Magnetic phase diagram of double-layered La2−2xCa1+2xMn2O7 manganite

Double-layered manganite La_2−2xCa_1+2xMn₂O₇ have been synthesized for compositions ‘x’=0.0, 0.1, 0.2, 0.3, 0.4 and 0.5 by solid state reaction method. From X-ray diffraction study, their crystal structures were found to be tetragonal perovskite with lattice parameters decreasing with increasing ‘x’. The decreasing lattice parameters affect the balance between in-plane, intra-bilayer and inter-bilayer exchange interactions, which is reflected on magnetotransport properties. The metal-to-insulator transition temperature is found to vary with composition and peaked around ‘x’=0.3. From ac-susceptibility study, 2D-ferromagnetic ordering was observed at higher temperatures for all compositions whereas 3D-ferromagnetic ordering was observed at quite low temperatures. In low-temperature region, decreasing susceptibility shows antiferromagnetic state for all compositions. On the basis of electrical and magnetic properties, a magnetic phase diagram is given.     

Magnetoresistive properties of Zn1−xCoxFe2O4 ferrites

The magnetic and magnetoresistive properties of spinel-type Zn_1−xCo_xFe₂O₄ (x=0, 0.2 and 0.4) ferrites are extensively investigated in this study. A large negative magnetoresistance (MR) effect is observed in Zn_1−xCo_xFe₂O₄ ferrites of spinel structure. These materials are either ferrimagnetic or paramagnetic at room temperature, and show a spin-(cluster) glass transition at low temperatures, depending on the chemical compositions. The MR curves as a function of magnetic fields, MR(H), are parabolic at all temperatures for paramagnetic polycrystalline ZnFe₂O₄. The MR for ZnFe₂O₄ at 110 K in the presence of 9 T applied magnetic field is 30%. On the other hand, MR(H) are linear for x=0.2 and 0.4 ferrimagnetic Zn_1−xCo_xFe₂O₄ samples up to 9 T. The MR effect is independent of the sintering temperatures, and can be explained with the help of the spin-dependent scattering and the Yafet–Kittel angle of Zn_1−xCo_xFe₂O₄ mixed ferrites.     

Magnetic properties of the compounds ThCO2Ge2 and ThCo2Si2

Rather old preparation of the compounds ThCo₂Ge₂ and ThCo₂Si₂ and their magnetic study in the temperature range 100–570 K, published by Omejec and Ban [Z. Anorg. Allg. Chem. 380 (1971) 111], indicated that both compounds ordered ferrromagnetically below 100 K. In order to verify the old data, polycrystalline samples of ThCo₂Ge₂ and ThCo₂Si₂ have been prepared by arc melting and subsequent annealing, and studied by X-ray diffraction at room temperature (RT), by superconducting quantum interference device (SQUID)-magnetization and AC-susceptibility measurements at 2–320 K, and by dc-magnetization measurements in variable magnetic fields up to 120 kOe at 5, 80, and 283 K. The magnetic measurements confirm the ferromagnetic ordering in both compounds, but with totally different Curie temperatures: ≈120(20) K for ThCo₂Ge₂ and above 320 K for ThCo₂Si₂. The paramagnetic values of ThCo₂Ge₂ and the ordering of both compounds are discussed and compared with the old results of Omejec and Ban.     

Ferromagnetic semiconductor Ge1−x−ySnxMnyTe with phase transformation of ferroelectric type

It is expected that joint existence of ferromagnetic properties and ferroelectric structural phase transition in diluted magnetic semiconductors IV-VI leads to new possibilities of these materials. Temperature of ferroelectric transition for such crystals can be tuned by the change of Sn/Ge ratio. Magnetic susceptibility, Hall effect, resistivity and thermoelectric power of Ge_1−x−ySn_xMn_yTe single crystals grown by Bridgeman method (x=0.083-0.115; y=0.025-0.124) were investigated within 4.2-300 K. An existence of FM ordering at T_C∼50 K probably due to indirect exchange interaction between Mn ions via degenerated hole gas was revealed. A divergence of magnetic moment temperature dependences at T?T_C in field-cooled and zero-field-cooled regimes is obliged to magnetic clusters which are responsible for superparamagnetism at T>T_C≈T_f (freezing temperature) and become ferromagnetic at T_C arranging spin glass state at T<T_f≈T_C. Phase transition of ferroelectric type at T≈46 K was revealed. Anomalous Hall effect which allows to determine magnetic moment was observed.     

Hyperfine interactions in some Aurivillius Bim+1Ti3Fem−3O3m+3 compounds

X-ray diffraction and Mössbauer spectroscopy were applied as complementary methods to investigate the structure and hyperfine interactions in the series of Bi_m+1Ti₃Fe_m−3O_3m+3 Aurivillius compounds with m=4, 6, 7 and 8. Samples were synthesized by the solid-state sintering method at various temperatures. As X-ray diffraction analysis proved, the compounds formed single phases at temperature above 993 K. Mössbauer studies have confirmed diffraction measurements. Compounds synthesized at 993 K contained residual hematite, however these sintered at elevated temperatures were single-phased materials. Room-temperature Mössbauer spectra of Bi_m+1Ti₃Fe_m−3O_3m+3 compounds revealed their paramagnetic properties, what is consistent with the literature data concerning the Néel temperature of these ceramics (T_N is smaller than room temperature). Detailed analysis of MS spectra allowed to state that iron ions may occupy both tetrahedral and octahedral sites in the crystallographic lattice of Aurivillius compounds.     

Selected properties of EuCo2(Si1−xGex)2 alloys

EuCo₂(Si_1−xGe_x)₂, x=0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1 samples were synthesised by induction melting followed by annealing at 900 °C and rapid quenching. X-ray powder diffraction and Auger electron spectroscopy studies revealed that solid solutions are formed only for x?0.2 and x?0.7. Magnetic susceptibility investigations for the solid solutions revealed a dominant divalent europium valence state in the germanium-rich samples and a dominant trivalent europium component in the silicon-rich samples. In the germanium-rich samples, a long-range antiferromagnetic ordering was observed. In all samples studied, additional magnetic transitions at various temperatures were detected, which could be attributed to small clusters containing different europium chemical surrounding from that in the predominant phase.     

Effect of fabrication parameters on the electrical conductivity of YxSr1−xTiO3 for anode materials

Yttrium-doped strontium titanate (Y_xSr_1−xTiO₃), as probable anode material for SOFC, was prepared by solid-state reaction. The solubility of yttrium in SrTiO₃ at different temperatures was examined and the electrical conductivities of Y_xSr_1−xTiO₃ were measured from 500 to 1000 °C. The effects of doping amount, fabrication atmosphere, and sintering temperature on the electrical conductivity of Y_xSr_1−xTiO₃ were investigated. Y_xSr_1−xTiO₃ with x=0.08 was found to give the maximum electrical conductivity, 71 S/cm at 800 °C in pure hydrogen. Reducing atmospheres and appropriate sintering temperatures play a positive role in improving the electrical conductivity.     

Leakage current, ferroelectric and structural properties in Pb1−xBaxTiO3 thin films prepared by chemical route

Single-phase perovskite structure Pb_1−xBa_xTiO₃ thin films (x=0.30, 0.50 and 0.70) were deposited on Pt/Ti/SiO₂/Si substrates by the spin-coating technique. The dielectric study reveals that the thin films undergo a diffuse type ferroelectric phase transition, which shows a broad peak. An increase of the diffusivity degree with the increasing Barium contents was observed, and it was associated to a grain decrease in the studied composition range. The temperature dependence of the phonon frequencies was used to characterize the phase transition temperatures. Raman modes persist above tetragonal to cubic phase transition temperature, although all optical modes should be Raman inactive. The origin of these modes was interpreted in terms of breakdown of the local cubic symmetry by chemical disorder. The absence of a well-defined transition temperature and the presence of broad bands in some interval temperature above FE-PE phase transition temperature suggested a diffuse type phase transition. This result corroborates the dielectric constant versus temperature data, which showed a broad ferroelectric phase transition in these thin films. The leakage current density of the PBT thin films was studied at different temperatures and the data follow the Schottky emission model. Through this analysis the Schottky barrier height values 0.75, 0.53 and 0.34 eV were obtained to the PBT70, PBT50 and PBT30 thin films, respectively.     

Percolation threshold near the second phase transition in diluted system of Gd2−x(La, Y)xIn

In this paper it is demonstrated that the second phase transition of Gd₂In intermetallic compound gets eliminated by diluting Gd_2−x(LaY)_xIn at a critical composition of x=0.5. The exchange coupling for intra-cluster interactions is estimated in the correlation ranges of 3.3 Å<R_C<3.6 Å (anisotropic source) and for inter-cluster interactions in the ranges of R_C>4 Å where the correlation length is defined as . The sign and strength of the exchange coupling are identified by the eigenvalues λ(k) and are obtained from zeros of the 4×4 matrix of J_ij^RR′ along the three directions of the reciprocal lattice for each dilution (x=0.25, 0.5, 0.75, 1). The transition temperature is calculated using the minimum eigenvalue λ_min (k=0, π) which agrees with the experiment. Magnetic field and temperature dependence of the magnetization and electrical resistivity measurements show that: (i) Elimination of the AFM phase is caused by breaking of some FM short-range exchange couplings, and (ii) Conduction electrons order antiferromagnetically at low temperatures and ferromagnetically at high temperatures.     

Temperature dependence of electrical resistivity for Ca-doped perovskite-type Y1−xCaxCoO3 prepared by sol-gel process

The temperature dependences of DC electrical resistivity for perovskite-type oxides Y_1−xCa_xCoO₃ (0?x?0.1), prepared by sol-gel process, were investigated in the temperature range from 20 K up to 305 K. The results indicated that with increase of doping content of Ca the resistivity of Y_1−xCa_xCoO₃ decreased remarkably, which was found to be caused mainly by increase of carrier (hole) concentration. In the whole temperature range investigated the temperature dependence of resistivity ρ(T) for the un-doped (x=0) sample decreased exponentially with decreasing temperature (i.e. ln ρ∝1/T), with a conduction activation energy ; the resisitivity of lightly doped oxide (x=0.01) possessed a similar temperature behavior but has a reduced E_a (0.155 eV). Moreover, experiments showed that the relationship ln ρ∝1/T existed only in high-temperature regime for the heavily doped samples (T?82 and ∼89 K for x=0.05 and 0.1, respectively); at low temperatures Mott's ln ρ∝T^−1/4 law was observed, indicating that heavy doping produced strong random potential, which led to formation of considerable localized states. By fitting of the experimental data to Mott's T^−1/4 law, we estimated the density of localized states N(E_F) at the Fermi level, which was found to increase with increasing doping content.     

Influence of vacancies on the electrical properties of the ZnCr2−xNixSe4 spinels

The effect of vacancies on the electronic transport in the ZnCr_2−xNi_xSe₄ paramagnetic single crystals is considered. For this purpose, the structure refinements, the high temperature electrical conductivity and the thermoelectric power measurements as well as the calculations of the vacancy model parameters were used. The electrical measurements have been done in the temperature range from 290 to 520 K for single crystals with x=0.001, 0.05, and 0.065. The above investigations provide evidence for polaron conduction in defective spinel materials. In particular: (1) at high temperatures a linear dependence between thermopower S and the electrical resistivity (ln ρ), a characteristic of small polarons, was observed, (2) an origin of small polarons in this case could be associated with a crystalline distortion, which is characterized by larger values of the anion parameter than u=0.375, which describes an ideal spinel structure, and (3) a large defectiveness, which is identified by the large value of the vacancy parameter of about β=11.5%. These effects are explained in terms of a polaron mechanism of the electrical conductivity including structural defects.     

Magnetic properties of the Pr1−xGdxCo4B compounds

In this work, we have investigated the effect of the substitution of Gd for Pr on the crystal structure and magnetic properties of the Pr_1−xGd_xCo₄B compounds for 0?x?1 using X-ray powder diffraction, magnetic measurements, and differential scanning calorimetry (DSC). These compounds have hexagonal CeCo₄B-type structure with the space group P6/mmm. The substitution of Gd for Pr leads to a decrease of the unit-cell parameters a and the unit-cell volume V, while the unit-cell parameter c increases slightly. Magnetic measurements indicate that all samples are ordered magnetically below room temperature. The Curie temperatures determined by DSC technique increase as Pr is substituted by Gd. The saturation magnetization at 5 K decreases upon Gd substitution up to x=0.6, and then increases again.     

Magnetism on Mg1−xZnxCyNi3

The magnetic phase diagram for Mg_1−xZn_xC_yNi₃ has been tentatively constructed based on magnetization and muon spin relaxation (μSR) measurements. The superconducting phase was observed to fade as x (y) increases (decreases). The low y samples show early stages of long-range ferromagnetism, or complete long-range ferromagnetism. In the phase diagram, the ferromagnetic phase exists in addition to the superconducting phase, suggesting that there is some correlation between superconductivity and ferromagnetism, even though the coexistence of ferromagnetism and superconductivity is not observed from the μSR measurements down to 20 mK for the superconducting sample (T_c=2.5 K, (x, y)=(0, 0.9)).     

Magnetic properties of half-metallic semi Heusler Co1−xCuxMnSb compounds

A study of the half-metallic character of the semi Heusler alloys Co_1−xCu_xMnSb (0?x?0.9) is presented. We investigated the saturation magnetization M_S at temperatures from 5 K to room temperature and the temperature dependence of the DC magnetic susceptibility χ above Curie temperature T_C. The magnetic moments at 5 K, for most compositions are very close to the quantized value of 4 μ_B for Mn³⁺ ion, the compound with 90% Co substituted by Cu is still ferromagnetic with M_S (5 K)=3.78 μ_B/f.u. These results emphasize the role of Co atoms in maintaining the ferromagnetic order in the material. The Curie temperature is decreased from 476 K to about 300 K as the Cu content increases from 0% to 90%. Above T_C, the χ⁻¹ vs T curves follow very well the Curie–Weiss law. The effective moment μ_eff and paramagnetic Curie temperature θ are derived. A comparison between the values of M_S at 5 K and μ_eff shows a transition from localized to itinerant spin system in these compounds.     

Spin-glass-like behavior in ZnxCryAlzSe4

The magnetic and electrical properties of the Al-doped polycrystalline spinels Zn_xCr_yAl_zSe₄ (0.13≤z≤0.55) with the antiferromagnetic (AFM) order and semiconducting behavior were investigated. A complex antiferromagnetic structure below a Néel temperature T_N≈23 K for the samples with z up to 0.4 contrasting with the strong ferromagnetic (FM) interactions evidenced by a large positive Curie-Weiss temperature θ_CW decreasing from 62.2 K for z=0.13 to 37.5 K for z=0.55 was observed. Detailed investigations revealed a divergence between the zero-field-cooling (ZFC) and field-cooling (FC) susceptibilities at temperature less than T_N suggesting bond frustration due to competing ferromagnetic and antiferromagnetic exchange interactions in the compositional range 0.13≤z≤0.4. Meanwhile, for z=0.55 a spin-glass-like behavior of cluster type with randomly oriented magnetic moments is observed as the ZFC-FC splitting goes up to the freezing temperature T_f=11.5 K and the critical fields connected both with a transformation of the antiferromagnetic spin spiral via conical magnetic structure into ferromagnetic phase disappear.     

Magnetocaloric effect of Gd5SixSn4−x Alloys

The crystal structure and magnetocaloric effect of Gd₅Si_xSn_4−x   (with x=2.4$x=2.4$, 2.6 and 2.8) alloys were studied by means of X-ray power diffraction (XRD) and magnetic measurements. From the XRD results, these alloys adopt a Gd₅Si₄-type structure for x=2.8$x=2.8$, Gd₅Si₄-type and Gd₅Si₂Ge₂-type mixed structures for x=2.4$x=2.4$ and 2.6, while some minor phases can also be found. The Curie temperatures of the Gd₅Si_xSn_4−x increases gradually when x increases from 276 K for x=2.4$x=2.4$, to 301.5 K for x=2.8$x=2.8$. Magnetic entropy changes of these alloys at a magnetic field change of 0–1.8 T are 1.88, 2.26 and 1.69 J/kg K for x=2.4$x=2.4$, 2.6 and 2.8, respectively. The temperature-dependent XRD analysis shows that there is no crystallographic transition for these alloys, which can explain their low magnetic entropy changes.     

Transport and magnetic properties of disordered LixVyO2 (x=0.8 and y=0.8)

The magnetic and electron transport properties of rhombohedral Li_xV_yO₂ (x=0.8 and y=0.8) are studied. The dc susceptibility of Li_xV_yO₂ can be well fitted to the modified Curie-Weiss law, which verified the paramagnetic ground state. The magnetic hysteresis and ac susceptibility also confirm this paramagnetism. The Li_xV_yO₂ exhibits semiconducting behavior, which is explained by thermal activated process at high temperature and variable-range hopping mechanism at low temperature. Anderson localization plays an important role in both the electron transport behavior and the magnetic behavior due to the site disorder between the Li⁺ ion and V⁴⁺ ion.     

Phase transition and extended X-ray absorption fine structure of melt-spun amorphous Fe100−xYx alloys

The phase diagram and local structure of melt-spun amorphous (a-) Fe_100−xY_x (22?x?62) alloys were investigated using AC and DC magnetic and extended X-ray absorption fine structure (EXAFS) measurements. The a-Fe–Y system shows reentrant spin glass (RSG) behavior for 42?x?58 and spin glass (SG) behavior for 60?x. Two SG transition temperatures, T_g and T_f, were obtained in the RSG state. The T_g, T_f and Curie temperature T_C decrease with increasing x, and the T_C and T_g vanish at x=60. A new magnetic phase diagram for the melt-spun a-Fe_100−xY_x alloys was obtained from magnetic measurements for higher Y concentration. The magnetic states of the a-Fe_100−xY_x alloys change remarkably around x=60 and an EXAFS study revealed that the average atomic distance between nearest-neighboring Fe atoms changes at approximately x=60.     

Magnetic properties of nanocrystalline Co1−xZnxFe2O4 prepared by forced hydrolysis method

Nanocrystalline zinc-substituted cobalt ferrite powders, Co_1−xZn_xFe₂O₄ (x=0, 0.2, 0.4), were for the first time prepared by forced hydrolysis method. Magnetic and structural properties in these specimens were investigated. The average crystallite size is about 3.0 nm. When the zinc substitution increases from x=0 to x=0.4, at 4.2 K, the saturation magnetization increases from 72.1 to 99.7 emu/g and the coercive field decreases from 1.22 to 0.71 T. All samples are superparamagnetic at room temperature and ferrimagnetic at temperatures below the blocking temperature. The high value of the saturation magnetization and the very thin thickness of the disorder surface layer of all samples suggests that this forced hydrolysis method is suitable not only for preparing two metal element systems but also for three or more ones.     

Dielectric properties of valence compensated Ca1−xBixTi1−xCrxO3 perovskite prepared using the sol-gel process

Ca_1−xBi_xNb_1−xCr_xO₃ (x=0.01-0.5) ceramic powders were synthesized using the sol-gel process. The single-phase solids can be presented at x=0.01 and 0.03. The coexistence of orthorhombic perovskite and the secondary phase of BiCrO₃ was verified, as presented for x=0.05-0.5. Grains with a micro-cube topography were obtained for x=0.3-0.5. The average grain size is about 0.4 and 1.1 μm for x=0.3 and 0.5, respectively. The highest dielectric constant peak was measured at around 55 °C for x=0.5 and at 75 °C for x=0.3. The high dielectric constant was caused by the formation of barrier layers at the interface of the bi-phase mixed ceramics. Space charge polarization contributed to the observed behavior.