Superconductivity and magnetism of La2Cu1−xZnxO4+δ chemically oxidized by NaClO

The structural, superconducting and magnetic properties of La₂Cu_1−xZn_xO_4+δ (0≤x≤0.1) chemically oxidized by NaClO at room temperature were studied. All the samples before and after oxidation are single phase with orthorhombic structure, as indicated by their powder X-ray diffraction analysis. The iodometric titration results indicate that Zn-substituted La₂Cu_1−xZn_xO₄ is more favorable for the insertion of the excess oxygen, as compared to the Zn-free La₂CuO₄. The T_c suppression rate resulting from Zn substitution in La₂Cu_1−xZn_xO_4+δ is −12.4 K/%. The effective magnetic moment induced by the non-magnetic Zn ion is the order of one Bohr magneton, which decreases with increasing the Zn concentrations in the range examined. The latter two results are qualitatively well consistent with those obtained in La_2−xSr_xCu_1−yZn_yO₄ with the Sr optimal doping. This reveals that the non-magnetic Zn ions play the same role in both of the La₂Cu_1−xZn_xO_4+δ with the excess oxygen content of about 0.1 and the La_2−xSr_xCu_1−yZn_yO₄ with the Sr optimal doping.     

Magnetic properties and phase diagram of ZnxNi1−xFe2O4: High-temperature series expansions

Using mean field theory and high-temperature series expansions (HTSEs), extrapolated with the Padé approximants method, the effect of Zn doping on magnetic properties of NiFe₂O₄ ferrite spinel has been studied. The nearest neighbour super-exchange interactions for intra-site (J_AA, J_BB) and inter-site (J_AB) of the Zn_xNi_1−xFe₂O₄ ferrites spinels, in the range 0≤x≤1, have been computed using the probability approach, based on Mössbauer data. The paramagnetic Curie-Weiss temperature θ and the Curie temperature T_C are calculated as a function of Zn concentration. The critical exponent γ associated with magnetic susceptibility is calculated. The spin correlation functions intra-plane and inter-plane have been also computed and compared with exchange couplings. The obtained theoretical results are in good agreement with experimental ones obtained by magnetic measurements and Mössbauer spectroscopy.     

Structural and Magnetic Properties of NiFe2−2xSnxCuxO4

The substituted nickel ferrite (NiFe_2−2xSn_xCu_xO₄, x=0, 0.1, 0.2, 0.3) was prepared by the conventional ceramic method. The effect of substitution of Fe³⁺ ions by Sn⁴⁺ and Cu²⁺ cations on the structural and magnetic properties of the ferrite was studied by means of ⁵⁷Fe Mössbauer spectroscopy, alternating gradient force magnetometry (AGFM) and Faraday balance. Whereas undoped NiFe₂O₄ adopts a fully inverse spinel structure of the type (Fe)[NiFe]O₄, Sn⁴⁺ and Cu²⁺ cations tend to occupy octahedral positions in the structure of the substituted ferrite. Based on the results of Mössbauer spectroscopic measurements, the crystal-chemical formula of the substituted ferrite may be written as (Fe)[NiFe_1−2xSn_xCu_x]O₄, where parentheses and square brackets enclose cations in tetrahedral (A) and octahedral [B] coordination, respectively. The Néel temperature and the saturation magnetization values of the NiFe_2−2xSn_xCu_xO₄ samples were found to decrease with increasing degree of substitution (x). The variation of the saturation magnetization with x measured using the AGFM method and that calculated on the basis of the Mössbauer spectroscopic measurements are in qualitative agreement.     

First-principles study of the effect of iron doping on the electronic and magnetic properties of TbMn2O5

We have studied the electronic and magnetic properties of TbFe_xMn_2−xO₅ (x=0, 0.125, 0.25) samples using first-principles density functional theory within the generalized gradient approximation (GGA) schemes. The crystal structure of TbMn₂O₅ is orthorhombic containing Mn⁴⁺O₆ octahedra and Mn³⁺O₅ pyramids. The structure changes to monoclinic symmetry for the Fe-doping at the Mn sites. Our spin-polarized calculations give an insulating ground state for TbMn₂O₅ and a metallic ground state for Fe-doped TbMn₂O₅. Based on the magnetic properties calculations, it is found that the magnetic moment enhances with increase in the Fe-content in TbMn₂O₅. Most interestingly, the enhanced magnetic moment is due to a substantial reduction of the magnetic moments at the Fe sites.     

Effect of Si substitution on electronic structure and magnetic properties of Heusler compounds Co2TiAl1−xSix

The electronic structures of Co-based Heusler compounds CoTiAl_1−xSi_x (x=0, 0.25, 0.5, 0.75 and 1) are calculated by first-principles using the full potential linearized augmented plane wave (FP-LAPW) method within GGA and LSDA+U scheme. Particular emphasis was put on the role of the main group elements. In recent years, the GGA calculations of Co₂TiAl (x=0) and Co₂TiSi (x=1) indicated that they are half-metallic, but the electronic structure of this compound with x=0.25, 0.5 and 0.75 has not been reported yet, neither theoretically nor experimentally. The calculated results reveal that these are half-metallic and exhibit an energy gap in the minority spin state and also show 100% spin polarization. The substitution of Al by Si leads to an increase in the number of valence electrons, with increasing x. Our calculated results clearly show that with the Si doping, the lattice parameter linearly decreases; bulk modulus increases, and the total magnetic moment increases. The calculated energy gap in the minority spin state, using GGA scheme, was smaller than that obtained by using LSDA+U scheme. The outcomes of this research also show that the Co-3d DOS and therefore, the magnetic properties of compounds are dependent on electron concentration of the main group elements and it will affect the degree of p-d orbital occupation.     

Structure and magnetic properties of Sn1−xMnxO2

The microstructure and magnetic properties have been investigated systematically for Sn_1−xMn_xO₂ polycrystalline powder samples with x=0.02-0.08 synthesized by a solid-state reaction method. X-ray diffraction revealed that all samples are pure rutile-type tetragonal phase and the cell parameters a and c decrease monotonously with the increase in Mn content, which indicated that Mn ions substitute into the lattice of SnO₂. Magnetic measurements revealed that all samples exhibit room temperature ferromagnetism. Furthermore, magnetic investigations demonstrate that magnetic properties strongly depend on doping content, x. The average magnetic moment per Mn atom decreases with increase in the Mn content, because antiferromagnetic super-exchange interaction takes place within the neighbor Mn³⁺ ions through O²⁻ ions for the samples with higher Mn doping. Our results indicate that the ferromagnetic property is intrinsic to the SnO₂ system and is not a result of any secondary magnetic phase or cluster formation.     

Enhanced ferroelectric, magnetic and magnetoelectric properties of Bi1−xCaxFe1−xTixO3 solid solutions

We report on the enhanced electromechanical, magnetic and magnetoelectric properties of Bi_1−xCa_xFe_1−xTi_xO₃ solid solutions. The crystal structure of the x≈0.25 compounds are close to the rhombohedral-orthorhombic phase boundary, and the solid solutions are characterized by increased electromechanical properties due to the polarization extension near the polar-nonpolar border. The homogenous weakly ferromagnetic state is established at x>0.15 doping. The chemical doping shifts the magnetic transition close to room temperature, thus enlarging the magnetic susceptibility of the compounds. The solid solutions at the morphotropic phase boundary exhibit a nearly twofold increase in piezoelectric response, whereas the magnetoelectric coupling shows five times enhancement in comparison with the parent bismuth ferrite.     

Magnetic,electronic and structural properties of ZnxFe3−xO4

A series of samples Zn_xFe_3−xO₄ have been prepared by the chemical coprecipitation technique and characterized by X-ray diffraction (XRD), vibrating sample magnetometry (VSM) and X-ray photoelectron spectroscopy (XPS). XRD demonstrates all the samples of Zn_xFe_3−xO₄ have a spinel structure same as Fe₃O₄. The magnetic hysteresis loops of Zn_xFe_3−xO₄ obtained from VSM indicate that the saturation magnetization has a maximum when x is ∼1/3. The chemical states of Fe atoms and Zn atoms in zinc ferrites have been measured using XPS and Auger electron spectroscopy (AES). The Fe 2p core-level XPS spectra and Zn L₃M₄₅M₄₅ Auger peaks have been analyzed and the results have been discussed in correlation with the samples’ magnetic properties. These results suggest most of Zn atoms occupy the tetrahedral sites and a small amount of them occupy the octahedral sites.     

Theoretical study of the electronic and magnetic properties of Co2Cr1−xVxAl

We have investigated the electronic and magnetic properties of the doped Heusler alloys Co₂Cr_1−xV_xAl(x=0, 0.25, 0.5, 0.75, 1) using first-principles density functional theory within the generalized gradient approximation (GGA) scheme. The calculated results reveal that with increasing V content the lattice parameter slightly increases; both cohesive energy and bulk modulus increase with increasing x. The magnetic moment of the Co(Cr) sites increases with V doping; the total spin moment of these compounds linearly decreases. We also have performed the electronic structure calculations for Co₂Cr_1−xV_xAl with positional disorder of Co-Y(Cr,V)-type and Al-Y(Cr,V)-type. It is found that formation of Al-Y-type disorder in Co₂Cr_1−xV_xAl alloys is more favorable than that of Co-Y-type disorder. Furthermore, we found that Co₂Cr_1−xV_xAl of the L2₁-type structure have a half-metallic character. And the stability of L2₁ structure will enhance, however, the Curie temperature decreases as the V concentration increases. The disorder between Cr(V) and Al does not significantly reduce the spin polarization of the alloys Co₂Cr_1−xV_xAl.     

Electronic structural properties and formation energy of Sn1−xPbxO2 solid solutions electrode

First-principles calculations based on density functional theory within the generalized gradient approximation have been performed for the Sn_1−xPb_xO₂ solid solution. The doped formation energies and electronic structures are also analyzed. Results show that the Sn_0.9375Pb_0.0625O₂ solid solution has the highest stability because of its minimum formation energy value of 0.04589 eV at a doping ratio of 0.0625. The SnO₂ lattice constants expand in a distorted rutile structure after Pb doping. The band structure and density of states calculations indicate that the band gap of SnO₂ narrowed due to the presence of the Pb impurity energy levels in the forbidden band, namely, Pb 6s energy band overlaps with the conductivity band in the F–Q direction. In addition, the number of electrons filled at the bottom of the conduction band increases from 0.13 to 3.96 after doping, resulting in the strengthening of the conductivity of the solid solution after doping of plumbum. The results provide a theoretical basis for the development and application of the Sn_1−xPb_xO₂ solid solution electrode.     

Sn1−xBixO2 and Sn1−xTaxO2 (0≤x≤0.75): A first-principles study

The structural, elastic, electronic and optical (x=0) properties of doped Sn_1−xBi_xO₂ and Sn_1−xTa_xO₂ (0≤x≤0.75) are studied using the first-principles pseudopotential plane-wave method within the local density approximation. The independent elastic constants C_ij and other elastic parameters of these compounds have been calculated for the first time. The mechanical stability of the compounds with different doping concentrations has also been studied. The electronic band structure and density of states are calculated and the effect of doping on these properties is also analyzed. It is seen that the band gap of the undoped compound narrowed with dopant concentration, which disappeared for x=0.26 for Bi doping and 0.36 for Ta doping. The materials thus become conductive oxides through the change in the electronic properties of the compound for x≤0.75, which may be useful for potential application. The calculated optical properties, e.g. dielectric function, refractive index, absorption spectrum, loss-function, reflectivity and conductivity of the undoped SnO₂ in two polarization directions are compared with both previous calculations and measurements.     

Interplay between charge and antiferromagnetic ordering in Bi0.6−xPrxCa0.4MnO3 (0≤x≤0.6) perovskite manganite

Structure, magnetic and transport properties of polycrystalline Bi_0.6−xPr_xCa_0.4MnO₃ (x=0.0, 0.1, 0.2, 0.3, 0.4, 0.5 and 0.6) have been studied. Systematic substitution of Pr at Bi site induces an interesting interplay between the charge ordering and antiferromagnetism. The charge ordering temperature (T_CO) decreases with increasing x. The antiferromagnetic (AFM) ordering temperature (T_N) increases sharply at both the extremes but remains nearly constant from x=0.2 to 0.4. At temperatures lower than T_N a transition to the glassy state is observed. The nature of this glass like state appears to be controlled by the Pr content, and at lower values of x this is akin to a spin glass, while at higher x it has a characteristic of cluster glass. The Pr doping also leads to enhancement in the magnetic moment. In the present work it has been proposed that the local lattice distortion induced due to size mismatch between the A-site cations and 6s² character of Bi³⁺ lone pair electron is responsible for the observed magnetic and electrical properties.     

First-principles investigations of Cr doping effects on electronic structure and magnetic properties in Sr2FeReO6

The electronic structures and magnetic properties of double perovskites Sr₂Fe_1−xCr_xReO₆ (x=0.0, 0.25, 0.5, 0.75, 1.0) have been studied within the local spin density approximation (LSDA) and LSDA+U schemes. The calculated results reveal that with increasing Cr content the cell volume shrinks 2.61%; the Fe/Cr site magnetic moment decreases while the Re-site moment increases. The total spin magnetic moment linearly decreases with the Cr doping from 3.00μB for x=0.00 down to 1.00μB for x=1.00 per formula unit. The magnetic coupling constants increase with increasing x. The electronic structure calculations indicate that the electronic concentration in the Re spin-down subband slightly increases resulting from the increase of bonding-antibonding interaction between the localised and the delocalised states in spin-down band; the coupling of O-2p_↑ and transition-metal-3d_↑ is substantially enhanced with the Cr doping. We discuss the origin of the anomalously high TC of Cr-doped Sr₂FeReO₆ compounds in terms of band hybridization effects.     

Room temperature ferromagnetism behavior of Sn1−xMnxO2 powders

In this paper, we have investigated Mn-doped SnO₂ powder samples prepared by solid-state reaction method. X-ray diffraction showed a single phase polycrystalline rutile structure. The atomic content of Mn ranged from ∼0.8 to 5 at%. Room temperature M-H loops showed a ferromagnetic behavior for all samples. The ferromagnetic Sn_0.987Mn_0.013O₂ showed a coercivity H_c=545 Oe, which is among the highest reported for dilute magnetic semiconductors. The magnetic moment per Mn atom was estimated to be about 2.54 μ_B of the Sn_0.9921Mn_0.0079O₂ sample. The average magnetic moment per Mn atom sharply decreases with increasing Mn content, while the effective fraction of the Mn ions contributing to the magnetization decreases. The magnetic properties of the Sn_1−xMn_xO₂ are discussed based on the competition between the antiferromagnetic superexchange coupling and the F-center exchange coupling mechanism, in which both oxygen vacancies and magnetic ions are involved.     

Magnetic and charge ordering properties of Bi0.6−xEuxCa0.4MnO3 (0.0≤x≤0.6)

We have studied structure, magnetic and transport properties of polycrystalline Bi_0.6−xEu_xCa_0.4MnO₃ (x=0.0, 0.1, 0.2, 0.3, 0.4, 0.5 and 0.6) perovskite manganites. Magnetic measurements show that the charge-ordering temperature (T_CO) decreases with increasing x up to x=0.4 and then slightly increases with further increasing x up to x=0.6. Further, the antiferromagnetic (AFM) ordering temperature (T_N) decreases with increasing x. At T<T_N a transition to metamagnetic glass like state is also seen. Eu doping also leads to enhancement in the magnetic moment and a concomitant decrease in resistivity up to x=0.2 and then an increase in resistivity up to x=0.5. We propose that the local lattice distortion induced by the size mismatch between the A-site cations and 6s² character of Bi³⁺ lone pair electron are responsible for the observed variation in physical properties.     

Structural and magnetic properties of Cu1−xMnxO nanocrystal prepared by combustion synthesis

Nanoscale Cu_1−xMn_xO powder is prepared by using the combustion synthesis technique with two different fuels. The structural properties of the powder are determined using Rietveld refinement of X-ray diffraction data, high-resolution transmission electron microscopy, and Fourier transform infrared spectroscopy, while its magnetic properties are analyzed by means of hysteresis loop and temperature dependence of magnetization. The results show that (1) the Cu_1−xMn_xO nanocrystal is of monoclinic CuO structure, with grain size of 10-30 nm varying with the type of fuel, the nitrate/fuel ratio (N/F), and the Mn concentration, the doping of Mn has a little influence on the lattice parameters; (2) when the Mn concentration is higher than 7%, a small amount of impurity phase of CuMn₂O₄ appears and annihilates the potential cation vacancies; (3) all of the samples with x≥5% exhibit low-temperature ferromagnetism with the Curie temperature of ∼90 K, which increases slightly by raising the Mn concentration; (4) the paramagnetic moment per Mn ion is around 2-4 bohr magneton above the Curie temperature, which decreases with increasing Mn concentration, implying that the nearest Mn ions are antiferromagnetically coupled and the ferromagnetic order could originate from the super-exchange of next nearest Mn ions along the [1 0 1?] direction.     

Synthesis, structural and magnetic properties of spin ladder compound Ca1−xCoxCu2O3

MCu₂O₃ (M=Ca and Co) system has two-leg spin ladder structure similar to that of the prototype SrCu₂O₃ system except that the rungs are buckled with an angle of 123° and 105° for CaCu₂O₃ and CoCu₂O₃ compounds, respectively. We have synthesized powder samples of (Ca_1−xCo_x)Cu₂O₃ (x=0.00-1.00) by the solid state reaction method and their structural and magnetic properties have been investigated. All the synthesized compounds crystallize in orthorhombic structure with space group Pmmn. Lattice parameters of (Ca_1−xCo_x)Cu₂O₃ decrease with the increase in Co content. DC magnetic susceptibility χ(T) results of the end products CaCu₂O₃ and CoCu₂O₃ show antiferromagnetic transition (T_N) at 27 and 215 K, respectively. Co doping into (Ca_1−xCo_x)Cu₂O₃ enhances its T_N systematically with increasing Co concentration. The χ(T) of CoCu₂O₃ shows a broad transition with the peak temperature around 215 K and it was found to be field independent up to 90 kOe. The ambiguity concerning the transition was ruled out by recording the temperature dependent X-ray diffraction pattern on CoCu₂O₃ system, which indicated that there is no structural transition in the investigated temperature range of 115-300 K. Further, specific heat measurement on CoCu₂O₃ confirms the magnetic phase transition by the appearance of a sharp peak at 215 K.     

Bulk Sn1−xMnxO2 magnetic semiconductors without room-temperature ferromagnetism

Polycrystalline Sn_1−xMn_xO₂ (0≤x≤0.05) diluted magnetic semiconductors were prepared by solid-state reaction method and their structural and magnetic properties had been investigated systematically. The three Mn-doped samples (x=0.01, 0.03, 0.05) undergo paramagnetic to ferromagnetic phase transitions upon cooling, but their Curie temperatures are far lower than room temperature. The magnetization cannot be attributed to any identified impurity phase. It is also found that the magnetization increases with increasing Mn doping, while the ratio of the Mn ions contributing to ferromagnetic ordering to the total Mn ions decreases.     

Preparation, characterization and magnetic properties of the doped barium hexaferrites BaFe12−2xCox/2Znx/2SnxO19, x=0.0-2.0

A series of powders of M-typed barium hexaferrites doped with Co, Zn and Sn of general formula BaFe_12-2xCo_x/2Zn_x/2Sn_xO₁₉ (x=0-2.0) were prepared by the co-precipitation/molten salt method. The structures, particle morphology and magnetic properties of the products were characterized by X-ray powder diffraction, vibrating sample magnetometer and ESEM/EDX. The results show that the crystallinity of the samples decreases with increase in the doping amount x. When x is less than 0.6, it is possible to obtain perfectly crystallized hexagonal BaFe_12-2xCo_x/2Zn_x/2Sn_xO₁₉, where the diameters of the particles are around 500 nm. The saturation magnetization of pure barium ferrite BaFe₁₂O₁₉ produced with this method is 71.9 A m² kg⁻¹ at room temperature and the intrinsic coercivity (H_c) is 367.8 kA m⁻¹. The doped barium hexaferrite powder obtained when x is between 0.3 and 0.4 exhibits high saturation magnetization and a temperature dependence of coercivity close to zero.     

Chemical pressure effect in CeFeAs1−xPxO0.95F0.05

We investigate the chemical pressure effect due to P doping in the CeFeAs_1−xP_xO_0.95F_0.05(0≤x≤0.4) system. The compound CeFeAsO_0.95F_0.05 without P doping is on the boundary between antiferromagnet (AFM) and superconductor. The AFM order of Ce³⁺ local moments causes a significant reentrance behavior in both resistivity and magnetic susceptibility. Upon P doping, T_c increases and reaches a maximum of 21.3 K at x=0.15, and then it is suppressed to lower temperatures. Meanwhile, the AFM order of Ce³⁺ ions remains nearly the same in the whole doping range (0≤x≤0.4). Our experimental results suggest a competition between superconductivity and Kondo effect in the Ce 1111 system.