A new family of rare earth compounds,the ternary silicides RE2RhSi3 (RE = Y,La, Ce,Nd, Sm,Gd, Tb,Dy, Ho,Er) - crystal structure electrical and magnetic properties

New ternary silicides RE₂RhSi₃ (RE = Y, La, Ce, Nd, Sm, Gd, Tb, Dy, Ho, Er) have been prepared. They crystallize with a hexagonal symmetry structure which is derived from the AlB₂-type. Si and Rh atoms are inside RE₆ distorted trigonal prisms and are ordered in a two dimensional sublattice perpendicular to the c axis. The a and c parameters are approximately twice those of the corresponding disilicides RESi₂. La₂RhSi₃ and Y₂RhSi₃ are not superconducting down to 1.6 K. Nd₂RhSi₃ is ferromagnetic at 15 K, but the other silicides order antiferromagnetically with metamagnetic phase transitions for certain of them.     

Magnetic properties of RCoSi2 compounds (R=rare earth)

New ternary silicides of composition RCoSi₂ (R=rare earth and Y) have been prepared and found to crystallize in the orthorhombic CeNiSi₂-type structure. Their magnetic properties have been studied by means of susceptibility measurements between 2 and 250 K. The Ce and Y compounds show essentially temperature independent Pauli paramagnetism. The compounds with R=Nd, Sm, Gd, Tb, Dy, Ho, Er and Tm show antiferromagnetic ordering below 20 K. The effective rare earh moments in the paramagnetic state agree well with the free ion values, and, for the heavy rare earths, the Néel temperatures vary with the De Gennes factor. There is no indication for a magnetic contribution from the Co sublattice.     

Critical bond lengths and their role in spontaneous magnetostriction of R2Fe17CX (R=Y,Nd, Gd,Tb, Er)

High-energy high-flux synchrotron X-rays have been used to study the spontaneous magnetostriction of R₂Fe₁₇ (R=Y, Nd, Gd, Tb, Er) and their carbides in the temperature range 10–1100 K. Addition of interstitial carbon greatly increases both the Curie temperatures (T_C) and the spontaneous magnetostrain of the compounds, while reduces the anisotropy of the magnetostrain by expanding the distances between rare-earth and neighboring Fe sites. The increase of T_C with carbon is due to the increased spatial separation of the Fe hexagon layers. On the basal plane, the Fe hexagons are squeezed and the contribution of Fe sublattice to spontaneous magnetostriction is attenuated, while that of rare-earth sublattice is enhanced. The average bond magnetostrain around Fe sites are in linear relation with their hyperfine field intensities.     

Magnetic order and hyperfine interactions in RFe6Al6 (R = rare earth)

The systems RFe₆Al₆(R = Y, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb) crystallize in the tetragonal body centered I4/mmm structure. In striking contrast to the magnetic behaviour of RFe₄Al₈ (weakly coupled R and Fe sublattices, complicated magnetic structure, low T_c ~ 130 K), in the RFe₆Al₆ systems all magnetic sublattices order simultaneously at a relatively high temperature. The magnetization curves start with low values at low temperatures and rise to very high values at T_max ~ 230 K and then drop to 0 at T_c ~ 330 K. All samples show strong hysteresis effects at temperatures just below T_max. Mossbauer studies of ⁵⁷Fe in the (f) and (j) sites and ¹⁵¹Eu, ¹⁵⁵Gd, ¹⁶¹Dy, ¹⁶⁶Er and ¹⁷⁰Yb in the (a) site yield all hyperfine interaction parameters and temperature dependence of the local magnetic moments. All Mossbauer and magnetization experimental results can be explained in a self consistent way with a simple molecular field model. The Fe in the (j) site plays the dominant role in its strong intrasublattice ferromagnetic exchange and its strong antiferromagnetic exchange with the rare earth site. The Fe in the (f) site have an antiferromagnetic intrasublattice exchange, they have a canted strcuture with the ferromagnetic component parallel to the (j) sublattice magnetization.     

Magnetic properties of RAu2Si2 rare earth compounds

The magnetic properties of the R Au₂Si₂ compounds with R = Ce-Er have been investigated. It was found that the compounds for which R = Ce, Sm, Gd, Tb and Dy are antiferromagnetically ordered at temperatures ranging from 5.7 to 15.9°K. PrAu₂Si₂ and NdAu₂Si₂ exhibit paramagnetic behavior for temperatures as low as 4.2°K. The magnetic structure is ferrimagnetic for the compounds in which R = Eu, Ho, and Er. The Eu compound is in the divalent state. The Néel and Curie points for this system do not follow the De-Gemnes function. Curie-Weiss Behavior is exhibited by all the compounds with effective moments in good agreement with that of a free tripositive lanthanide ion. The difference in magnetic properties between R Au₂Si₂ and the isomorphous R Fe₂Si₂ series is discussed.     

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.     

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.     

Crystals and magnetic structure of RMn2Si2 (R = Pr, Nd, Y) and YMn2Ge2

Crystallographic and magnetic properties of PrMn₂Si₂, NdMn₂Si₂, YMn₂Si₂ and YMn₂Ge₂ intermetallics were studied by X-ray, neutron diffraction and magnetometric measurements. The crystal structure of all four compounds was confirmed to be body-centered tetragonal (space group I4/mmm). All were found to be antiferromagnetic with Néel points at 368, 380, 460 and 395 K respectively. Neutron diffraction results indicate that their magnetic structure consists of ferromagnetic layers composed of Mn ions piled up along the c-axis. Each layer is antiferromagnetically coupled to adjacent layer. The magnetic space group is I_p4/m′m′m′. No magnetic ordering of the R sublattice was observed at 1.8 K in the case of R = Pr and Nd.     

Influence of Ho substitution for Nd on magnetic properties of the Nd1−xHoxMn2Ge2 germanides

The structure and magnetic properties of Nd_1−xHo_xMn₂Ge₂ (0.0≤x≤1.0) germanides were studied by X-ray diffraction (XRD), differential scanning calorimetry (DSC) techniques and AC magnetic susceptibility measurements. All compounds crystallize in the ThCr₂Si₂-type structure with the space group I4/mmm. Substitution of Ho for Nd leads to a linear decrease in the lattice constants and the unit cell volume, and the magnetic interactions in the Mn sublattice cross over from a ferromagnetic character to an antiferromagnetic one. A typical SmMn₂Ge₂-like behavior is observed for x=0.6 and 0.8. The results are collected in a phase diagram.     

Influence of Si and Co substitutions on magnetoelastic properties of R2Fe17 (R=Y, Er and Tm) intermetallic compounds

The magnetostriction of the off-stoichiometric R₂Fe₁₇-type intermetallic compounds based on R₂Fe_14−xCo_xSi₂ (R=Y, Er, Tm and x=0, 4) was measured, using the strain gauge method in the temperature range 77-460 K under applied magnetic fields up to 1.5 T. All compounds show sign change and reduction in magnetostriction values compared to the R₂Fe₁₇ compounds by Si substitution. For Y₂Fe₁₄Si₂ and Er₂Fe₁₄Si₂, saturation behaviour is observed near magnetic ordering temperature (T_C), whereas for Tm₂Fe₁₄Si₂, saturation starts from T>143 K. Also, Co substitution has different effects on the magnetostriction of R₂Fe₁₄Si₂ compounds. In Er₂Fe₁₀Co₄Si₂ and Tm₂Fe₁₀Co₄Si₂, saturation occurs below the spin reorientation temperature (T_SR). In addition, in Er₂Fe₁₄Si₂, a sign change occurs in the anisotropic magnetostriction (Δλ) as well as the volume magnetostriction (ΔV/V) at their T_SR values. The volume magnetostrictions of the Tm-containing compounds show an anomaly around their T_SR. In R₂Fe₁₄Si₂ compounds, parastrictive behaviour is also observed in ΔV/V near their T_C values. In addition, the magnetostriction of the sublattices is investigated. Results show that in R₂Fe₁₄Si₂ compounds, the rare-earth sublattice contribution to magnetostriction is negative and comparable to the iron sublattice, whereas, in R₂Fe₁₀Co₄Si₂ compounds, the rare-earth sublattice contribution is positive and larger than Fe sublattice. These results are discussed based on the effect of Si and Co substitutions on the anisotropy field of these compounds. Influence of the spin reorientation transition on the magnetostriction of these compounds is discussed in terms of the anisotropic sublattice interactions.     

Magnetic properties and structural chemistry of ternary silicides (RE,Th, U)Ru2Si2 (RE = RARE EARTH)

Ternary silicides (RE, Th, U)Ru₂Si₂ have been synthesized from the elements. All the compounds (RE = Y, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) were found to be isotypic and to crystallize with the structure type of ThCr₂Si₂ (ordered derivative of the BaAl₄-type). The magnetic behavior of these alloys was studied in the temperature range 1.5 K < T < 1100 K. Magnetic susceptibilities at temperatures T > 300 K closely follow a typical Van Vleck paramagnetism of free RE³⁺-ions. In the case of CeRu₂Si₂ susceptibilities are well described for 20 K < T < 1100 K by a Van Vleck paramagnetism of widely spaced multiplets; the observed effective paramagnetic moment μ_eff = 2.12 BM indicates a high percentage (85%) of Ce³⁺. SmRu₂Si₂ yields an effective moment μ_eff = 0.54 BM, which compares reasonably well with the Hund's rule J = 5/2 ground level for free Sm⁺ and a low-lying excited level with J = 7/2. For temperatures T > 15 K the magnetic susceptibility as a function of temperature follows the “Van Vleck behavior” for free Sm³⁺. At low temperatures ferromagnetic ordering was encountered for (Pr, Nd, Ho, Er, Tm)Ru₂Si₂, whereas antiferromagnetic ordering was observed for (Sm, Gd, Tb, Dy)Ru₂Si₂. The ordering temperatures are generally below 55 K. No superconductivity was found for temperatures as low as 1.8 K.     

3d-4f magnetic interactions and crystalline electric field in the R2Fe14B compounds : Magnetization measurements and Mössbauer study of Gd2Fe14B

Magnetization measurements on Gd₂Fe₁₄B single crystals show that the Fe anisotropy favors the c-axis of the tetragonal structure, as in Y₂Fe₁₄B. The exchange interactions between Gd and Fe spins are deduced from the temperature dependence of the Gd magnetization. A Mössbauer study with¹⁵⁵Gd shows the main axis of the electric field gradient to have different directions at the two rare-earth sites. Scaling the values obtained in Gd₂Fe₁₄ B yields values of exchange interactions between Nd and Fe spins (～ 400 K) and of 2^nd order crystal-field parameters acting on Nd ions (～ 300 K) in isomorphous Nd₂Fe₁₄B.     

Magnetic and electronic structure studies of the perovskite oxide Nd2/3Sr1/3MnO3 from the first principle calculation

Generalized gradient approximation (GGA) and GGA + U (U denotes on-site Coulomb interactions) methods are applied to investigate the magnetic and electronic structures of the perovskite oxide Nd_2/3Sr_1/3MnO₃. Under GGA the compound prefers ferrimagnetic ordering in which Nd sublattice is spin-antiparallel to Mn sublattice. Nd 4f states cross over the Fermi level under GGA, leading the ferrimagnetic Nd_2/3Sr_1/3MnO₃ to a metallic character. The on-site Coulomb interactions should be included to emphasize the localized feature of Nd 4f states. Under GGA + U, the spins of Nd and Mn sublattices tend to be parallel in the ground state, and fully spin-polarized Mn 3d electrons yield a half-metallic band structure for the ferromagnetic Nd_2/3Sr_1/3MnO₃. The ferromagnetic coupling between Nd and Mn sublattices is ascribed to the super-exchange interaction between Nd 4f and Mn 3d (t2g) electrons via O 2p electrons.     

Magnetocaloric effect in R2Fe17 (R=Sm,Gd, Tb,Dy, Er)

A series of R₂Fe₁₇ (R=Sm, Gd, Tb, Dy, Er) have been synthesized. The magnetocaloric effect (MCE) of these compounds has been investigated by means of magnetic measurements in the vicinity of their Curie temperature. The Curie temperature of Er₂Fe₁₇ is 294 K. The maximum magnetic entropy change of Er₂Fe₁₇ under 5 T magnetic field is ∼3.68 J/kg K. In the R₂Fe₁₇ (R=Sm, Gd, Tb, Dy, Er) system, the maximum magnetic entropy change under 1.5 T magnetic field is 1.72, 0.89, 1.32, 1.59, 1.68 J/kg K corresponding to their Curie temperature (400, 472, 415, 364, 294 K), respectively.     

Exchange-striction of rare earth-Al2 laves phase compounds

The exchange-striction of the cubic Laves phase compounds R-Al₂ (R =Gd, Tb, Dy, and Ho) has been determined at 0 K from measurements of thermal expansion. The results are interpreted in terms of rare earth sublattice (R-R) interactions, using the molecular field approximation. It is found that the signs of the strain derivatives of the molecular field constants are positive for Dy-Al₂ and Ho-Al₂ and negative for Gd-Al₂ and Tb-Al₂ compounds.     

Tetragonal rare earth (R) Iron borides,R1+εFe4B4 (ε≅0.1), with incommensurate rare earth and iron substructures

Crystallographic and magnetic properties of a new structural series of ternary borides with composition R_1+εFe₄B₄ (R = Ce, Pr, Nd, Sm, Gd, Tb, 0.11(Pr) ≤ε≤ 0.15(Tb) are reported. The compounds are built of incommensurate substructures of rare earth atoms (linear strings ?? c?), iron atoms (chains of edge sharing tetrahedra ?? c?),and boron atom pairs. A single crystal X-ray diffraction study of one representative (Sm_1.13Fe₄B₄) based on a commensurate structure model (composition : Sm₁₇(Fe₄B₄)₁₅, a = 7.07 Å, c ≡ 17c_Sm ≡ 15c_Fe= 58.69 Å, space group P4₂/n) revealed a periodic twist modulation of the Fe tetrahedra chains around c?. Magnetic susceptibility measurements on single crystals of another representative (Nd_1.11Fe₄B₄) revealed ferromagnetic ordering at T_c = 13 K. Above this temperature the magnetic properties are dominated by ferromagnetic inclusions (Fe₂B, Nd₂Fe₁₄B).     

Magnetic properties of ternary RMn2Si2 and RMn2Ge2 compounds

Magnetic properties of RMn₂Si₂ and RMn₂Ge₂ compounds, where R is a rare earth metal, have been investigated by magnetometric measurements. RMn₂Ge₂ (where R is a light rare earth) and LaMn₂Si₂ are ferromagnets. Remaining compounds have antiferromagnetic properties. DyMn₂Si₂ and ErMn₂Si₂ show ferromagnetic properties at low temperatures. It was confirmed that the value of Curie (or Néel) temperature for the Mn sublattice decreases with increasing c constant.     

Magnetic properties and structural data of ternary silicides: (RE,Th,U) Os2Si2 (RE= rare earth)

New ternary silicides (RE,Th,U) Os₂Si₂ have been synthesized from the elements. All the compounds (RE= Y,La,Ce,Pr,Nd,Sm,Gd,Tb,Dy,Ho,Er,Tm,Yb, Lu) were found to be isotypic and to crystallize with the ordered BaAl₄-type of structure (ThCr₂Si₂-type). Magnetic properties of these alloys — studied in the temperature range 1.5<T<1100 K — reveal a typical Van Vleck paramagnetism of free RE³⁺ ions at temperatures higher than 300 K. The observed effective paramagnetic moment of CeOs₂Si₂, μ(eff)=0.98 BM, is compatible with a rather low concentration (15%) of Ce³⁺. The effective moment of SmOs₂Si₂, μ(eff)=0.47 BM, is in reasonable agreement with a Hund's rule $\text{J=}\text{5}\text{2}$ ground level for free Sm³⁺. For temperatures above 25 K, the magnetic susceptibility as a function of temperature corresponds to the Van Vleck behavior for free Sm³⁺ (closely spaced multiplet, $\text{J=}\text{5}\text{2}$,$\text{J=}\text{7}\text{2}$. Magnetic ordering temperatures of REOs₂Si₂ silicides are generally below 42 K. (Pr,Nd,Ho,Er,Tm) Os₂Si₂ exhibit ferromagnetic ordering whereas (Sm,Gd, Tb,Dy) Os₂Si₂ show antiferromagnetic behavior. Above 1.8 K none of the samples was found to be superconducting.     

Spontaneous magnetostriction in R2Fe14B (R=Y,Nd, Gd,Tb, Er)

Thermal expansion anomalies of R₂Fe₁₄B (R=Y, Nd, Gd, Tb, Er) stoichiometric compounds were studied by X-ray diffraction with high-energy synchrotron radiation using a Debye–Scherrer geometry in temperature range of ∼10–1000 K. A large invar effect with a corresponding large temperature dependence of lattice parameters ∼10–15 K above their Curie temperatures (T_c) are observed. The a-axes show a larger invar effect than the c-axes in all compounds. The spontaneous magnetostrain of the lattices and bonds are calculated. The iron sublattice is shown to dominate the volumetric spontaneous magnetostriction of the compounds and the contribution from the rare-earth sublattice is roughly proportional to the spin magnetic moment of the rare earths. The bond-length changes are consistent with the theoretical spin-density calculation. The average bonds magnetostrain around Fe sites is approximately proportional to their magnetic moments.     

A magnetic study of the ThCr2Si2-type RPd2Ge2 (R=Pr, Nd) compounds. Magnetic structure of PrPd2Ge2 from powder neutron diffraction

The magnetic properties of the PrPd₂Ge₂ and NdPd₂Ge₂ compounds have been investigated by magnetic measurements, specific heat measurements and neutron diffraction experiments. The PrPd₂Ge₂ compound orders antiferromagnetically below T_N=5.0(2) with an original modulated magnetic structure characterized by a magnetic cell three times larger than the chemical one by tripling of the c parameter. The palladium atom is non magnetic and the Pr moments are parallel to the c-axis with a value of ≈2.0 μ_B at 2 K. The specific heat measurements clearly detect a low temperature transition for the NdPd₂Ge₂ compound, interpreted as a Nd sublattice antiferromagnetic ordering below 1.3(2) K.