnetic metamagnet with a Néel temperature of 16 K, while the Pt analog orders at T_N=12 K.     

PrCo2Al8 and Pr2Co6Al19: Crystal structure and electronic properties

The praseodymium cobalt aluminides, PrCo₂Al₈ and Pr₂Co₆Al₁₉, were prepared by reaction of the elemental components in an arc-melting furnace, followed by heat treatment at 900 °C for several days. Their chemical composition was checked by scanning electron microscopy and energy dispersive spectroscopy, and their crystal structure was refined from single crystal X-ray diffraction data. PrCo₂Al₈ adopts the CaCo₂Al₈ type of structure, crystallizing with the orthorhombic space group Pbam, with four formula units in a cell of dimensions at room temperature: , , . Pr₂Co₆Al₁₉ crystallizes in the monoclinic space group C2/m, with four formula units in a cell of dimensions at room temperature: , , and β=103.903(1)°. Its structure belongs to the U₂Co₆Al₁₉ type. The crystal structures of both compounds studied can be viewed as three-dimensional structures resulting from the packing of Al polyhedra centred by the transition elements. Along the c-axis, the coordination polyhedra around the Pr atoms pack by face sharing to form strands, which are separated one from another by an extended Co-Al network. Magnetic measurements have revealed that PrCo₂Al₈ orders antiferromagnetically at , with a clear metamagnetic transition occurring at a critical field H_c=0.9(1) T. The temperature dependence of the susceptibility of Pr₂Co₆Al₁₉ does not provide any evidence for long-range magnetic ordering in the temperature domain 1.7-300 K. At low temperatures (T<10 K), the susceptibility saturates in a manner characteristic of a non-magnetic singlet ground state. At high temperatures, the magnetic susceptibility of each compound follows a Curie-Weiss law, with the effective magnetic moment per Pr atom of 3.48(5)μ_B and 3.41(2)μ_B for PrCo₂Al₈ and Pr₂Co₆Al₁₉, respectively. These values are close to the theoretical value of 3.58μ_B expected for a free Pr³⁺ ion and exclude any contribution due to the Co atoms. Both compounds exhibit in the temperature range 5-300 K metallic-like electrical conductivity, and their Seebeck coefficient is of the order of several μV/K.     

Synthesis and crystal structure of RMgSi2 compounds (R=La, Ce, Pr, Nd), a particular example of linear intergrowth

A new series of rare earth compounds with stoichiometry RMgSi₂ (R=La, Ce, Pr, Nd) is reported. The single crystal X-ray diffraction showed that CeMgSi₂, which melts congruently at 1200 °C, crystallizes in a new tetragonal structure type (I4₁/amd, tI32, a=4.2652(4) Å, c=36.830(4) Å, Z=8; wR₂=0.042 (19 parameters, 393F₀²), R₁=0.018 (297F₀>4σF₀). The crystal structure of CeMgSi₂ can be formally built up by alternating along the z direction four CeMg₂Si₂-type CeMg₂Si₂ slabs with four AlB₂-type CeSi₂ slabs, one after the other. The structural model obtained from a CeMgSi₂ single crystal has been confirmed for the La, Pr and Nd homologous compounds by means of Rietveld refinement. The trend of the unit-cell parameters, plotted versus the R³⁺ ionic radius, shows a linear behaviour, which strongly suggests a trivalent state for the Ce atoms. An analysis of the features of this new structure is reported, in comparison with the other known CeMg₂Si₂/AlB₂-type linear intergrowth compounds.     

Lattice effects in cubic La2Mo2O9: Effect of vacuum and correlation with transport properties

This study aims to investigate correlations between lattice effects and transport properties in cubic La₂Mo₂O₉. High temperature neutron diffraction data, recorded in air and under vacuum, are used to follow the evolution with temperature of selected structural parameters, i.e. bond lengths and angles. Results suggest a possible correlation with the experimentally observed decrease of the activation energy for oxygen migration at high temperature. The effect on the structural properties of the low oxygen partial pressure used during the measurements in vacuum is negligible and this represents a valuable information in view of possible applications of the material in solid state devices.