Emission (Gd3+ and Sm3+) and ESR (Gd3+) studies of La1−xLnxB3O6 (Ln = Gd,Sm; 0 ≤ x ≤ 0.2 for Gd; 0 ≤ x ≤ 0.1 for Sm) phosphors

Polycrystalline powders of rare-earth doped La_1?xGd_xB₃O₆ (0?≤?x?≤?0.2) and La_1?xSm_xB₃O₆ (0.0?≤?x?≤?0.1) phosphors were successfully prepared by a B₂O₃ flux method. All the phosphor samples are well characterized by powder X-ray diffraction (XRD), infrared (IR), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) methods and fluorescence lifetime of Sm³⁺ ion. The XRD patterns show that La_1?xM_xB₃O₆ (M?=?Gd and Sm) adopt monoclinic with the I2/a space group. The SEM–EDS results confirmed the doping of Gd and Sm into LaB₃O₆ lattice. The IR and Raman spectra of these solid solutions gave distinctive bands corresponding to planar BO₃ and tetrahedral BO₄ groups. The photoluminescence (PL) spectra of La_1?xGd_xB₃O₆ gave a strong emission band, ⁶P_J?→?⁸S_7/2, at 310 nm. The PL spectra of La_1?xSm_xB₃O₆ phosphor showed orange-red emission at 598 nm when excited using light of wavelength of 402 nm. The results were obtained by the transition ⁴G_5/2?→?⁶H_7/2 of Sm³⁺ ions. The influence of dopant concentration on the emission profiles was studied. The ESR spectra of La_1?xGd_xB₃O₆ (x?=?0.02) gave a typical U-spectrum and spin-Hamiltonian parameters are deduced.

     

Mixed-valence La0.80(Ag1−x Sr x )0.20MnO3 manganites with magnetocaloric effect

We report the effect of the simultaneous inclusion of Ag¹⁺ and Sr²⁺ cations on the crystal structure and the magnetocaloric effect (MCE) of La_0.80(Ag_1?x Sr _x )_0.20MnO₃ manganites (x = 0.0, 0.25, 0.50, 0.75, 1.0) synthesized by the solid-state reaction method. X-ray photoelectron spectroscopy was used to verify chemical composition and the amount of Mn³⁺–Mn⁴⁺ cations, while the magnetic performance was evaluated by means of a Physical Property Measuring System. The progressive substitution of Ag¹⁺ by Sr²⁺ causes the increase of the number of Mn⁴⁺ cations, together with increasing ionic radii for the A-site contents up to x = 0.75, both favoring the enhancement of the double-exchange interaction and hence, the MCE. Excellent values of magnetic entropy change (?4.6 J/kg K, μ _oΔH = 5.0 T) were observed for the x = 0.25 manganite, while for the x = 0.50 sample interesting refrigerant capacity (129 J/kg, μ _oΔH = 2.0 T) and a wide interval of temperature at the full-width at half maximum δT _FWHM of the magnetic entropy change curve were recorded (101 K, μ _oΔH = 2.0 T) caused by two successive magnetic transitions. Magnetic performance was explained in terms of the effect of the cation substitution on the double-exchange interaction and the tolerance factor.     

Improving the physical properties of polycrystalline-deficient Pr0.8Sr0.2−x□xMnO3 (0 ≤ x ≤ 0.2) compounds for electronic devices

Deficient strontium effects upon structural and spectroscopic properties of Pr_0.8Sr_0.2MnO₃ have been investigated. Pr_0.8Sr_0.2?x□_xMnO₃ (0?≤?x?≤?0.2) powder samples have been elaborated by the conventional ceramic method. All the samples crystallized in the orthorhombic perovskite system with Pnma (for x?=?0 and 0.05) and Pbnm (for x?=?0.1 and 0.2) space groups. The impedance spectroscopy measurements, the AC conductivity was investigated in the frequency range 40 to 5?×?10⁶ Hz and in the temperature range 80–500 K. DC measurements show that the studied compounds exhibit a semiconductor behavior in the temperature range studied. We have demonstrated that the conduction mechanism is governed by the hopping process at high temperatures as observed for doped perovskite materials. The AC conductivity results were well described by the Jonscher power law. The evolution of the frequency exponent s was determined in order to investigate the conduction mechanism in deficient structures. A discrepancy between the results obtained with the parent sample and deficient structures was observed. Analysis of the complex impedance shows that our structures obey Cole–Cole model. Nyquist plots were obtained using the Maxwell–Wagner equivalent circuit model. The evolution of the real and imaginary parts ε′ and ε″ of the permittivity was studied as a function of frequency, temperature, and strontium deficiency. Both ε′ and ε″ exhibit a strong dependence on these parameters. A step-like decrease in the dielectric constant ε′ was observed which may have originated from the space charge polarization and blocking electrode effect. The dielectric loss ε″ decreased with increasing frequency but increased with temperature for all studied samples. This result was correlated with the conduction mechanism which is governed by grain boundaries at low frequencies and grains at high frequencies. In addition, it affected the capacitance values in each frequency interval.

     

Thermal Diffusivity of La1−x Sr x MnO3 (x < 0.3)

Perovskite manganites are interesting because of their colossal magnetoresistance. In this work high resolution thermal diffusivity measurements of La_1–x Sr _x MnO₃ (0 x 0.3) single crystals in the temperature range from 250 to 400 K are presented. A photopyroelectric device in the standard back configuration has been used. The thermal diffusivity through second-order magnetic phase transitions, as well as through first- and second-order structural phase transitions has been measured. The critical parameters of the sample with x = 0.3 at the ferromagnetic-to-paramagnetic transition have been obtained, and are close to the values predicted by the Ising model.     

Magnetocaloric study of monovalent-doped manganites Pr0.6Sr0.4−x Na x MnO3 (x = 0–0.2)

A systematic investigation of structural, magnetic, and magnetocaloric properties is reported for a series of monovalent sodium-doped manganites Pr_0.6Sr_0.4?x Na _x MnO₃ (x = 0, 0.05, 0.1, 0.15, and 0.2). Rietveld refinements of the X-ray diffraction patterns show that all powder samples are single-phased and crystallized in the orthorhombic structure with Pnma space group. Magnetic characterization and Arrott plot confirm the second-order phase transition at Curie temperature T _C decreasing from 310 K for x = 0 down to 272 K for x = 0.2. Magnetic entropy change is largest for x = 0 reaching 1.95 J kg^?1 K^?1 at 2 T field. This corresponds to a large relative cooling power of 102 J kg^?1 . Magnetic field sensitivity of magnetic entropy change and relative cooling power are analyzed and discussed.     

Effect of Non-magnetic Ti4+ Ion Doping at Mn-site on Magnetocaloric Properties and Critical Behavior in AMn1-xTixO3 (0 ≤ x ≤ 0.2) Compounds

Journal of Low Temperature Physics - In this paper, we present a thorough study for the critical behavior of AMn1-xTixO3 (A?=?La0.5Pr0.2Sr0.3, x?=?0.0 and 0.2)...     

Effect of Fe Substitution on the Structural,Magnetic and Magnetocaloric Properties of Pr0.6La0.1Mg0.3Mn1−x Fe x O3 (0≤x≤0.3) Perovskite Manganites Prepared by Sol Gel Method

Studies of the structural, magnetic, and magnetocaloric properties of polycrystalline Pr_0.6La_0.1Mg_0.3Mn_1?x Fe _x O₃ (0≤x≤0.3) perovskite manganites were carried out. The compounds were synthesized using the sol–gel method. X-Ray diffraction (XRD) analysis using Rietveld refinement shows that all our compounds crystallize in the orthorhombic structure with the Pnma space group. The surface morphology and elemental analysis of both samples were carried out by scanning electron microscopy (SEM) and the energy dispersive X-ray technique (EDX), respectively. Magnetization measurements versus temperature under magnetic applied field of 0.05 T showed that all our investigated samples display a ferromagnetic-paramagnetic transition. The substitution of Mn by Fe leads to an increase of the Curie temperature T _C from 64 K for x=0 to 380 K for x=0.3. The Arrott plots show that the phase transition is of second order. A large magnetic entropy change |ΔS _M | deduced from isothermal magnetization curves has been recorded in the parent compound Pr_0.6La_0.1Mg_0.3MnO₃ reaching a maximum of 0.79 J/kg K under a magnetic applied field of 2 T close to T _C . Our results on magnetocaloric properties suggest that the Pr_0.6La_0.1Mg_0.3MnO₃ compound is attractive as a possible refrigerant for low temperature magnetic refrigeration.     

Appearance of Griffiths Phase in La0.7−x Pr x Ba0.3MnO3 (0 ≤x≤ 0.2)

Polycrystalline La_0.7?x Pr _x Ba_0.3MnO₃ (0 ≤x≤ 0.2) samples were prepared using solid-state reaction and checked by X-ray diffraction. Magnetization measurements versus temperature and applied magnetic field were used to investigate their magnetic properties. For samples with x= 0.2, the Griffiths phase is observed when the inverse of susceptibility (1/ χ vs. T) is analyzed.     

Critical behavior in Fe-doped manganites La0.67Ba0.22Sr0.11Mn1−x Fe x O3 (0 ≤ x ≤ 0.2)

The critical properties of the manganese perovskite La_0.67Ba_0.22Sr_0.11Mn_1?x Fe _x O₃ (0 ≤ x ≤ 0.2) around the paramagnetic (PM)–ferromagnetic (FM) phase transition were investigated using modified Arrott plots and Kouvel–Fisher method based on the data of static magnetic measurements recorded around the curie temperature T _C. Based on the evaluated critical exponents for the compounds with different x values (0.378 ≤ β ≤ 0.411, 1.247 ≤ γ ≤ 1.393, and 4.018 ≤ δ ≤ 4.73) we concluded that the PM–FM phase transition in the compound with x = 0 belongs to the three-dimensional Heisenberg universality. However, the substitution of Fe³⁺ for Mn³⁺ resulted in shifting the value of γ toward the 3D-Ising model value and a slight increase in β. This behavior was discussed and correlated with the random distribution of Fe³⁺ at the Mn³⁺ sites and the consequent suppression the double exchange interaction.     

Effect of Fe-doping on Magnetocaloric Properties of AMn1?x Fe x O3 Compounds (0≤x≤0.2)

We have investigated the effect of iron substitution on the magnetocaloric properties of manganites with La_0.75Ca_0.08Sr_0.17Mn_1?x Fe _x O₃ (x=0, 0.075, 0.15, 0.175, and 0.2) nominal composition. The magnetocaloric effect (MCE) was estimated, in terms of isothermal magnetic entropy change (???S _M ), using the M(T,?? ₀ H) data and employing the thermodynamic Maxwell equation. The large magnetic entropy in AMn_1?x Fe _x O₃ is attributed to the field-induced suppression of short-range charge-orbital ordering and antiferromagnetic fluctuations present above T _C . The increase of the Fe concentration x is accompanied by a decrease of (???S _M ), from 5.205 to 0.95?J/kg?K for x=0 and 0.20, respectively, with ?? ₀ H=5?T. For all samples, we find quite large values of (???S _M ), which are very close to that provided for Gd, the prototypical magnetocaloric material.     

Effect of annealing temperature on the electromagnetic properties of La0.8Sr0.2MnO3 prepared by sol–gel process

Journal of Materials Science: Materials in Electronics - La0.8Sr0.2MnO3 (LSMO) powder was prepared using the sol–gel method and treated at different annealing temperatures (AT), and the...     

Conduction in nanostructured La1?x Sr x FeO3 (0 ≤ x ≤ 1)

We investigated electrical properties of nanostructured La_1?x Sr _x FeO₃ (0 ?? x ?? 1) from 300 K?C400 K. The nanostructured La_1?x Sr _x FeO₃ (0 ?? x ?? 1) was synthesized by citrate gel method requiring no pH control. X-ray diffraction pattern showed that single phase LaFeO₃ with an orthorhombic structure was formed. The structure changed into rhombohedral for x = 0.5 and it became cubic for x = 1.0. For x ?? 0.5, our material showed non-linear current-voltage characteristics and for x > 0.5 it showed linear current-voltage characteristics. Poole Frenkel type conduction mechanism was found to be operative in LaFeO₃ from 300 K?C400 K. The experimental values of field-lowering coefficient were by 2.56?C6.41 times higher than the predicted value and were attributed to the presence of localized fields. The increase in conductance with Sr content was due to formation of Fe⁴⁺ ions in addition to Fe³⁺ with the increase in Sr content. Impedance spectroscopy and ac conductivity analysis of La_1?x Sr _x FeO₃ (0 ?? x ?? 1) was also carried out in the temperature range from 300 K?C400 K and frequency was varied from 20 Hz - 2 MHz. The ac conduction followed the correlated barrier hopping model in La_0.9Sr_0.1FeO₃.     

Structural, magnetic, infrared and Raman studies of La0.8Sr x Ca0.2-x MnO3 (0 ≤ x ≤ 0.2)

We report the results of magnetic, X-ray powder diffraction, infrared and temperature dependent Raman spectra of the La_0.8Sr _x Ca_0.2-x MnO₃ (0 ≤ x ≤ 0.2) manganite. The structure refinement using the Rietveld method indicates that the partial substitution of strontium for calcium (for x ≥ 0.15) modifies the orthorhombic structure of the CaMnO₃ perovskite towards a rhombohedral phase. Magnetic measurement confirms the increase in the Curie temperature from 180 K for La_0.8Ca_0.2MnO₃ to 307 K for La_0.8Sr_0.2MnO₃, respectively. It is argued that the substitution with the larger Sr²⁺ ion strengthens the double-exchange interaction and gives rise to the observed increase of transition temperatures. All manganites show two IR active vibrational modes around 400 and 600 cm^?1. Moreover, when x ≤ 0.1, the absorption band around 400 cm^?1 splits into two peaks. In addition, we have analyzed the frequencies and widths of the observed Raman modes as a function of temperature for all samples with various Sr content. The mode splitting is attributed to both magnetic ordering and large orthorhombic distortion in doped rhombohedral manganites.     

Structural,electrical and magnetic properties of polycrystalline La0.67(Ca1−x Sr x )0.33MnO3 manganites

Polycrystalline La_0.67(Ca_1?x Sr _x )_0.33MnO₃ with different substitution level of strontium element, were synthesized via solid state reaction. Structure of samples was characterized by X-ray diffraction (XRD). XRD patterns reveal that La_0.67Ca_0.33MnO₃ exhibits orthorhombic structure with space group Pnma. Phase transitions from orthorhombic to rhombohedral take place as Ca ions were gradually substituted by Sr ions. The XRD data were further analyzed by Rietveld refinement technique. The data show that Mn–O–Mn bond angle increases as x increases. Microstructures obtained from SEM show that substitution of Sr ions has demoted the grain growth and densification process during sintering. The substitution of Sr ions has greatly influenced the hopping integral of electron via double exchange interaction, thus affecting the electrical properties and magnetic properties as well. The resistivity decreases and the metal–insulator transition temperature (T _p ) shifts to higher temperature as x increases. The magnetoresistance (MR) effect gradually decreases and MR peak shifts to higher temperature as x increases. The magnetization measured at room temperature is found to be increasing as x increases.     

Ultrasonic Anomaly Near the Charge Ordering Transition in Sr-Doped Nd0.3La0.2Ca0.5−x Sr x MnO3 Manganites

Sr doping in the charge-ordered compound Nd_0.3La_0.2Ca_0.5?x Sr _x MnO₃ has been systematically studied to examine its effect on ultrasonic velocity and elastic moduli as well as magnetic and electrical transport properties. DC electrical resistivity, ρ and AC susceptibility, χ′ measurements showed all samples exhibit metal-insulator (MI) behavior accompanied by ferromagnetic-paramagnetic (FM-PM) transition where the MI transition temperature, T _MI and FM-PM transition temperature, T _C increased with Sr content indicating the enhancement of double-exchange mechanism. Analysis of the resistivity change with respect to temperature, dlnρ/dT ^?1 versus T indicates onset of charge-ordering (CO) state where its CO transition temperature, T _CO decreased with Sr content indicating weakening of the CO state. On the other hand, both absolute longitudinal and shear velocities as well as elastic moduli measured at 80 K increased significantly with Sr doping indicating improvement in elastic properties, which is suggested to be due to the increase in formation of ferromagnetic domains. A longitudinal velocity anomaly characterized by a slope change around the vicinity of T _CO was observed for all samples. The longitudinal elastic anomaly is attributed to the Jahn–Teller (JT) effect of Mn³⁺ ions where analysis of the anomaly using the mean-field theory suggests involvement of the JT effect in the samples, which transforms from dynamic to static type with decreasing temperature. The elastic anomaly shifted down from 222 K (x=0) to 205 K (x=0.05) indicating that the static JT effect was weakened with Sr content.     

Influence of the sintering process on the PTCR effect of chip-type Ba1.022–x Sm x TiO3 ceramics prepared by the reduction sintering-reoxidation method

We investigated the effects of sintering temperature and reoxidation annealing on the positive temperature coefficient of resistance (PTCR) effect of Ba_1.022–x Sm _x TiO₃ ceramics that were sintered at 1,180–1,260 °C for 30 min in a reducing atmosphere and reoxidized at 800 °C for 1 h. Results indicated that the room-temperature (RT) resistivity and resistance jump of the ceramics decreased with increasing sintering temperature; moreover, the samples exhibited a remarkable PTCR effect with a resistance jump of 3.3 orders of magnitude and achieved a low RT resistivity of 374.4 Ω cm at a lower sintering temperature. Furthermore, the higher grain-boundary resistivity of the ceramics obtained at a high reoxidation temperature after sintering at low temperature was estimated using an impedance analyzer. In addition, the voltage versus current behavior was investigated in present study.     

Investigation of wide range magnetoresistance in La0.7Ca0.3−xAgxMnO3 (0 ≤ x ≤ 0.2) system

We synthesized magnetoresistive compounds with nominal compositions La_0.7Ca_0.3?xAg_xMnO₃ (0 ≤ x ≤ 0.2) by solid state reaction method with different sintering temperatures. All the samples exhibited orthorhombic structure with variable lattice parameters. The metal-insulator transitions were observed below room temperature in most of the samples. Depending upon the composition and sintering temperature, the samples showed very high magnetoresistance in narrow range or significant magnetoresistance over wide range of temperature. The ac susceptibility measurement revealed compositional dependence of Curie temperature.