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.     

Ferroelectric phase transition of Ba1− x Sr x Ti0.6Zr0.4O3 ceramics

Perovskite type Ba_{1? x} Sr _x Ti_0.6Zr_0.4O₃ (with x = 0.0, 0.1, 0.2, 0.4 and 0.5) ceramics have been synthesized through solid oxide reaction route. The room temperature XRD study suggests the compositions have single phase cubic symmetry. Microstructural studies have shown a step decrease in grain size. The dielectric study reveals that the materials are of relaxor type and undergo a diffuse type ferroelectric phase transition. The diffusivity increases with increase in Sr contents in the studied composition range. The transition temperature decreases with increase in Sr contents due to the decrease in grain size.     

Dielectric properties and phase transitions of (Pb0.87La0.02Ba0.1)(Zr0.6Sn0.4−xTix)O3 ceramics with compositions near AFE/RFE phase boundary

The electrical properties and phase transition behavior of (Pb_0.87La_0.02Ba_0.1)(Zr_0.6Sn_0.4−xTi_x)O₃ solid solutions (PLBZST, 0.04≤x0.2) were investigated by the X-ray diffraction, permittivity, pyroelectric current, and P-E electric hysterisis loops. As the composition x increased from 0.04 to 0.2, the antiferroelectric ceramics (x≤0.07, AFE) with tetragonal phase changed to the ferroelectric relaxors (RFE, 0.09≤x). AFE ceramics showed a peculiar diffuse phase transition and dielectric relaxation at the low temperature (down to −100 °C) due to a frustration between AFE and FE state. With an increase in composition x, electrically field-induced AFE-FE switching field (E_AFE-FE) and AFE-paraelectric (PE) phase transition temperature (T_c) are depressed in the temperature (T)-Ti composition (x) phase diagram, a FE-AFE-PE triple phase point (T_tr) with the lowest transition temperature occurred at x=0.09. The pyroelectric currents under an application of various external electric field (E) were measured to identify a T-E phase diagram of the PLBZST compound.     

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.     

Structural and dielectric properties in the (Ba1−xCax)(Ti0.95Zr0.05)O3 ceramics

Lead-free (Ba_1−xCa_x)(Ti_0.95Zr_0.05)O₃ (x = 0.05-0.40) (BCZT) ceramics were prepared by solid-state reaction technique. XRD results show that the samples in the composition range of 0.05 ≤ x ≤ 0.25 exhibit pure perovskite structures and undergo a polymorphic phase transitions from orthorhombic to tetragonal phase around room temperature. The biphasic structures are detected at x ≥ 0.30 and the dielectric peaks become broad and dielectric constants decrease with increasing Ca content. Ca replacement at Ba site leads to diffuseness, whereas Ca occupancy at Ti site leads to decrease of the T_c.     

Luminescent properties of HTP AgGd1−xW2O8:Eux and AgGd1−x(W1−yMoy)2O8:Eux phosphor for white LED

Intense red phosphors, AgGd_1−xEu_x(W_1−yMo_y)₂O₈ (x=0.0-1.0, y=0.0-1.0), have been synthesized through traditional solid-state reaction and characterized by X-ray diffraction (XRD) and photoluminescence (PL). XRD results reveal that AgGd_1−xEu_xW₂O₈ synthesized at 1000 °C has a tetragonal crystal structure, which is named as high temperature phase (HTP) AgGdW₂O₈. All phosphors compositions with Eu³⁺ show red and green emission on excitation either in the charge-transfer or Eu³⁺ levels. Analysis of the emission spectra with different Eu³⁺ concentrations reveal that the optimum dopant concentration for Eu³⁺ is x=0.6 in the HTP AgGd_1−xEu_xW₂O₈ (x=0.0-1.0). Studies on the AgGd_0.4Eu_0.6(W_1−yMo_y)₂O₈ (y=0.0-1.0) and AgGd_1−xEu_x(W_0.7Mo_0.3)₂O₈ (x=0.0-1.0) show that the emission intensity is maximum for compositions with y=0.3 and x=0.5, respectively, and a decrease in emission intensity is observed for higher y or x values. The Mo⁶⁺ and Eu³⁺ co-doped AgGd(WO₄)₂ phosphors show higher emission intensity in comparison with the singly Eu³⁺-doped AgGd(WO₄)₂ in UV region. The intense emission of the tungstate/molybdate phosphors under 394 and 465 nm excitations, respectively, suggests that these materials are promising candidates as red-emitting phosphors for near-UV/blue GaN-based white LED for white light generation.     

XRD, microstructural and EPR susceptibility characterization of combustion synthesized nanoscale Mg1−xNixO solid solutions

The lattice parameter a(x) of the stoichiometric Mg_1−xNi_xO (0?x?1) solid solutions prepared by urea-based combustion synthesis with fuel to oxidizer ratio (ψ=1) was determined by X-ray diffraction. It was found that the dependence of the lattice parameter a(x) on the composition deviated more from the linear Vegard's model (VM) when compared to Kuzmin-Mironova (KM) model. a(x) in the Mg_1−xNi_xO system differs nontrivially from the predictions of both VM and KM models. For x=0.4 (Mg_0.6Ni_0.4O), the maximum deviation was about 2 and 1.7 pm, respectively. The increase in the intensity of (1 1 1) peak in XRD with increase of nickel concentration confirms that the substitution induces changes at the unit cell level. Nelson-Riley function (NRF) and Williamson-Hall plots are used to calculate micro strain in the solid solution. This analysis indicates that the micro strain is maximum for the compositions 60-40 (Mg_0.6Ni_0.4O), 50-50 (Mg_0.5Ni_0.5O) and 40-60 (Mg_0.4Ni_0.6O). The crystallite size was estimated using Williamson-Hall plot. We conclude that almost similar sized crystallite is formed in all the compositions studied. Porosity determined using XRD increases with a raise in the nickel concentration. The SEM morphology provides corroborative evidence. EPR susceptibilities of solid solution Mg_1−xNi_xO are determined at room temperature. Variable temperature of EPR allowed to check the Curie-Weiss law for solid solution. The linearity of C_M(x) and Θ(x) with concentration of nickel has ruled out chemical clustering in the samples.     

Magnetic phase diagrams of Ho1−xDyxNi2B2C

We performed the magnetization measurement on Ho_1−xDy_xNi₂B₂C single crystals (x=0.1, 0.2, 0.3, 0.4, and 0.6) with magnetic field applied perpendicular and parallel to the c-axis. But only for the magnetic field perpendicular to the c-axis, the increase of Dy³⁺ concentration affects the magnetically ordered states of HoNi₂B₂C compound and makes the phase diagram more complicated. The antiferromagnetic ordering state attributed to Dy³⁺ sublattice starts to appear from a case of x=0.2 and finally the magnetic phase diagram becomes analogous to that of DyNi₂B₂C as x is increased which is consistent with the neutron scattering result.     

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.     

Mössbauer study of the re-entrant spin-glass behaviour in the mixed spinel ferrites Mg(0.9+x)Fe2(1−x)Ni0.1TixO4 (x=0.5 and 0.6)

Samples of the mixed spinel ferrite series Mg_(0.9+x)Fe_2(1−x)Ni_0.1Ti_xO₄ with x=0.5 and 0.6, prepared by solid state reaction of the appropriate oxides, have been investigated with ⁵⁷Fe Mössbauer spectroscopy. The as-prepared samples are found to be mainly superparamagnetic due to magnetic cluster formation. Samples after at least three times reheated exhibit spectra, which can be rather interpreted by a transversal relaxation of the spin above and spin-glass behaviour below the respective freezing temperatures T_f. External-field spectra reveal the canting to occur only on the octahedral sites. From the derived transition temperatures and thresholds together with data from earlier investigated sample with x=0.7 a compositional magnetic phase diagram for this spinel series is obtained.     

Entropy changes accompanying the magnetic phase transitions in low Si-doped Ce2Fe17−xSix Alloy

A summary of the results of ac susceptibility and isothermal magnetization measurements on polycrystalline samples of Ce₂Fe_17−xSi_x with nominal composition of x=0.0, 0.1, 0.2 and 1.0 is presented. These data reveal that the substitution of small amounts of Si for Fe produce a significant increase in temperature at which ferromagnetism appears, to the extent that, at x=1, characteristics of the anti ferromagnetic to paramagnetic transition (at temperature T_N) have disappeared completely. The nature of the various magnetic phase transitions — identified through the use of Arrott plots — and the accompanying magnetic entropy change, ΔSm, are both affected significantly by small amounts of Si substitution. In particular, while the peak entropy change is modest (occurring at x=0.1), the temperature interval over which a substantial entropy change occures is significant, approaching 150 K, an important criterion for improving the overall effectiveness of such materials for magnetic refrigeration.     

Dielectric, ferroelectric and pyroelectric properties of Pb[(Ni1/3Sb2/3)xTiyZrz]O3 ceramics

In the present study, various Pb[(Ni_1/3Sb_2/3)_xTi_yZr_z]O₃ where x+y+z=1, x=0.08 and y=0.44-0.49, ceramics in the morphotropic phase boundary (MPB) range were studied by dielectric and pyroelectric methods. The results of the investigations revealed an MPB composition range of y≅0.46. The study of the dielectric properties of these compounds as a function of temperature suggests that with increase in y the permittivity maximum increases and transition temperature shifts towards higher temperature. Well-saturated polarization versus electric field (P-E) hysteresis loops were obtained and values of P_r were calculated. The samples revealed good pyroelectric properties for y=0.44 and y=0.45 at room temperature with large figures of merit F_v=0.019 m²/C and F_D=1.34×10^-5Pa^1/2.     

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.     

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.     

Effect of Sn-doping on the structural,magnetic and magnetocaloric properties of La0.67Ba0.33Mn1−xSnxO3 compounds

Magnetocaloric effect (MCE) in fine-grained perovskite manganites of the type La_0.67Ba_0.33Mn_1−xSn_xO₃ (x=0.05, 0.1 and 0.15) were prepared by the solid-state method. The prepared samples remain single phase and exhibit paramagnetic to ferromagnetic phase transition (T_C) at 340, 325 and 288 K for x=0.05, 0.1 and 0.15, respectively. From the measured magnetization data of La_0.67Ba_0.33Mn_1−xSn_xO₃ compounds as a function of field (2 T), the associated magnetic entropy change close to their respective Curie temperatures and the relative cooling power (RCP) have been determined. Large MCE has been obtained in all samples and |ΔS_M|_max reached the highest value of 2.49 J/kg K at T_C (288 K) for the sample x=0.15, with H=2 T.     

Phase transition, structural and electrical properties of Pb(Zn1/3Nb2/3)O3-doped Pb(Ni1/3Nb2/3)O3-PbTiO3 ceramics prepared by solid-state reaction method

Phase pure perovskite (1−x−y)Pb(Ni_1/3Nb_2/3)O₃-xPb(Zn_1/3Nb_2/3)O₃-yPbTiO₃ (PNN-PZN-PT) ferroelectric ceramics were prepared by conventional solid-state reaction method via a B-site oxide mixing route. The PNN-PZN-PT ceramics sintered at the optimized condition of 1185 °C for 2 h exhibit high relative density and rather homogenous microstructure. With the increase of PbTiO₃ (PT) content, crystal structure and electrical properties of the synthesized PNN-PZN-PT ceramics exhibit successive phase transformation. A morphotropic phase boundary (MPB) is supposed to form in (0.9−x)PNN-0.1PZN-xPT at a region of x=32-36 mol% confirmed by X-ray diffraction (XRD) measurement and dielectric measurement. The MPB composition can be pictured as providing a “bridge” connecting rhombohedral ferroelectric (FE) phase and tetragonal one since crystal structure of the MPB composition is similar to both the rhombohedral and tetragonal lattices. Dielectric response of the sintered PNN-PZN-PT ceramics also exhibits successive phase-transition character. 0.64PNN-0.1PZN-0.26PT exhibits broad, diffused and frequency dependent dielectric peaks indicating a character of diffused FE-paraelectric (PE) phase transition of relaxor ferroelectrics and 0.40PNN-0.1PZN-0.50PT exhibits narrow, sharp and frequency independent dielectric peaks indicating a character of first-order FE-PE phase transition of normal ferroelectrics. The FE-PE phase transition of 0.56PNN-0.1PZN-0.34PT is nearly first-order with some diffused character, which also exhibits the largest value of piezoelectric constant d₃₃ of 462pC/N.     

Structural, chemical and magnetic investigations of polycrystalline Zn1−xMnxO

Present study reports the detailed structural and magnetic, as well as chemical analysis of polycrystalline Zn_1−xMn_xO (where x=0, 0.005, 0.01, 0.03, 0.05 and 0.1) samples synthesized by the high-temperature solid state reaction route. X-ray diffraction studies reveal the presence of secondary phase for higher Mn-doping concentrations (x≥0.03). Secondary phase formation having spinel structure is confirmed and reported as an evidence for the first time using transmission electron microscopy study. Chemical investigations using X-ray photoelectron spectroscopy showed the presence of Mn in two valence states. From the observed results we are of the opinion that Zn²⁺ ions, mainly present at or near grain boundaries, diffuse into manganese oxide to form a stable spinel phase Zn_xMn_3−xO₄ at or near the grain boundaries of ZnO/Zn_1−xMn_xO. Magnetization measurements did not show any magnetic transition down to 5 K.     

Magnetic and optical properties of spinel FexCo3−xO4 thin films

Magnetic and optical properties of Fe_xCo_3−xO₄ thin films grown by sol–gel method have been investigated as the Fe composition (x  ) increases from 0 to 2. X-ray diffraction measurements revealed that the normal- and inverse-spinel phases coexist for 0.76?x?0.93$0.76?x?0.93$. The normal-spinel phase is dominant below x=0.76$x=0.76$ while the inverse-spinel phase above x=0.93$x=0.93$. The lattice constant of the inverse-spinel phase is found to be larger than that of the normal-spinel phase. For both phases the lattice constant increases with increasing x. The Fe_xCo_3−xO₄ films containing the inverse-spinel phase exhibit net magnetization that increases with increasing x  . Conversion electron Mössbauer spectrum measured on the x=0.93$x=0.93$ sample showed that Fe²⁺ ions prefer the octahedral sites, indicating the formation of the inverse-spinel phase. Analysis on the measured optical absorption spectra for the samples by spectroscopic ellipsometry indicates a dominance of the normal-spinel phase for low x in which Fe³⁺ ions mostly occupy the octahedral sites. Observation of a crystal-field transition at 1.6 eV originating from tetrahedral Fe³⁺ ion confirms the existence of the inverse-spinel phase for high x.     

Effect of Ni doping on structural and magnetic properties of Co1-xNixFe1.9Mn0.1O4

Nickel-substituted iron-deficient cobalt ferrite containing small quantity of manganese having the chemical composition Co_1−xNi_xFe_1.9Mn_0.1O₄ with x=0.2, 0.4, 0.6 and 0.8, were prepared by the standard double sintering ceramic technique. The thermal decomposition process of the powder (i.e. grounded starting materials) was studied by thermo-gravimetric analysis (TGA). The compositional analysis was carried out by EDAX pattern. The infrared spectroscopy studies show the presence of tetrahedral and octahedral group complexes within the spinel phase. Microstructural features were studied by scanning electron microscopy, grain size found to be decreasing with increasing Ni content. Room temperature hysteresis measurement was carried out under the field of 6 kOe for all samples which reveal monotonic decrease of magnetization at 6 kOe (M_6 kOe). The coercive field (H_c) decreases up to concentration of Ni²⁺ (x=0.6) and a small increase was observed for x=0.8. Initial permeability (μ_i) plotted against temperature at 10 kHz shown sharp drop at Curie temperature and values observed at transition are found to be dependent on the nickel content.     

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.