Structural, magnetic and magnetocaloric properties of the Gd5Si4−xSbx (x=0.5-3.5) phases

Substitution of Sb for Si in the Gd₅Si₄ phase results in the formation of ternary Gd₅Si_4−xSb_x phases with three different structure types. For x≤0.38 the Gd₅Si₄-type structure (Pnma space group) with all interslab T-T dimers intact exists (T is Si or Si/Sb mixture), in the x=1.21-1.79 region the Sm₅Ge₄-type structure (Pnma) with all interslab dimers broken is found. A further increase in the Sb concentration (x=2.27-3.1) leads to the appearance of the Eu₅As₄-type structure (Cmca) with broken but equivalent interslab T?T bonds. The Gd₅Si_4−xSb_x phases with 1.21≤x≤3.1 undergo ferromagnetic transitions in the temperature range from 164 to 295 K. Magnetocaloric effect in terms of the isothermal entropy change, ΔS, reaches the maximum values of -3.7(4), -4.2(6) and -4.6(7) J/kg K for the Gd₅Si₂Sb₂, Gd₅Si_1.5Sb_2.5 and Gd₅SiSb₃ samples, respectively.     

Field and temperature induced colossal strain in Gd5(SixGe1−x)4

Gd₅(Si_xGe_1−x)₄, known for its giant magnetocaloric effect, also exhibits a colossal strain of the order of 10,000 ppm for a single crystal near its coupled first-order magnetic-structural phase transition, which occurs near room temperature for the compositions 0.41≤x≤0.575. Such colossal strain can be utilised for both magnetic sensor and actuator applications. In this study, various measurements have been carried out on strain as a function of magnetic field strength and as a function of temperature on single crystal Gd₅Si₂Ge₂ (x=0.5), and polycrystalline Gd₅Si_1.95Ge_2.05 (x=0.487) and Gd₅Si_2.09Ge_1.91 (x=0.52). Additionally a giant magnetostriction/thermally induced strain of the order of 1800 ppm in polycrystalline Gd₅Si_2.09Ge_1.91 was observed at its first order phase transition on varying temperature using a Peltier cell without the use of bulky equipment such as cryostat or superconducting magnet.     

Effects of high Fe substitution for Mn on phase transition and magnetic properties of YFexMn12−x compounds

YFe_xMn_12−x (x=7-10) compounds were synthesized; their structure and magnetic properties were investigated, the results reveal that a higher Fe concentration x makes the crystal phase change from ThMn₁₂-type to Th₂Zn₁₇-type, with the phase transition point x=9; the Curie temperature increases with increasing x, which becomes 290 K for x=8.8 and 150 K for x=7; and the magnetization also increases monotonically with increasing x until the phase transition point.     

Magnetic phase diagram of Tb3−xHoxCu4Sn4 system

Magnetic phase diagram of Tb_3−xHo_xCu₄Sn₄ was determined on the basis of magnetic and heat capacity data. X-ray diffraction data proved that these compounds crystallize in the orthorhombic Gd₃Cu₄Ge₄-type structure. The compounds are antiferromagnets at low temperatures and the reciprocal magnetic susceptibility obeys the Curie-Weiss law. The paramagnetic Curie temperatures are negative and their absolute values decrease with increasing Ho content. An anomalous concentration dependence of the Néel temperature is observed.     

Phase analysis and magnetocaloric properties of Zr substituted Gd-Si-Ge alloys

The structure, microstructure, magneto-structural transition and magnetocaloric effect have been investigated in series of (Gd_5−xZr_x)Si₂Ge₂ alloys with 0≤x≥0.20. X-ray powder diffraction analysis revealed the presence of orthorhombic structure for Zr containing alloys at room temperature in contrast to the monoclinic structure observed in the parent Gd₅Si₂Ge₂ alloy. The microstructural studies reveal that, low Zr addition (x≤0.1) resulted in low volume fraction of detrimental Gd₅Si₃-type secondary phase compared to that present in the parent alloy. All the Zr containing alloys have shown the presence of only second order magnetic transition unlike the parent alloy showing both first order structural and second order magnetic transition. A moderate (ΔS)_M value of −5.5 J/kg K was obtained for the x=0.05 alloy at an enhanced operating temperature of 292 K compared to −7.8 J/kg K at 274 K of the parent alloy for an applied field of 2 T. The interesting feature of Zr (x=0.05) containing alloy is the wide operating temperature range of ∼25 K than that of ∼10-12 K for the parent, which resulted in enhanced net refrigerant capacity of 103 J/kg compared to that of 53 J/kg for the parent alloy.     

Diffuse phase transition in Ba5NdTi3−xZrxNb7O30 ferroelectric ceramics

Polycrystalline samples of Ba₅NdTi_3−xZr_xNb₇O₃₀ (x=0, 1, 2, 3) compounds of the tungsten-bronze (TB) structural family were prepared by a high-temperature solid-state reaction technique. X-ray study of the compounds shows the formation of single phase compounds in the orthorhombic crystal system at room temperature. Detailed studies of the dielectric properties (dielectric constant and loss tangent) as a function of temperature (−50 to 350°C) at four different frequencies, 1, 10, 100 and 1000 kHz show relaxor behavior and diffuse phase transition of the compounds. Study of temperature dependence of resistivity shows that these compounds have negative temperature coefficients of resistance (NTCR).     

Structure dependence of near-infrared stimulated blue emission in polycrystalline Ln2(WO4)3 (Ln=Gd and Lu) doped with Tm and Yb

Tm- and Yb-doped gadolinium tungstate, (Gd_xTm_yYb_1−x−y)₂(WO₄)₃ (x=0.7-0.9; y=0.001-0.01), have been prepared by the polymerized complex method to achieve a homogeneous dispersion of dopants and to stabilize the host structure. Decomposition (900 °C 5 h) of the precursors with x=0.8-0.9 yielded a pure monoclinic phase, while that of x=0.7 resulted in formation of an orthorhombic impurity. The monoclinic phase exhibits bright up-converted blue emission due to the ¹G₄→³H₆ transition of Tm³⁺ (472 nm) upon excitation into the Yb³⁺:²F_7/2→²F_5/2 absorption band as a result of energy transfer from Yb to Tm. The orthorhombic impurity acts as a strong quencher of emission, and the quenching mechanism has been discussed on the basis of structural and spectroscopic properties of orthorhombic Lu₂(WO₄)₃:Tm,Yb prepared by the same method.     

Structural transition and enhanced magnetization in Bi1−xYxFeO3

Bi_1−xY_xFeO₃ (x=0-0.2) powders were prepared to study the effect of Y substitution on their structural and magnetic properties. A structural symmetric breaking from the rhombohedral R3c to orthorhombic Pnma at around x=0.10 was identified across a ferroelectric-paraelectric phase. A parabolic dependence of the magnetization upon substitution was obtained with a maximum at the phase transition boundary and a switching behavior for x=0.20. The composition-driven magnetic structure evolution was proposed to account for the magnetic properties in Bi_1−xY_xFeO₃.     

Preparation of five-layered Si/SixGe1−x nano-films by RF helicon magnetron sputtering

Five-layered Si/Si_xGe_1−x films on Si(1 0 0) substrate with single-layer thickness of 30 nm, 10 nm and 5 nm, respectively were prepared by RF helicon magnetron sputtering with dual targets of Si and Ge to investigate the feasibility of an industrial fabrication method on multi-stacked superlattice structure for thin-film thermoelectric applications. The fine periodic structure is confirmed in the samples except for the case of 5 nm in single-layer thickness. Fine crystalline Si_xGe_1−x layer is obtained from 700 °C in substrate temperature, while higher than 700 °C is required for Si good layer. The composition ratio (x) in Si_xGe_1−x is varied depending on the applied power to Si and Ge targets. Typical power ratio to obtain x = 0.83 was 7:3, Hall coefficient, p-type carrier concentration, sheet carrier concentration and mobility measured for the sample composed of five layers of Si (10 nm)/Si_0.82Ge_0.18 (10 nm) are 2.55 × 10⁶ /°C, 2.56 × 10¹² cm⁻³, 1.28 × 10⁷ cm⁻², and 15.8 cm⁻²/(V s), respectively.     

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.     

Structural stability and magnetic properties of Bi1−xLa(Pr)xFeO3 solid solutions

In this work, X-ray diffraction data taken on Bi_1−xLa_xFeO₃ solid solutions are used to verify the following structural phase transitions: “polar rhombohedral-antipolar orthorhombic” at x≈0.16 and “commensurate-incommensurate” within the orthorhombic phase at x≈0.18. In contrast, in the Bi_1−xPr_xFeO₃ series, the polar rhombohedral phase transforms into an antipolar orthorhombic one at x≥0.13. The polar rhombohedral phase near the morphotropic phase boundary exhibits an isothermal transformation into an antipolar orthorhombic phase, though the transformation occurs much faster in the case of La-doped compounds. The incommensurate structural phase was not detected in Bi_1−xPr_xFeO₃ solid solutions. The ternary structural phase diagram is constructed for (Bi,La,Pr)FeO₃ systems. In addition, the polar rhombohedral phase exhibits a magnetic field-induced transition from the modulated antiferromagnetic state into a homogeneous weak ferromagnetic state whereas the antipolar phase is a weak ferromagnetic state in the absence of an external field.     

Investigations on structural and optical properties of Zn1−xGdxS nanoparticles

Zn_1−xGd_xS (x = 0.00, 0.02 and 0.04) nanoparticles were synthesized by facile chemical co-precipitation method using PVP as a surfactant. ZnS nanoparticles could be doped with Gd ions during synthesis without altering the XRD patterns of ZnS. Also, the pattern of the powders showed cubic zincblende structure. The particle size obtained from the XRD studies lies in the range 3-5 nm, whereas from TEM analysis it is 4 nm for x = 0.02 sample. The UV-Vis absorption spectra revealed that Zn_1−xGd_xS nanoparticles exhibit strong confinement effect as the blue shift in the absorption spectra with that of the undoped ZnS. The photoluminescence spectra showed enhanced luminescence intensity and the entry of Gd into host lattice.     

Growth and properties of magnetron cosputtering grown MnxGe1−x on Si (001)

We have grown Mn_xGe_1−x films (x=0, 0.06, 0.1) on Si (001) substrates by magnetron cosputtering, and have explored the resulting structural, morphological, electrical and magnetic properties. X-ray diffraction results show there is no secondary phase except Ge in the Mn_0.06Ge_0.94 film while new phase appears in the Mn_0.1Ge_0.9 film. Nanocrystals are formed in the Mn_0.06Ge_0.94 film, determined by field-emission scanning electron microscopy. Hall measurement indicates that the Mn_0.06Ge_0.94 film is p-type semiconductor and hole carrier concentration is 6.07×10¹⁹ cm⁻³ while the Mn_xGe_1−x films with x=0 has n-type carriers. The field dependence of magnetization was measured using alternating gradient magnetometer, and it has been indicated that the Mn_0.06Ge_0.94 film is ferromagnetic at room temperature.     

Na1−xLixNbO3 ceramics studied by X-ray diffraction, dielectric, pyroelectric, piezoelectric and Raman spectroscopy

Na_1−xLi_xNbO₃ ceramics with composition 0.05≤x≤0.30 were prepared by solid-state reaction method and sintered in the temperature range 1100-1150 °C. These ceramics were characterised by X-ray diffraction as well as dielectric permittivity measurements and Raman spectroscopy. Dielectric properties of ceramics belonging to the whole composition domain were investigated in a broad range of temperatures from 300 to 750 K and frequencies from 0.1 to 200 kHz. The Rietveld refinement powder X-ray diffraction analysis showed that these ceramics have a single phase of perovskite structure with orthorhombic symmetry for x≤0.15 and two phases coexistence of rhombohedral and orthorhombic above x=0.20. The evolution of the permittivity as a function of temperature and frequency showed that these ceramics Na_1−xLi_xNbO₃ with composition 0.05≤x≤0.15 present the classical ferroelectric character and the phase transition temperature T_C increases as x content increases. The polarisation state was checked by pyroelectric and piezoelectric measurements. For x=0.05, the piezoelectric coefficient d₃₁ is of 2pC/N. The evolution of the Raman spectra was studied as a function of temperatures and compositions. The results of the Raman spectroscopy study confirm our dielectric measurements, and they indicate clearly the transition from the polar ferroelectric phase to the non-polar paraelectric one.     

Structure and superconductivity of Mg1−xPbxB2

A series of polycrystalline samples of Mg_1−xPb_xB₂ (0≤x≤0.10) were prepared by a solid state reaction method and their structure, superconducting transition temperature and transport properties were investigated by means of X-ray diffraction (XRD) and resistivity measurements. Mg_1−xPb_xB₂ compounds were shown to adopt an isostructural AlB2-type hexagonal structure in a relatively small range of lead concentration, x≤0.01. The crystalline lattice constants were evaluated and were found to exhibit slight length compression as x increases. The superconducting transition temperature (T_c) steadily decreases with Pb doping. It is suggested that the mechanism of superconductivity reduction by lead doping can be attributed to the chemical pressure effect.     

The magnetic phase transitions and magnetocaloric effect in MnNi1−xCoxGe alloys

The magnetic phase transitions and the magnetocaloric effects in MnNi_1−xCo_xGe (x=0.38 and 0.40) alloys were investigated. The substitution of Co for Ni in the MnNiGe antiferromagnet results in the metamagnetic transitions from antiferromagnetic to ferromagnetic state, which associates with very small thermal and magnetic hystereses. Positive and negative values of magnetic entropy changes are exhibited around the metamagnetic transition temperature and Curie temperature, respectively. The relatively large refrigerant capacity in low magnetic field along with the good reversibility suggest that MnNi_1−xCo_xGe (x=0.38 and 0.40) alloys are potential candidates for magnetic refrigeration.     

Coexistence of superconductivity and magnetism in the La0.87−xLnxSr0.13FeAsO (Ln=Sm, Gd, Dy) system

The interplay between the superconducting phase and spin density wave order phase was studied. We report the magnetic and superconducting properties of the hole-doped FeAs-based superconducting compound La_0.87−xLn_xSr_0.13FeAsO (Ln=Sm, Gd, Dy; 0≤x≤0.06). Both resistivity and magnetic susceptibility measurements show that the superconducting transition temperature decreases with increase in composition of magnetic ions. The hysteresis loop of the La_0.87−xLn_xSr_0.13FeAsO sample shows a superconducting hysteresis in addition to a paramagnetic background. The experiment demonstrates that the magnetism and superconductivity coexist in hole-doped FeAs-based superconducting compounds. Among these three magnetic rare-earth elements, the influence of Dy³⁺ doping on superconductivity is more evident than that of Gd³⁺ doping, while the influence of Sm³⁺ doping is the weakest. The trend is consistent with the variation of the lattice parameter along c-axis.     

Ferroelectricity in antiferromagnetic phases of Eu1−xY xMnO3

This work reports an experimental investigation of the ferroelectric character of magnetic phases of the orthorhombic Eu_1−xY _xMnO₃ system at low temperatures. The temperature dependence of the polarization curves clearly reveals the existence of a re-entrant improper ferroelectric phase for x=0.2, 0.3 and 0.5. A ferroelectric phase is also stable for x=0.4, and we have no experimental evidence for its vanishing down to 7 K. From these and early results obtained using other experimental techniques, the corresponding (x,T) phase diagram was traced, yielding significant differences with regard to the ones previously reported.     

The magnetic behavior of La1−xTbxMn2Si2 (0≤x≤0.3) in weak magnetic fields

The structure and magnetic properties of La_1−xTb_xMn₂Si₂ (0≤x≤0.3) were studied by X-ray powder diffraction and DC magnetization measurements. All the compounds crystallize in ThCr₂Si₂-type structure. Substitution of Tb for La led to a linear decrease in the lattice constants and the unit-cell volume. A ferromagnetic phase for x≤0.15, and an antiferromagnetic phase for x=0.3 have been observed at about room temperature, whereas the compounds with x=0.2 and 0.25 exhibit a magnetic phase transition from ferromagnetism to antiferromagnetism.     

Elemental depth profiling of a-Si1−xGex:H films by elastic recoil detection analysis and secondary ion mass spectrometry

The hydrogen content in a-Si_1−xGe_x:H thin films is an important factor deciding the density and the optical band gap. We measured the elemental depth profiles of hydrogen together with Si and Ge by elastic recoil detection analysis (ERDA) combined with Rutherford backscattering (RBS) using MeV He²⁺ ions. In order to determine the hydrogen depth profiles precisely, the energy- and angle-dependent recoil cross-sections were measured in advance for the standard sample of a CH₃⁺-implanted Si substrate. The cross-sections obtained here are reproduced well by a simple expression based on the partial wave analysis assuming a square well potential (width: r₀ = 2.67 × 10⁻¹³ cm, depth: V₀ = −36.9 MeV) within 1%. For the a-Si_1−xGe_x:H films whose elemental compositions were determined by ERDA/RBS, we measured the secondary ions yields of HCs₂⁺, SiCs₂⁺, H⁻, Si⁻ and Ge⁻ as a function of Ge concentration x. As a result, it is found that the useful yield ratios of HCs₂⁺/SiCs₂⁺, H⁻/Si⁻ and Ge⁻/Si⁻ are almost constant and thus the elemental depth profiles of the a-Si_1−xGe_x:H films can be also determined by secondary ion mass spectrometry (SIMS) within 10% free from a matrix effect.