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.     

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.     

Magnetic and transport properties of single-crystal Yb3Cu4Ge4

The magnetic and transport properties of single-crystal Yb₃Cu₄Ge₄ with the Gd₃Cu₄Ge₄-type orthorhombic structure are presented. Magnetization along the b-axis at 2 K saturates to 2.8_μB/Yb$2.8{\mu }_{\mathrm{B}}/\mathrm{Yb}$ at 3 kOe, while that along the a- and c-axes at 2 K are gradually increasing to the value of 1.5_μB/Yb$1.5{\mu }_{\mathrm{B}}/\mathrm{Yb}$ and 0.39_μB/Yb$0.39{\mu }_{\mathrm{B}}/\mathrm{Yb}$ at 50 kOe, respectively. The electrical resistivity within the ab-plane shows a metallic behavior in contrast to a broad maximum at around 30 K for that along the c-axis. Each resistivity for the principal axis suddenly decreases below 8 K. The specific heat shows a λ-type$\lambda \mathrm{-}\mathrm{type}$ sharp peak at 7.8 K. The electronic specific heat coefficient is estimated to be 29.4 mJ/mol Yb K² by fitting the magnetic part of the specific heat below 3 K. The magnetic entropy released up to T_C is 68% of that of R ln 2, expected for the doublet ground state. It is revealed that Yb₃Cu₄Ge₄ is categorized to a weak heavy-fermion system showing a ferromagnetic transition at 7.8 K with uniaxial anisotropy along the b-axis.     

Valence fluctuation in Ce2Co3Ge5 and crystal field effect in Pr2Co3Ge5

Polycrystalline samples of ternary rare-earth germanides R₂Co₃Ge₅ (R=La, Ce and Pr) have been prepared and investigated by means of magnetic susceptibility, isothermal magnetization, electrical resistivity and specific heat measurements. All these compounds crystallize in orthorhombic U₂Co₃Si₅ structure (space group Ibam). No evidence of magnetic or superconducting transition is observed in any of these compounds down to 2 K. The unit cell volume of Ce₂Co₃Ge₅ deviates from the expected lanthanide contraction, indicating non trivalent state of Ce ions in this compound. The reduced value of effective moment (μ_eff≈0.95 μ_B) compared to that expected for trivalent Ce ions further supports valence-fluctuating nature of Ce in Ce₂Co₃Ge₅. The observed temperature dependence of magnetic susceptibility is consistent with the ionic interconfiguration fluctuation (ICF) model. Although no sharp anomaly due to a phase transition is seen, a broad Schottky-type anomaly is observed in the magnetic part of specific heat of Pr₂Co₃Ge₅. An analysis of C_mag data suggests a singlet ground state in Pr₂Co₃Ge₅ separated from the singlet first excited state by 22 K and a doublet second excited state at 73 K.     

Magnetic properties of NdAu2Ge2

Physical properties of NdAu₂Ge₂, crystallising with the tetragonal ThCr₂Si₂-type crystal structure, were investigated by means of magnetic, calorimetric and electrical transport measurements as well as by neutron diffraction. The compound exhibits antiferromagnetic ordering below T_N=4.5 K with a collinear magnetic structure of the AFI-type. The neodymium magnetic moments are parallel to the c-axis and amount to 1.04(4) μ_B at 1.5 K. The observed magnetic behaviour is strongly influenced by crystalline electric field effect.     

Magnetocaloric effect in high-energy ball-milled Gd5Si2Ge2 and Gd5Si2Ge2/Fe nanopowders

Evolution of structure and magnetocaloric properties in ball-milled Gd₅Si₂Ge₂ and Gd₅Si₂Ge₂/0.1 wt% Fe nanostructured powders were investigated. The high-energy ball-milled powders were composed of very fine grains (70–80 nm). Magnetization decreased with milling time due to decrease in the grain size and randomization of the magnetic moments at the surface. The magnetic entropy change (ΔS_M) was calculated from the isothermal magnetization curves and a maximum value of 0.45 J/kg K was obtained for 32 h milled Gd₅Si₂Ge₂ alloy powder for a magnetic field change of 2 T while it was still low in Fe-contained alloy powders. The thermo-magnetic measurements revealed that the milled powders display distribution of magnetic transitions, which is desirable for practical magnetic refrigerant to cover a wide temperature span.     

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.     

Structure and low-temperature properties of Ba8Ni6Ge40

Structural, magnetic, heat capacity, electrical and thermal transport properties are reported on polycrystalline Ba₈Ni₆Ge₄₀. Ba₈Ni₆Ge₄₀ crystallizes in a cubic type I clathrate structure with unit cell a=10.5179 (4) Å. It is diamagnetic with susceptibility χ_dia=−1.71×10^-6 emu/g Oe. An Einstein temperature 75 K and a Debye temperature 307 K are estimated from heat capacity data. It exhibits n-type conducting behavior below 300 K. It shows high Seebeck coefficients (−111×10^-6 V/K), low thermal conductivity (2.25 W/K m), and low electrical resistivity (8.8 mΩ cm) at 300 K.     

Structure and magnetic entropy change of suck-cast Gd60Co26Al6Ge8 alloy

The Gd₆₀Co₂₆Al₆Ge₈ alloy has been prepared by the copper-mold suck-casting and its phase component has been investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy-dispersive spectroscopy (EDS). It is shown that this alloy consists of primary crystalline Gd₅Ge₃ phase and amorphous matrix. The glass transition temperature (T_g) and crystallization temperatures (T_x) occur at 292 and 320 °C, respectively. The maximal magnetic entropy change (ΔS_M) under 0-5 T field is about 7.6 J (kg⁻¹ K⁻¹) at 155 K and the refrigeration capacity (RC) is about 768 J kg⁻¹, which makes Gd₆₀Co₂₆Al₆Ge₈ bulk metallic glass matrix composite a promising candidate for magnetic refrigerant.     

Magnetic ordering and low-temperature thermodynamic properties of ErFe2Ge2

Polycrystalline sample of ErFe₂Ge₂ was investigated by means of magnetic susceptibility, heat capacity and electrical resistivity measurements, as well as by powder neutron diffraction. All these experiments yielded an evidence of magnetic ordering setting at about 3 K. The low-temperature neutron data revealed the formation of a sine-modulated commensurate antiferromagnetic structure characterized by the propagation vector k=(0, 0, ). The erbium magnetic moment is aligned parallel to the crystallographic a-axis. At T=1.55 K it is equal to 7.06(5) μ_B.     

Effect of Fe-substitution on microstructure, hysteresis behaviour and magnetocaloric effect in Gd5Si2Ge2 Alloys

Effect of Fe-substitution on the phase formation, partitioning behaviour of Fe in the co-existing phases, magneto-structural transition, magnetic entropy change and associated hysteresis losses has been investigated in Gd₅Si₂Ge₂ alloy. The virgin alloy crystallizes in monoclinic Gd₅Si₂Ge₂-type phase, while Fe-substituted alloys form mixed monoclinic Gd₅Si₂Ge₂-type and orthorhombic Gd₅Si₄-type phases. Electron probe microanalysis reveals that Fe does not dissolve in the matrix, but influences the magneto-structural transitions. Magneto-structural characterization of the Fe-containing alloys reveals that the Fe-substitution suppresses the structural transition observed at 273 K in virgin alloy. A maximum magnetic entropy change, ΔS_M of 6.5 J/kg-K at 273 K was observed for a field change of 2 T in Gd₅Si₂Ge₂ alloy. The Fe-substituted alloys exhibit lower value of ΔS_M but with reduced hysteresis losses.     

Spectral properties of Nd-doped Sr3Ga2Ge4O14 crystal

Neodymium doped strontium gallogermanate crystals were grown successfully by the Bridgman technique. The linear thermal expansion coefficients for the c- and a-axes were measured as 5.8 × 10⁻⁶ °C⁻¹ and 6.5 × 10⁻⁶ °C⁻¹. Absorption spectra, and fluorescence spectra, as well as fluorescence decay curves of Nd³⁺-doped Sr₃Ga₂Ge₄O₁₄ crystal, have been recorded at room temperature and used to calculate the absorption and stimulated emission cross-sections. Based on the Judd-Ofelt theory, three intensity parameters were obtained. The luminescent quantum efficiency of the ⁴F_3/2 level was determined to be approximately 73.8% for this material. Compared with other Nd³⁺-doped laser crystals, Nd³⁺-doped Sr₃Ga₂Ge₄O₁₄ crystal displays special laser properties due to its disorder structure.     

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 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 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.     

Preferential surface oxidation of Gd in Gd5Ge4

Gd oxidizes preferentially at the (0 1 0) surface of Gd₅Ge₄. This is consistent with thermodynamic data for the bulk oxides. Upon oxidation in vacuum, the gadolinium oxide displaces or covers the Ge. Oxidation is more extensive at 600 K than at 300 K, because more oxygen is incorporated into the surface and the shift of the Gd binding energy is larger.     

Anisotropic magnetic behavior of PrAg2Ge2—a crystal field study

A crystal field (CF) analysis of the experimental, single crystal magnetic susceptibility data (300-1.8 K) along and perpendicular to the [0 0 1] axis, of the Ag based rare earth intermetallic compound PrAg₂Ge₂, has been carried out for the first time, thus yielding first reliable set of CF parameters for the system. The susceptibility feature at 12 K is possibly due to CF effects rather than the magnetic order as proposed earlier. This removes the issue of the transition temperature being too large to scale properly with the de Gennes factor. We have used the set of CF parameters to find the Stark energies of the ground state and the excited states together with their corresponding eigenvectors, and the thermal variation of the magnetic specific heat. Possible explanation of the absence of magnetic ordering of the Pr sublattice and the nature of variation of the CF parameters with the substitution of transition-metal ion in PrAg₂Ge₂ is studied and discussed in relation to PrAu₂Ge₂. All computations have been carried out using the intermediate coupling scheme including the J-mixing.     

Neutron diffraction study of magnetic ordering in PrCu2Si2, PrCu2Ge2, PrFe2Ge2 and NdFe2Ge2

A neutron diffraction study of polycrystalline PrCu₂Si₂ [1], PrCu₂Ge₂ [2], PrFe₂Ge₂ [3] and NdFe₂Ge₂ [4] intermetallics carried out at liquid helium temperature shows the presence of a collinear antiferromagnetic order below T_N = 19 ± 1 K [1], T_N = 16 ± 1 K [2], T_N = 9 ± 1 K [3] and 13 ± 1 K [4]. Magnetic moment, parallel to the c-axis is localized on RE ions only. The magnetic structure of these compounds consists of ferromagnetic layers perpendicular to the c-axis coupled antiferromagnetically with sequence +-+- for PrCu₂Si₂ and PrCu₂Ge₂ and +--+ for PrFe₂Ge₂ and NdFe₂Ge₂. The RE moments amount close to the free ion values for Fe containing compounds but are smaller in those containing Cu suggesting a fairly strong influence of crystal field.     

Effect of Si/Ge ratio on resistivity and thermopower in Gd5SixGe4−x magnetocaloric compounds

The effect of Si/Ge ratio on resistivity and thermopower behavior has been investigated in the magnetocaloric ferromagnetic Gd₅Si_xGe_4−x compounds with x=1.7-2.3. Microstructural studies reveal the presence of Gd₅(Si,Ge)₄-matrix phase (5:4-type) along with traces of secondary phases (5:5 or 5:3-type). The x=1.7 and 2.0 samples display the presence of a first order structural transition from orthorhombic to monoclinic phase followed by a magnetic transition of the monoclinic phase. The alloys with x=2.2 and 2.3 display only magnetic transitions of the orthorhombic phase. A low temperature feature apparent in the AC susceptibility and resistivity data below 100 K reflects an antiferromagnetic transition of secondary phase(s) present in these compounds. The resistivity behavior study correlates with microstructural studies. A large change in thermopower of −8 μV/K was obtained at the magneto-structural transition for the x=2 compound.     

Structure, magnetic and electrical transport properties of cosputtered Fe0.5Ge0.5 nanocomposite films

Fe_0.5Ge_0.5 nanocomposite films with different film thicknesses were fabricated using cosputtering. The films are composed of Ge, Fe and Fe₃Ge₂, and are ferromagnetic at room temperature. The saturation magnetization and magnetic interaction including dipolar interaction and exchange coupling increase with the increasing film thickness. The electrical conductance mechanism turns from metallic to semiconducting and the saturation Hall resistivity ρ_xys increases with the decreasing film thickness. At 28 nm, ρ_xys is ∼137 μΩ cm at 2 K, about 150 times larger than that of pure Fe film (0.9 μΩ cm) and four orders larger than that of bulk Fe. The ρ_xy-H curves of all the films show the same linearity character in low-field range even though the temperature-independent slope is different at different film thicknesses. At high temperatures, the skew scattering mechanism is dominant. At low temperatures, side-jump effect should be dominant at large resistivity ρ_xx regime for the thin films, and the skew scattering is dominant at small ρ_xx regime for the thick films.