Magnetic structures of R2RhSi3 (R=Ho, Er) compounds

Powder X-ray and neutron diffraction and magnetic measurements have been performed on R₂RhSi₃ (R=Ho and Er) compounds at low temperatures. The compounds crystallize in a derivative of the hexagonal AlB₂-type structure. The crystal structure parameters have been refined on the basis of the X-ray and neutron diffraction patterns collected in the paramagnetic region. These compounds are antiferromagnets with Néel temperatures of 5.2 K for Ho₂RhSi₃ and 5 K for Er₂RhSi₃. Both compounds exhibit collinear magnetic structures, described by the propagation vector k=(1/2,0,0) for Ho₂RhSi₃ and k=(0,0,0) for Er₂RhSi₃. This magnetic order is stable in the temperature range between 1.5 K and the Néel temperature.     

Magnetic and electronic properties of RCoxGe2 (R = Pr, Nd) compounds

Magnetization, magnetic susceptibility, neutron diffraction and X-ray photoemission spectroscopy measurements were performed on polycrystalline samples: PrCo_0.85Ge₂ and NdCo_0.82Ge₂, crystallizing in an orthorhombic structure of the CeNiSi₂-type. The magnetometric data indicate that both compounds are antiferromagnetic at low temperatures, PrCo_0.85Ge₂ below 5 K and NdCo_0.82Ge₂ below 2.1 K. The neutron diffraction data indicate an antiferromagnetic structure in PrCo_0.85Ge₂ at 1.5 K and give no evidence of any magnetic ordering in NdCo_0.82Ge₂. The X-ray photoemission data indicate that the valence bands are formed predominantly by R 4f5d6s and Co 3d bands. The spin-orbit splitting values determined from the Pr and Nd, 3d_5/2 and 3d_3/2 XPS spectra are equal to 20.9 eV for the Pr compound and 23.0 eV for the Nd compound. The analysis of these spectra performed on the basis of the Gunnarsson–Schönhammer model revealed a small hybridization between 4f-electrons of the rare earths with the conduction band which implies rather good stability of the f shell in these compounds.     

New Zr6CoAs2-type R6MnSb2 and R6MnBi2 compounds (R=Y, Lu, Dy, Ho)

A powder X-ray diffraction investigation of the new ternary compounds Zr₆CoAs₂-type R₆MnSb₂ and R₆MnBi₂ (R=Y, Lu, Dy, Ho) is reported. The compounds Ho₆MnSb₂ (a=0.8070(2) nm, c=0.4230(1) nm), Lu₆MnSb₂ (a=0.7930(1) nm, c=0.4173(1) nm), Y₆MnBi₂ (a=0.8242(1) nm, c=0.4292(1) nm), Dy₆MnBi₂ (a=0.8211(1) nm, c=0.4286(1) nm), Ho₆MnBi₂ (a=0.8164(1) nm, c=0.4250(1) nm) and Lu₆MnBi₂ (a=0.8019(2) nm, c=0.4185(1) nm) crystallize in the hexagonal Zr₆CoAs₂-type structure (space group P6b2m No. 189). The Zr₆CoAs₂-type structure is a superstructure of the Fe₂P-type structure.     

Magnetic structures of rare earths R in RCoC2 and RNiC2 compounds

A comparative survey is given on the variety of magnetic structures of the series of RCoC₂ and RNiC₂ with R=Pr, Nd, Tb, Dy, Ho, Er and Tm, which have been analysed by neutron diffraction. Rare earth structure relevant features are summarized. All compounds, except those with Pr, order magnetically at low temperatures. Magnetic order is confined to the rare earths; Co and Ni sites remain non-magnetic. RCoC₂ become ferromagnets; RNiC₂ order antiferromagnetically in different spin configurations. The type of order and R dependent moment configurations are explained by RKKY exchange and additional crystal field interactions.     

Neutron diffraction studies of the magnetic structure of Ho3Pd4Ge4

Ho₃Pd₄Ge₄ crystallizes in the orthorhombic Gd₆Cu₈Ce₈-type of structure (space group Immm) in which the Ho atoms occupy two nonequivalent crystallographic positions: 2a and 4j. Neutron diffraction measurements indicate that the Ho moments in the 4j site below 6.7 K form a collinear antiferromagnetic structure with the magnetic moments parallel to the a axis, whereas the Ho moments in the 2a site below 5 K form a sine-wave modulated structure with the magnetic moments parallel to the c axis.     

New RRh5Ge3 compounds of the new SmRh5Ge3 structure type and their magnetic properties (R=Sm, Gd, Tb)

Powder X-ray diffraction results and macroscopic magnetic properties of new ternary RRh₅Ge₃ compounds (R=Sm, Gd, Tb) are reported. The compounds SmRh₅Ge₃ (a=2.2744(4) nm, c=0.3888(1) nm), GdRh₅Ge₃ (a=2.2711(5) nm, c=0.3872(1) nm) and TbRh₅Ge₃ (a=2.2628(7) nm, c=0.3851(1) nm) crystallize in the hexagonal SmRh₅Ge₃-type structure (space group P6₃/m; No. 176). The GdRh₅Ge₃ and TbRh₅Ge₃ compounds are Curie–Weiss paramagnets down to 5 K.     

Magnetic ordering in Th3P4-type Tb4Sb3 compound

The nature of the magnetic ordering of Tb₄Sb₃ compound (Th₃P₄-type, cubic; cI28, space group , No. 220, a = 0.91518(7) nm) has been investigated by using the techniques of magnetization and neutron diffraction. AC and DC magnetisation measurements indicate antiferromagnetic ordering at 108 K in zero magnetic field that is accompanied by a field-induced metamagnetic transition to a ferromagnetic state, in fields above 0.3 T. Neutron diffraction experiment in zero applied magnetic field shows that below T_N = 112(4) K Tb₄Sb₃ exhibits an antiferromagnetic flat spiral-type ordering with propagation vector K₁ = [±1/8, ±1/8, ±1/8]. The magnetic moment of Tb atoms is found to be M_Tb = 6.7(3) μ_B at 80 K. The magnetic moment of Tb atoms lie in the (1 1 1) plane of Tb₄Sb₃ unit cell (the cone axis arranges along [1 1 1] direction with cone angle β = 90°). Below T_N2  50 K, Tb₄Sb₃ shows second antiferromagnetic transition with K₂ = [1/2, 1/2, 1/2] with possible re-orientation of Tb magnetic moments.     

Structural investigation of ternary RIr3B2 compounds (R=Ce and Pr)

Structural studies were performed for the ternary RIr₃B₂ compounds (R=Ce and Pr) from as cast samples. The crystal structure of the ternary boride CeIr₃B₂ (CeCo₃B₂ structure type, space group P6/mmm, a=5.520(3) Å, c=3.066(2) Å, Z=1, V=80.91 ų, ρ_x=15.154 g cm⁻³) was refined to R₁=0.0470, wR₂=0.1240 from single-crystal X-ray diffraction data. The new ternary boride PrIr₃B₂ was found to be isostructural with the CeIr₃B₂ compound. Its lattice parameters a=5.5105(2) Å, c=3.1031(1) Å were obtained from a Rietveld refinement of X-ray powder diffraction data.     

Crystal structure of R3Ge4 compounds (R Er, Ho, Tm, Lu)

The crystal structure of binary germanides R₃Ge₄ (R Er, Ho, Tm, Lu) has been determined by means of powder X-ray diffraction. For Er₃Ge₄ a full-structure determination has been performed using the Rietveld method (306 reflections, space group Cmcm,

Full-size image (2K)

). The location of the atoms in Er₃Ge₄ is similar to that in the W₃CoB₃ structure, with the Ge atoms substituting for Co and B. For the other R₃Ge₄ compounds (RHo, Tm and Lu) the lattice parameters are given.     

The origin of the large magnetocaloric effect in RCo2 (R=Er, Ho and Dy)

The phase transitions of the RCo₂ (R=Er, Ho and Dy) compounds are of first-order type and a metamagnetic transition is observed above the Curie temperature. Owing to their large magnetic entropy change, the RCo₂ compounds are competitive candidates as the working substance for magnetic refrigeration. In this paper we discuss the origin of this large magnetic entropy change.     

Magnetic ordering in HoCoSi and TbCoGe

The crystal and magnetic structures of HoCoSi and TbCoGe were determined by neutron diffraction on polycrystalline samples. Both compounds exhibit the orthorhombic TiNiSi-type of crystal structure and order magnetically, at low temperatures. In HoCoSi at T = 1.7 K magnetic moments of holmium atoms form a conical spiral. It transforms with increasing temperature into a ferromagnetic structure. The Curie point of HoCoSi is 13 K. The magnetic moment of the Ho³⁺ ion is 6.5(1) μ_B at 1.7 K. In TbCoGe, a noncollinear ferromagnetic F₁C_z and a sine-modulated ordering are present at 1.5 K. The former disappears at 17.5 K and the latter at 20.5 K, which is the Néel point of TbCoGe. The magnetic moment localized on the Tb³⁺ ion at 1.5 K amounts to 8.9(1) μ_B in a noncollinear ferromagnetic phase and 1.5(2) in a modulated phase.     

The magnetic ordering in the Ho5Si3 and Ho5Ge3 compounds

A neutron diffraction investigation has been performed on the Ho₅Si₃ and Ho₅Ge₃ compounds (hexagonal Mn₅Si₃-type, hP16, P6₃/mcm) to study their magnetic structure. The results prove that these intermetallic phases show a complex sine-modulated type magnetic ordering, both presenting on cooling two subsequent antiferromagnetic orderings (T_N1 and T_N2).Between T_N1 = 24(2) and T_N2 = 16(4) K Ho₅Si₃ shows a first antiferromagnetic ordering of the sine-modulated type with a propagation vector K₁ = [0, 0, ±0.284(1)]; then, below T_N2 the sine-modulated type ordering is conserved, but by the two propagation vectors K₁ = [0, 0, ±0.2773(7)] and K₂ = [±1/5, ±1/5, 0].For Ho₅Ge₃, between T_N1 = 27(2) and T_N2 = 18(4) K, the sine-modulated ordering is realized through the propagation vectors K₁ = [0, 0, ±3/10] and K₂ = [0, 1/2, 0], whilst below T_N2 the ordering takes place with propagation vectors K₁ = [0, 0, ±3/10], K₂ = [0, 1/2, 0], K₃ = [0, 0, ±2/5] and K₄ = [±1/5, ±1/5, 0]. For both the Ho₅Si₃ and Ho₅Ge₃ compounds, the dimensions of the magnetic unit cell are 5a × 5a × 10c times the crystal unit cell of Mn₅Si₃-type.     

Crystal structure of the Nd(Ru0.6Ge0.4)2 and ErRuGe compounds

Using X-ray powder and single crystal diffraction, the crystal structures of the Nd(Ru_0.6Ge_0.4)₂ and ErRuGe compounds were investigated. The compounds belong to the KHg₂ and TiNiSi type structure, respectively.     

Crystal structures of R2Pd2Pb (R = Y, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, and Lu) compounds

The crystal structures of the R₂Pd₂Pb (R=Y, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, and Lu) compounds were determined using X-ray powder diffraction. The investigated compounds crystallize with Mo₂FeB₂ structure type (space group P4/mbm, Pearson code tP10). The importance of stabilization by polar intermetallic R–Pd bonding is underscored by a bonding analysis derived from electronic band structure calculations.     

Magnetic properties and magnetic structure of the Mn5Si3-type Tb5Si3 compound

Neutron diffraction and magnetization measurements have been performed on the Tb₅Si₃ compound (hexagonal Mn₅Si₃-type, hP16, P6₃/mcm) to understand its magnetic structure and magnetic properties. The temperature-dependent neutron diffraction results prove that this intermetallic phase shows a complex flat spiral magnetic ordering, presenting three subsequent changes in magnetization at on cooling. However, the magnetization data depict two transitions at 72 K (T_N1) and 55 K (T_N2). The extended temperature range between and over which the neutron diffraction patterns slowly evolve might correspond to the high-temperature antiferromagnetic transition at T_N1 and low-temperature antiferromagnetic transition at T_N2 of the magnetic data. Between Tb₅Si₃ shows a flat spiral antiferromagnetic ordering with a propagation vector K₁ = [0,0, ±1/4]; then, between the flat spiral type ordering is conserved, but by two coexisting propagation vectors K₁ = [0,0, ±1/4] and K₂ = [0,0, ±0.4644(3)]. The terbium magnetic moments arrange in the XY(ab) plane of the unit cell. Below the magnetic component with K₁ = [0,0, ±1/4] vanishes and magnetic structure of Tb₅Si₃ is a flat spiral with K₂ = [0,0, ±0.4644(3)], only. Low field magnetization measurements confirm the occurrence of complex, multiple magnetic transitions. The field dependence of the magnetization indicates a metamagnetic transition at a critical field of 3 T.     

Evolution of magnetic hardness in the HfFe6Ge6-type RMn6Sn6−xGax and RMn6Sn6−xInx compounds (R=Tb, Dy; 0.2≤x≤1.4)

The HfFe₆Ge₆-type RMn₆Sn_6−xX_x′ solid solutions (R=Tb, Dy, X′=Ga, In; x≤1.4) have been studied by powder magnetization measurements. All the series are characterized by ferrimagnetic ordering and by a decrease in Curie temperatures with the substitution (ΔT_c/Δx≈−39 K for X′=Ga and ΔT_c/Δx≈−75 K for X′=In). The RMn₆Sn_6−xGa_x systems are characterized by a strong decrease in the spin reorientation temperature with substitution (ΔT_t/Δx≈−191 K and −78 K for R=Tb and Dy, respectively) while this transition almost does not change in systems containing indium. The coercive fields drastically decrease with the substitution in the TbMn₆Sn_6−xGa_x system while the substitution of In for Sn has a weaker effect. The coercive fields of the Dy compounds do not vary greatly with the substitution in both series. The behaviour of the TbMn₆Sn_6−xGa_x is compared with the evolutions observed in the TmMn₆Sn_6−xGa_x series. This comparison strongly suggests that the replacement of Sn by Ga changes the sign of the A₀² crystal field parameter.     

Temperature dependent neutron powder diffraction study of the Laves phase compound TbCo2

The structure, magnetization and magnetostriction of Laves phase compound TbCo₂ are investigated by temperature dependent high resolution neutron powder diffraction. The compound crystallizes in the cubic Laves phase C15 structure above its Curie temperature T_C and exhibits a rhombohedral distortion (space group ) below T_C. By an appropriate extrapolation of the temperature factor of Co atom above T_C, the Rietveld refinement of the neutron powder diffraction data of the rhombohedral structure converges satisfactorily and reveals that the moments of Co1(3b) and Co2(9e) are almost equal. Tb moment follows well the Brillouin function. The total magnetic moment of TbCo₂ is about 5.8μ_B/f.u., the anisotropic magnetostriction constant λ₁₁₁ is about 4.6 × 10⁻³ and the volume magnetostriction ω_s is about 8.7 × 10⁻³ at 14 K.     

Magnetic structure of the CeScSi-type RScGe compounds (R = Pr, Nd, Tb)

Subsequent magnetic transitions were recently reported for the CeScSi-type RScGe (R = rare earth) equiatomic intermetallic compounds. The compounds TbScGe and NdScGe order ferromagnetically at T_C = 216 K and T_C = 200 K, respectively whereas PrScGe orders antiferromagnetically at T_N = 140 K. In addition, PrScGe demonstrates two other magnetic transitions at T_C1 = 88 K and T_C2 = 80 K in an applied field of 5 kOe. An investigation by neutron diffraction has been now carried out on these phases in an attempt to solve the magnetic structures corresponding to each ordering, and in this article the results obtained are reported. Below the Curie point, the magnetic structure of TbScGe and NdScGe is collinear ferromagnetic. The magnetic moment of Tb atoms coincides with the Z-axis of CeScSi-type unit cell (M_Tb = 8.63μ_B at 2 K), whereas the magnetic moment of Nd atoms has the θ = 52(2)° angle with Z-axis (M_Nd = 3.53(2)μ_B at 2 K). Below the Néel temperature, T_N = 140 K the magnetic structure of PrScGe consists of antiferromagnetic (0 0 2) rare-earth double layers with magnetic moments of the rare earth atoms collinearly ordered. The magnetic moments of Pr atoms (M_Pr = 1.72(3)μ_B at 100 K) have the θ = 62(2)° angle with the Z-axis. Between T_C1 = 82 K and T_C2 = 62 K the conversion of the commensurate antiferromagnetic collinear type structure to the ferrimagnetic collinear type structure with propagation vector K = [0, 0, 1/2] was observed: the magnetic moments of Pr double layers became sine modulated along the Z-axis. Below T_C2 = 62 K the magnetic structure of PrScGe compound consists of ferrimagnetic (0 0 1/2) layers (amplitude of Pr magnetic moment M_Pr = 3.31(9)μ_B at 5 K).     

Crystallographic and magnetic properties of HfFe6Ge6-type REFe6Sn4Ge2 compounds (RE = Y, Gd–Er)

The REFe₆Sn₄Ge₂ (RE = Y, Gd–Er) compounds have been synthesized and studied by powder X-ray diffraction and magnetisation measurements. These compounds crystallize in the hexagonal HfFe₆Ge₆ structure although the parent ternary compounds REFe₆X₆ (X = Ge, Sn) display more complicated orthorhombic crystal structure. This evolution is discussed and interpreted on the basis of the relaxation of some RE–X contacts in the quaternary compounds. The iron sublattice order antiferromagnetically above room temperature (554 ≤ T_N ≤ 560 K) while the paramagnetic RE compounds display a second transition at low temperature (7.3 ≤ T_t ≤ 42.7 K). The magnetisation versus field curves display a metamagnetic behaviour at 4.2 K. The corresponding value of the magnetisation suggests a non-collinear ordering of the RE sublattice.