Magnetostructural phase transitions of DyFe4Ge2: Part II Neutron diffraction

We present the temperature magnetic phase diagram of the compound DyFe₄Ge₂ determined from neutron diffraction data for the entire magnetically ordered regime. DyFe₄Ge₂ undergoes at a simultaneous structural and magnetic transition of second order (or weakly first order) followed by two subsequent isostructural first-order magnetic transitions at and T_ic1=28K:

The re-entrant lock-in magnetic phase is stable in the high-temperature range T_ic2–T_N and in the low-temperature range 1.5 K–T_ic1 while the incommensurately modulated magnetic phase is sandwiched in the intermediate range T_ic1–T_ic2 between the two commensurate phases. The wave vector q₂ has a temperature-dependent length with a minimum in the middle of the incommensurate range and corresponds to a multiaxial amplitude modulated phase. Symmetry analysis leads for both propagation vectors in Cmmm to a twofold and fourfold splitting of the tetragonal Dy 2b site and the Fe 8i sites, respectively. The low temperature and the phases correspond to 3D canted magnetic structures described by the irreducible representations (Irreps) Γ₂+Γ₃ while the high-temperature q₁ phase to 2D canted magnetic structures described by a single Irrep Γ₂. The T_ic2 transition is connected with reorientations of both Fe and Dy moments.     

Magnetic structure of the Sm5Ge4-type Tb2Ti3Ge4

The orthorhombic Sm₅Ge₄-type Tb₂Ti₃Ge₄ shows square modulated non-collinear magnetic ordering with wave vector K=[±1/3, 1/2, 1/2] at 2 K. The terbium magnetic moments lie in the bc plane and magnetic moment value of 7.5(2) μ_B/Tb is obtained at 2 K.     

Magnetic structure of the La3NiGe2-type Tb3NiGe2 and Mn5Si3-type Tb5NixGe3−x (x=0 and 0.3)

We present a neutron powder diffraction investigation of the magnetic structure of La₃NiGe₂-type Tb₃NiGe₂ and Mn₅Si₃-type Tb₅Ni_xGe_3−x (x=0, 0.3) compounds. It is found that below∼135 K Tb₃NiGe₂ exhibits a commensurate b-collinear ferrimagnetic ordering with C_2h′={1, m_z, 1′×2_z, 1′×1?} magnetic point group. The Mn₅Si₃-type Tb₅Ge₃ and Tb₅Ni_0.3Ge_2.7 compounds are found to present a flat spiral type antiferromagnetic ordering at 85 and ≥89 K, respectively. The Ni for Ge substitution is found to decrease the flat spiral ordered magnetic unit cell from a×a×40c of Tb₅Ge₃ (below 40 K) down to a×a×5c for Tb₅Ni_0.3Ge_2.7 (below ∼10 K).     

Magnetic order of Mn5Si3-type Tb5Sb3 and Tb5Si1.5Sb1.5

Neutron diffraction study has been performed on the Tb₅Sb₃ and Tb₅Si_1.5Sb_1.5 compounds (hexagonal Mn₅Si₃-type, hP16, P6₃/mcm) to understand their magnetic structures. The temperature dependence of neutron diffraction results proves that these intermetallics show a complex magnetic ordering. The Tb₅Sb₃ presents five subsequent changes in magnetic structure at ∼150, 119, 85, 70 and 54 K on cooling: paramagnet→antiferromagnetic flat spiral→ferromagnetic cone→antiferromagnetically canted ferromagnetic cone→canted AF→sine modulated AF. The Tb₅Si_1.5Sb_1.5 shows two subsequent changes in magnetic structure at 123 and 66 K: paramagnet→sine modulated antiferromagnet I→sine modulated antiferromagnet II. The Tb₅Si₃, Tb₅Sb₃ and Tb₅Si_1.5Sb_1.5 have the different magnetic structure in the full temperature range.     

Magnetic structure of the Mn5Si3-type Er5Ge3 compound

The Er₅Ge₃ compound (Mn₅Si₃-type, hP16, P6₃/mcm) at 4 K shows magnetic ordering of the antiferromagnetic type. Its magnetic structure consists of sine modulated collinear magnetic moments of Er that are parallel to the c axis (with a propagation vector k=[0 0 ±0.3]). This corresponds to the magnetic unit cell (a a 10c), the values of the magnetic moment of the Er atoms being, as a general formula, M_z≈M₀ cos [2π(Z–1/4)(1–kZ)], with M₀=9.2(2) μ_B at 4 K.     

Low-temperature neutron diffraction study of the crystal and magnetic phase transitions in DyCrO4

The crystal and magnetic structures of DyCrO₄ were studied using neutron powder diffraction. Complete diffraction data at 3.6, 17, 27, and 40 K show that a crystal structural phase transition from tetragonal I4₁/amd to orthorhombic Imma symmetry is found to take place between 27 and 40 K. This transition does not involve a significant change in the unit cell volume. Strong ferromagnetic reflections are observed at 3.6 and 17 K, and can be fit well using the magnetic model of space group Im'ma', with the moments of both Dy³⁺ and Cr⁵⁺ ions aligning along the y-axis. Detailed temperature dependent magnetic intensities of 101/011 and 211/121 peaks reveal a Curie temperature of T_c=22.35(15) K.     

Crystal structure and magnetic properties of TbFe0.4Ge2 compound

Neutron diffraction and magnetic measurements were performed on polycrystalline TbFe_0.4Ge₂ which crystallizes with the orthorhombic structure of the CeNiSi₂-type. Despite the presence of some clear anomalies in the low-temperature magnetic susceptibility, the neutron diffraction experiment did not reveal any long-range magnetic ordering of the Tb magnetic moments down to 1.57 K.     

Magnetic structures of R3Cu4Si4 (R=Dy, Ho and Er)

Polycrystalline samples of R₃Cu₄Si₄ (R=Dy, Ho, Er) intermetallics were studied with neutron diffraction methods. All of them crystallize in the orthorhombic structure of Gd₃Cu₄Ge₄-type and order antiferromagnetically at low temperatures. Magnetic moments localized at the rare earth atoms, that occupy two non-equivalent 2d and 4e sublattices, order simultaneously in Dy₃Cu₄Si₄. The order is described by the propagation vector accompanied by , δ=0.025(2). In Ho₃Cu₄Si₄ two propagation vectors are needed to model the magnetic order. These are: for the 4e sublattice, which disorders as the first when the temperature increases, and for the 2d sublattice. A similar situation is observed for Er₃Cu₄Si₄ where the propagation vectors are: k=(0,1−δ,0), δ=0.097(2) for the 4e sublattice, which disorders as the first with increasing temperature, and , δ=0.0015(6) for the 2d sublattice.     

Magnetic structure of TmCu2Ge2

TmCu₂Ge₂ compound crystallizes in the tetragonal ThCr₂Si₂-type crystal structure. The neutron diffraction reveals the presence of an incommensurate antiferromagnetic order below T_N=2.5 K. The Tm magnetic moment of 5.0(1) μ_B at 0.47 K is parallel to the c-axis. The order is described by the propagation vector k=[k_x, k_x, 0], where k_x=0.117(3). The increase of the values of the components k_x near the Néel temperature is observed.     

Magnetic order in CaMn2Sb2 studied via powder neutron diffraction

This paper reports a neutron powder diffraction study of CaMn₂Sb₂ in the temperature range of 20–300 K. Collinear long-range antiferromagnetic order of manganese ions occurs below 85 K, where a transition is observed in the dc magnetic susceptibility measured with a single crystal. Short-range magnetic order, characterized by a broad diffraction peak corresponding to a d-spacing of approximately 4 Å (2θ≈22°), is also observed above 20 K. The long-range antiferromagnetic order is indexed by the chemical unit cell, indicating a propagation vector k=(0 0 0), with a refined magnetic moment of 3.38 μ_B at 20 K. Two possible magnetic models have been identified, which differ in spin orientation for the two manganese ions with respect to the ab plane. The model with spins oriented at a 25±2° angle relative to the ab plane gives an improved fit compared to the other model in which the spins are constrained to the ab plane. Representational analysis can account for a model involving a c-axis component only by the mixing of two irreducible representations.     

Understanding the magnetic ground state of rare-earth intermetallic compound Ce4Sb3: Magnetization and neutron diffraction studies

Magnetization and neutron diffraction studies have been performed on Ce₄Sb₃ compound (cubic Th₃P₄-type, space group I4¯3d, no. 220). Magnetization of Ce₄Sb₃ reveals a ferromagnetic transition at ∼5 K, the temperature below which the zero-field-cooled and field-cooled magnetization bifurcate in low applied fields. However, a saturation magnetization (M_S) value of only ∼0.93μ_B/Ce³⁺ is observed at 1.8 K, suggesting possible presence of crystal field effects and a paramagnetic/antiferromagnetic Ce³⁺ moment. Magnetocaloric effect in this compound has been computed using the magnetization vs. field data obtained in the vicinity of the magnetic transition, and a maximum magnetic entropy change, −ΔS_M, of ∼8.9 J/kg/K is obtained at 5 K for a field change of 5 T. Inverse magnetocaloric effect occurs at ∼2 K in 5 T indicating the presence of antiferromagnetic component. This has been further confirmed by the neutron diffraction study that evidences commensurate antiferromagnetic ordering at 2 K in zero magnetic field. A magnetic moment of ∼1.24μ_B/Ce³⁺ is obtained at 2 K and the magnetic moments are directed along Z-axis.     

Neutron diffraction study of the U(Pd1−xFex)2Ge2 magnetic structure

The neutron diffraction and magnetic susceptibility studies have shown that the magnetic structure of UPd₂Ge₂ changes dramatically even under very low iron doping. Though the general magnetic structure of pure UPd₂Ge₂ and of 1%Fe-doped samples is the same, the temperature intervals of existence of different magnetic phases are different. The values of transition temperatures, where (i) the ‘square’ modulated longitudinal spin-density wave (LSDW) structure with the propagation vector k=(0; 0; ) starts to transform into the sinusoidal modulated LSDW structure and (ii) the commensurate phase transforms into incommensurate one, shift under the 1%Fe doping to the higher temperatures (from 50 to 65 K and from 80 to 90 K, respectively). In the pure and 1%Fe-doped UPd₂Ge₂, the magnetic transition from the commensurate to incommensurate phase is accompanied by the drastic decrease of the propagation vector k_z. In the 2%Fe-doped sample, besides the Néel point of T_N=135 K, we have found two additional characteristic temperatures of 65 and 93 K. Below 65 K, the material has a simple antiferromagnetic (AF) structure with the propagation vector k=(0; 0; 1) and, at 65 K<T<T_N, the magnetic structure is LSDW with sinusoidal modulation. Over almost the total region 65 K<T<T_N, the LSDW magnetic structure is incommensurate. Only at about 93 K, the propagation vector passes the commensurate value of , whereas at 65<T<93 K and at 93 K<T<T_N. We have found that the magnetic susceptibility and the uranium magnetic moment are sensitive to the transition. With increasing iron concentration to x0.15, the simple AF structure with k=(0; 0; 1) develops over all temperature region up to the Néel point. Below T_N, the uranium magnetic moments are always parallel to the tetragonal c-axis.     

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.     

Phase transitions in BaCeO3: neutron diffraction and Raman studies

Polycrystalline samples and small single crystals of the perovskite BaCeO₃ were studied by neutron diffraction and Raman spectrometry between 300 and 1200 K. The controversy about the phase transitions originally deduced from our previous Raman study and those observed since by neutron diffraction by Knight has stimulated this work. Pretransitional effects which are detected by Raman much before long-range ordering takes place can partly explain the above disagreement. A continuous monitoring of the structural changes by neutron diffraction and by Raman spectroscopy including polarization analysis has allowed discussion of the transition mechanisms: The first transition Pnma–Imma takes place at 573 K and is of second order. Although some modes soften when the temperature is raised as in many of these perovskite compounds the transition is likely partly displacive partly order–disorder. The Raman modes which disappear transform in modes at the X point of the Brillouin zone of the Imma phase. The second transition Imma–R c takes place at 673 K and is first order. The last transition R c–Pm3m occurs above 1200 K and the transition temperature which can be deduced by extrapolation to zero Raman intensity is in good agreement with neutron results. This second order transition is progressive and begins at about 400 K, the intermediate R c structure appearing as an attempt for slowing down the structural evolution toward the cubic perovskite form.     

Magnetic properties of the intermetallic compound Ce5Ge4

Magnetic and magnetocaloric properties of the compound Ce₅Ge₄ have been studied. This compound has orthorhombic Sm₅Ge₄-type structure (space group Pnma, no. 62) and orders ferromagnetically at ~12 K (T_C). The paramagnetic Curie temperature is ~−20 K suggesting the presence of competing ferromagnetic and antiferromagnetic interactions in this compound. The magnetization does not seem to saturate even in fields of 90 kOe at 3 K consistent with the presence of competing interactions. Saturation magnetization value (extrapolated to 1/H→0) of only 0.8μ_B/Ce³⁺ is obtained compared to the free ion value of 2.14μ_B/Ce³⁺. This moment reduction in the ordered state of Ce₅Ge₄ could be due to partial antiferromagnetic/paramagnetic ordering of the Ce moments and may also be due to crystalline electric field effects. Magnetic entropy change near T_C, calculated from the magnetization vs. field data, is found to be moderate with a maximum value of ~9 J/kg/K at ~11 K for a field change of 90 kOe.     

Direct evidence for the magnetic ordering of Nd ions in NdMn2Si2 and NdMn2Ge2 by high resolution inelastic neutron scattering

We have investigated the low energy nuclear spin excitations in NdMn₂Si₂ and NdMn₂Ge₂ by high resolution inelastic neutron scattering. Previous neutron diffraction investigations gave ambiguous results about Nd magnetic ordering at low temperatures. The present element-specific technique gave direct evidence for the magnetic ordering of Nd ions. We found considerable difference in the process of the Nd magnetic ordering at low temperature in NdMn₂Si₂ and NdMn₂Ge₂. Our results are consistent with those of magnetization and recent neutron diffraction measurements.     

A comparative study of the magnetoelastic properties of the YFe10V2 and NdFe10V2 compounds

The magnetoelastic properties of iron-rich REFe₁₀V₂ (RE=Nd, Y) compounds were studied via magnetostriction and thermal expansion measurements in the 5–300 K range of temperature in up to 6 T external fields. Results of thermal expansion analysis show that the spontaneous magnetostriction of the compounds mostly originates from itinerant magnetization. Besides, the small volume striction appearing in the thermal expansion of the Nd compound close to 50 K suggests the existence of a basal to conical spin re-orientation transition. The volume magnetostriction isotherms of both compounds take minimum values for external field corresponding to the anisotropy field. In addition, the anisotropic and the volume magnetostriction traces of the NdFe₁₀V₂ take marked maxima under low field, with a relatively large initial magnetostrictivity, again more pronounced at the conical–axial spin re-orientation transition (T_SR=130 K). Analysis of the anisotropic magnetostriction of the Nd compound leads to the conclusion that the contribution of Nd–Fe interactions is negligible. The temperature dependence of volume magnetostriction is in good agreement with prediction of a phenomenological model based upon a fluctuating local band theory. This analysis shows that the difference between the forced volume strictions of Y and Nd compounds below and above T_SR originates from the Nd sublattice magnetization.