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.     

In situ energy dispersive X-ray diffraction study of iron disilicide thermoelectric materials

The dynamic phase transformation and structure of rapidly solidified Fe_1−xCo_xSi₂ (0.02?x?0.06) thermoelectric materials were in situ investigated under high temperatures and high pressures by energy dispersive X-ray diffraction using synchrotron radiation. The FeSi₂ alloys which solidified as α-Fe₂Si₅ and ε-FeSi eutectic structures, were transformed to the semiconducting β-FeSi₂ phase upon heating by the main reaction α+ε→β and the subsidiary reaction α→β+Si. The low heating rates and Co contents were found to be beneficial for the β phase formation. The decomposition temperature of β→α+ε was weakly dependent on heating rate, but significantly suppressed by the high pressures.     

A novel high-k ‘Y5V’ barium titanate ceramics co-doped with lanthanum and cerium

Structural, dielectric, and ferroelectric properties of a novel high-k ‘Y5V’ (Ba_1−xLa_x)(Ti_1−x/4−yCe_y)O₃ ceramics (where x=0.03 and y=0.05, denoted by BL3TC5) with the highest ‘Y5V’ dielectric response (ε′>10 000) among rare-earth-doped BaTiO₃ ceramics to date are investigated in detail using SEM, TEM, XRD, DSC, EPR, Raman spectroscopy (RS), temperature and frequency, electric field dependences of dielectric permittivity (ε′), and temperature and electric field dependences of ferroelectric hysteresis loops. The BL3TC5 diffusion of ferroelectric phase transition occurs around dielectric peak temperatures (T_m) near a room temperature characteristic of dielectric thermal relaxation. Powder XRD data and defect complex model were given. “Relaxor” behavior associated with an order/disorder model and formation of a solid solution were discussed. The EPR results provided the evidence of Ti vacancies as compensating for lattice defects. High-k relaxor nature of BL3TC5 is characterized by an average cubic structure with long-range lattice disordering and local polar ordering; a slow change of the ε′ (T) and P_r(T) curves around T_m; no phase transition observed by DSC; and a broad, red-shifted A₁ (TO₂) Raman phonon mode at 251 cm⁻¹ accompanying the disappearance of the “silent” mode at 305 cm⁻¹ and a clear anti-resonance effect at 126 cm⁻¹ at room temperature.     

Urbach rule and disordering processes in Cu6P(S1−xSex)5Br1−yIy superionic conductors

Compositional behavior of Urbach absorption edge is studied as well as the effect of compositional disordering on the parameters of exciton-phonon interaction, phase transition temperatures and electric conductivity in Cu₆P(S_1−xSe_x)₅Br_1−yI_y superionic solid solutions. The effect of different types of disordering on the optical absorption processes and specific features of compositional changes in the absorption edge spectra under S→Se and Br→I anion substitution in the mixed crystals are investigated. (x, T) phase diagrams for Cu₆P(S_1−xSe_x)₅X (X=I, Br) solid solutions are studied.     

Structural and photoluminescence properties of thermally evaporated Cd1−xMnxS nano-crystalline films

Thin films of Cd_1−xMn_xS (0≤x≤0.5) were formed on glass substrates by resistive vacuum thermal evaporation. All the films were deposited at 300 K and the films were annealed at 373, 473 and 573 K for 1 h in a vacuum of 10⁻⁶ mbar. Atomic force microscopy (AFM) studies showed that all the films investigated were in nano-crystalline form with a grain size in the range 36-82 nm. All the films exhibited a wurtzite structure of the host material. The lattice parameters varied linearly with composition following Vegard’s law in the entire composition range. Photoluminescence studies showed that two distinct emission bands were observed for each Cd_1−xMn_xS compound. One corresponds to internal transition and the other one is due to the transition of Mn²⁺ ions in interstitial sites or in small ‘Mn’ chalcogenic clusters.     

Spin polarization of Fe-rich ferromagnetic compounds in Ru2−xFexCrSi Heusler alloys

We report spin polarization P of Ru_2−xFe_xCrSi Heusler alloys by the Andreev reflection technique. Ru_2−xFe_xCrSi with L2₁-type structure and saturation magnetic moment of per formula unit is theoretically predicted to be half-metals in the wide range of the composition x. We had clarified that the experimental results of saturation magnetic moment in Fe-rich compounds had coincided with the theoretical prediction. Therefore, we have measured the differential conductance of Ru_2−xFe_xCrSi/Pb planar-type junctions. The P value of Ru_2−xFe_xCrSi was determined by fitting the differential conductance with the modified Blonder-Tinkham-Klapwijk theory. We have found that the behavior of P for Ru_2−xFe_xCrSi was independent of the composition x in the Fe-rich region; P=0.53 for both of x=1.5 and 1.7. The spin polarization is the similar value to Co-based Heusler alloys.     

Structure and dielectric properties of (Na0.50Bi0.50)1−xBaxTiO3: 0≤x≤0.10

Solid solution of (1−x)Na_0.5Bi_0.5TiO₃-xBaTiO₃ is investigated in the composition range 0.00≤x≤0.10. It is shown that the system exhibits rhombohedral structure up to x=0.055 and then becomes ‘nearly cubic’ for x≥0.06. Temperature dependent dielectric measurements reveals three peaks in the imaginary part of the dielectric constant for compositions exhibiting rhombohedral as well as ‘nearly cubic’ structures. The first of these three peaks exhibits Vogel-Fulcher type relaxation behaviour.     

Optical and physical properties of different composition of InxSe1−x thin films

Thin film binary alloys of In_xSe_1−x (0.05?x?0.30) have been prepared by the thermal evaporation technique. The optical transmission and reflection spectrum of these films were measured in the range 300-1100 nm. Both refractive index, n and extinction coefficient k have been determined from transmission and reflection measurements in terms of Murmann's equations. The dispersion of the refractive index is discussed in terms of the single-oscillator Wemple-DiDomenico model. The width of band tail is determined and the optical absorption edge is described using the ‘non-direct transition’ model proposed by Tauc. Finally, the relationship between the optical gap and chemical composition in In_xSe_1−x amorphous system is discussed in terms of the average heat of atomization H_s and average coordination number N_c. The results of these calculations can be used rationalize the observed optical properties of these materials. Finally, the chemical bond approach has been also applied to interpret the decrease of the glass optical gap with increasing In content.     

Carbon doping in MgB2: role of boron and carbon px(y) bands

We have studied the changes in the electronic structure and the superconducting transition temperature T_c of Mg(B_1−xC_x)₂ alloys as a function of x with 0≤x≤0.3. Our density-functional-based approach uses the coherent-potential approximation to describe the effects of disorder, the Gaspari-Gyorffy formalism to estimate the electron-phonon matrix elements and the Allen-Dynes equation to calculate T_c in these alloys. We find that the changes in the electronic structure of Mg(B_1−xC_x)₂ alloys, especially near the Fermi energy E_F, come mainly from the outward movement of E_F with increasing x, and the effects of disorder in the B plane are small. In particular, our results show a sharp decline in both B and C p_x(y) states for 0.2≤x≤0.3. Our calculated variation in T_c of Mg(B_1−xC_x)₂ alloys is in qualitative agreement with the experiments.     

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.     

Effective medium theory for the inhomogeneous PdMnxFe1−x alloys

Ternary PdMn_xFe_1−x alloys are known to form a microinhomogeneous random mixture of PdMn and PdFe phases. The unconventional ρ(x) dependence of dc resistivity and singularities in low frequency optical conductivity spectra of alloys are described footing within the effective medium approach. The essential point of the model proposed is the anomalous role of insulating interfaces, whose proliferation at intermediate x gives rise to the observed maximum of resistivity near x?0.8.     

Structure of the low-temperature phase of Rb3D(SeO4)2 by single-crystal neutron diffraction

Crystal structure of Rb₃D(SeO₄)₂ has been investigated at 25 K (below the transition temperature T_c=95.4 K) by single-crystal neutron diffraction. Accompanying the transition, the SeO₄ groups, which are all equivalent in the phase above the transition (space group A2/a), split into eight nonequivalent groups in a superlattice (a×2b×2c, space group A2) in the low-temperature phase. Based on the D atom positions obtained, each of the SeO₄ groups was identified to be in the state closer to a HSeO₄⁻ ion or to a SeO₄²⁻ ion and the dipole arrangement of SeO₄-D-SeO₄ dimer was revealed. This dipole arrangement has ‘ferri’ structure along the polar b-axis, but ‘antiferro’ structure in the plane perpendicular to the b-axis. These results are consistent with the characteristics found in the earlier dielectric measurements.     

Compositional dependence of the optical properties of amorphous semiconducting glass Ge10AsxSe(90−x) thin films

Optical properties of ternary chalcognide amorphous Ge₁₀As_xSe_(90−x) (with 10?x?25 at%) thin films prepared by thermal evaporation have been measured in visible and near-infrared spectral region. The straightforward analysis proposed by Swanepoel has been successfully employed, and it has allowed us to determine the average thickness , and the refractive index, n, of the films, with high accuracy. The refractive index, n and the average thickness has been determined from the upper and lower envelopes of the transmission spectra measured at normal incidence, in the spectral range 400-2500 nm. The absorption coefficient α, and therefore extinction coefficient k, have been determined from the transmission spectra in the strong-absorption region. The dispersion of the refractive index is discussed in terms of the single oscillator Wemple-DiDomenico model, and the optical absorption edge is described using the ‘nondirect transition’ model proposed by Tauc. Likewise, the optical energy gap is derived from Tauc's extrapolation. The relationship between the optical gap and chemical composition in Ge₁₀As_xSe_(90−x) amorphous system is discussed in terms of the average heat of atomization H_s and average coordination number N_c. Finally, the chemical bond approach has been also applied successfully to interpret the decrease of the glass optical gap with increasing As content.     

The a.c. susceptibility third harmonic component of NdO1−0.14F0.14FeAs: A flux dynamic magnetic analysis

In this contribution we present the analysis of the third harmonic susceptibility data of the new superconductor NdFeAs_1−0.14F_0.14. ‘Cole-Cole’ polar plots respect to the magnetic frequency of the exciting field are presented and discussed. Data show that NdFeAs_1−0.14F_0.14 exhibit a ‘bulk pinning’ with a 3D flux dynamic character. A comparison of the responses of high T_c materials and an evaluation of theoretical critical states is also presented.     

The large low-field magnetic entropy changes in Ni43Mn46Sn11−xSbx alloys

A series of Ni₄₃Mn₄₆Sn_11−xSb_x (x=0, 1, and 3) alloys were prepared by an arc melting method. The martensitic transition shifts to higher temperature with the increasing Sb content. The isothermal magnetization curves and Arrott plots around martensitic transition temperatures show a typical metamagnetic behavior. Under a low applied magnetic field of 10 kOe, large magnetic entropy changes around the martensitic transition temperature are 10.4, 8.9, and 7.3 J/kg K, for x=0, 1, and 3, respectively. The origin of the large magnetic entropy changes and potential application for Ni₄₃Mn₄₆Sn_11−xSb_x alloys as working substances in magnetic refrigeration are discussed.     

Crystal structure and cation distribution in the solid solution series 2(ZnX)-CuInX2 (X=S, Se, Te)

The solid solution series (2ZnX)_x (CuInX₂)_1−x (X=S, Se, Te) were studied by the combination of laboratory and synchrotron X-ray and by neutron powder diffraction. Within the homologous series the tetragonal distortion ¼-u increases in the sequence S→Se→Te whereas the tetragonal deformation η=c/2a decreases. Besides that, with increasing 2ZnX content in CuInX₂ the anion position parameter u increases as expected. The cation site occupancy in the chalcopyrite type phase of single phase tetragonal samples was obtained by Rietveld analysis of the neutron diffraction data. A non-statistic Zn distribution could be deduced for all three systems. The high temperature in situ diffraction experiments with synchrotron radiation on CuInX₂ powder samples revealed the Cu-In anti-site occupation as the driving force of the temperature dependent phase transition from the chalcopyrite to the zinc-blende type structure.     

Highly cation-deficient manganese perovskite, La1−xMn1−yO3 with x=y

Oxidative (δ>0) nonstoichiometry in the perovskite ‘LaMnO_3+δ’ has been known to be manifested not with O interstitials but rather with cation vacancies of equal amounts at the two cation sites, La and Mn, i.e. La_1−xMn_1−yO₃ with x=y. Here, we report the fabrication of samples with record-high cation-vacancy concentrations (x>0.12 or δ>0.4) by means of a variety of high-pressure oxygenation techniques. Linear (negative) dependence of the cell volume on x was observed within the whole x range investigated, down to 56.9 Å³ (per formula unit) for a sample oxygenated at 5 GPa and 1100 °C using Ag₂O₂ as an excess oxygen source. With increasing degree of cation deficiency in La_1−xMn_1−xO₃, the ferromagnetic transition temperature was found to follow a bell shape with respect to x exhibiting a maximum of ∼250 K about x≈0.1. For moderately oxygenated samples large magnetoresistance effect was evidenced.     

Enhancement in soft magnetic and ferromagnetic ordering behaviour through nanocrystallisation in Al substituted CoFeSiBNb alloys

The effect of substituting Al for Si in Co₃₆Fe₃₆Si_4−xAl_xB₂₀Nb₄, (X=0, 0.5, 1.0, 1.5, 2.0 at%) alloys prepared in the form of melt-spun ribbons have been investigated. All the alloys were amorphous in their as-cast state. The onset of crystallization as observed using differential scanning calorimetry (DSC) was found to rise at low Al content up to X=1 at% beyond which there was a decreasing trend. The alloys also exhibited glass transition at ‘T_g’. Microstructural studies of optimally annealed samples indicated finer dispersions of nanoparticles in amorphous matrix which were identified as bcc-(FeCo)Si and bcc-(FeCo)SiAl nanophases by X-ray diffraction technique. Alloy with optimum content of Al around X=1 at% exhibited stability in coercivity at elevated temperatures. Though Al addition is known to lower magnetostriction, such consistency in coercivity may also be attributed towards lowering in the nanoparticle size compared to X=0 alloy. In the nanostructured state, the alloy containing optimum Al content (X=1) exhibited further enhancement in ferromagnetic ordering or the Curie temperature by 100 K compared to alloy without Al. Such addition also attributed to better frequency response of coercivity and low core losses.     

Structural,thermal and electrical properties of the semiconductor system Ag(1−x)CuxInSe2

This paper presents a study of bulk samples synthesized of the Ag_1−xCu_xInSe₂ semiconductor system. Structural, thermal and electrical properties, as a function of the nominal composition (Cu content) x=0.0, 0.2, 0.4, 0.6, 0.8, and 1.0 were studied. The influence of x on parameters such as melting temperature, solid phase transition temperature, lattice parameters, bond lengths, crystallite size t (coherent domain), electrical resistivity, electrical mobility and majority carrier concentration was analyzed. The electrical parameters are analyzed at room temperature. In general, it is observed that the properties of the Ag_1−xCu_xInSe₂ system for x≤0.4 are dominated by n-AgInSe₂, while for x>0.4, these are in the domain of p-CuInSe₂. The crystallite size t in the whole composition range (x) is of the order of the nanoparticles. Secondary phases (CuSe, Ag₂Se and InSe) in small proportion were identified by XRD and DTA.