Magnetic properties of Mg1-pMnpTe2 near p = 0.5

Precise magnetization measurements and neutron diffraction measurements are carried out for Mg_1-pMn_pTe₂ near the critical concentration p = 0.5 for the antiferromagnetic ordering. A magnetization property which is similar to micto-magnetism is observed for p = 0.35 and p = 0.45 samples. The susceptibility shows an anomaly at T_f and field-cooling effect is notable below T_f. Neutron diffraction experiments show that most of the manganese moments are ordered antiferromagnetically for p = 0.53 while small fractions of Mn²⁺ are ordered for p = 0.45 and p = 0.35.     

On the coexistence of spin and lattice polarons in the La0.67−xEuxCa0.33MnO3 CMR system

The electrical and magnetic transport properties of the La_0.67−xEu_xCa_0.33MnO₃ system exhibit lowering of insulator to metal and paramagnetic to ferromagnetic transition temperature (T_C) with the increase of Eu concentration in addition to possessing CMR property. The temperature variation of electrical resistivity and magnetic susceptibility for x=0.21 is found to have two distinct regions in the paramagnetic state for T>T_P; one with the localization of lattice polaron in the high-temperature region (T>1.5T_P) satisfying the dynamics of variable range hopping (VRH) model and the other being the combination of the spin and lattice polarons in the region T_P<T<1.5T_P. The resistivity variation with temperature and magnetic field, the cusp in the resistivity peak and CMR phenomenon are interpreted in terms of coexistence of spin and lattice small polarons in the intermediate region (T_P<T<1.5T_P). The spin polaron energy in the La_0.46Eu_0.21Ca_0.33MnO₃ system is estimated to be 106.73±0.90 meV and this energy decreases with the increase of external magnetic field. The MR ratio is maximal with a value of 99.99% around the transition temperature and this maximum persists till T→0 K, at the field of 8 T.     

Effects of double filling of Pb and Ba on thermoelectric properties of PbxBayCo4Sb11.5Te0.5 compounds by HPHT

Skutterudite compounds Pb_xBa_yCo₄Sb_11.5Te_0.5 (x≤0.23,y≤0.27) with bcc crystal structure have been prepared by the high pressure and high temperature (HPHT) method. The study explored a chemical method for filling Pb and Ba atoms into the voids of CoSb₃ to optimize the thermoelectric figure of merit ZT in the system of Pb_yBa_xCo₄Sb_11.5Te_0.5. The structure of Pb_xBa_yCo₄Sb_11.5Te_0.5 skutterudites was evaluated by means of X-ray diffraction. The Seebeck coefficient, electrical resistivity and power factor were performed from room temperature to 710 K. Compared with Co₄Sb_11.5Te_0.5, the thermal conductivity of Pb and Ba double-filled samples was reduced evidently. Among all filled samples, Pb_0.03Ba_0.27Co₄Sb_11.5Te_0.5 showed the highest power factor of 31.64 μW cm⁻¹ K⁻² at 663 K. Pb_0.05Ba_0.25Co₄Sb_11.5Te_0.5 showed the lowest thermal conductivity of 2.73 W m⁻¹ K⁻¹ at 663 K, and its maximum ZT value reached 0.63 at 673 K.     

Magnetoresistance and electron paramagnetic resonance study of La0.67−yYyBa0.33MnO3/LaAlO3 thin films

Magnetoresistive La_0.67−yY_yBa_0.33MnO₃/LaAlO₃ thin films were prepared by the sol-gel spin-coating method. Our resistivity and the electron spin resonance (ESR) measurements indicate that the main factor determining the metal-insulator transition temperature T_m is the cation disorder represented by the cation radii variance σ², and that ferromagnetic insulating regions coexist in the ferromagnetic metallic phase. In the paramagnetic phase, the dissociation energy of spin clusters and the polaron hopping energy obtained from the ESR intensity and linewidth also displayed a prominent dependence on σ². Polaron localization due to Jahn-Teller distortions appears to be responsible simultaneously for the decrease in the ferromagnetic order and for the increase in the orbital order.     

Effect of 3d metal ion doping on the structure and superconductivity of (Tl0.5Pb0.5)Sr2CaCu2O7

(Tl_0.5Pb_0.5)Sr₂Ca(Cu_2−xM_x)O₇ (M=Co, Ni and Zn) have been synthesized and investigated by means of X-ray diffraction, scanning electron microscope, electrical resistivity and magnetic susceptibility measurements. X-ray diffraction patterns show that all studied samples contain the nearly single ‘1212’ phase. They crystallize in a tetragonal unit cell with a=3.8028-3.8040 Å and c=12.0748-12.1558 Å. In (Tl_0.5Pb_0.5)Sr₂Ca(Cu_2−xM_x)O₇ system (M=Co or Ni), the superconducting critical temperature T_c decreases linearly with both Co and Ni concentrations and the rate of T_c decrease is around −6.5 and −7.0 K/at%, respectively. For (Tl_0.5Pb_0.5)Sr₂Ca (Cu_2−xZn_x)O₇ system, the dependence of T_c on the Zn dopant concentration deviates from a linear behavior and the Zn substitution suppresses T_c much less (−2.5 K/at%) than the Co and Ni substitutions. The suppression in T_c in Co and Ni doped samples are attributed to the magnetic pair-breaking mechanism and the reduction in the carrier concentration. The suppression of T_c in Zn doped samples is not caused by the reduction in carrier concentration which should remain constant, but rather due to nonmagnetic pair-breaking mechanism induced by disorder as well as the filling of the local Cu d_x²−y² state due to the full d band of Zn ions.     

Analysis of low temperature specific heat in Nd0.5Sr0.5MnO3 and R0.5Ca0.5MnO3 (R=Nd,Sm, Dy and Ho) compounds

We report on the specific heat C(T) of doped manganites Nd_0.5Sr_0.5MnO₃, Nd_0.5Ca_0.5MnO₃, Sm_0.5Ca_0.5MnO₃, Dy_0.5Ca_0.5MnO₃ and Ho_0.5Ca_0.5MnO₃ in the temperature range 2?T?300 K using modified rigid ion model (MRIM). The present specific heat results are in general satisfactory agreement with experimental data except at very low temperatures (i.e. T?12 K). Also a sharp peak observed in the experimental results for these compounds around 5 K could not be revealed by our computed results as they arise due to Schottky-like anomaly. Besides, we have reported the cohesive and the thermal properties of these compounds. The results obtained by us are discussed in detail.     

Structure and electrical properties of SrO-borovanadate (V2O5)0.5(SrO)0.5−y(B2O3)y glassses

SrO-borovanadate glasses with nominal composition (V₂O₅)_0.5(SrO)_0.5−y(B₂O₃)_y, 0.0≤y≤0.4 were prepared by a normal quench technique and investigated by direct current (DC) electrical conductivity, inductively coupled plasma (ICP) spectroscopy, infrared (IR) spectroscopy and X-ray powder diffraction (XRD) studies in an attempt to understand the nature of mechanism governing the DC electrical conductivity and the effect of addition of B₂O₃ on the structure and electrical properties of these glasses. XRD patterns confirm the amorphous nature of the present glasses and actual compositions of the glasses were determined by ICP spectroscopy. The temperature dependence of DC electrical conductivity of these glasses has been studied in terms of different hopping models. The IR results agree with previous investigations on similar glasses and it has been concluded that similar to SrO-vanadate glasses, metavandate chain-like structures of SrV₂O₆ and individual VO₄ units also occur in SrO-borovanadate glasses. The SrV₂O₆ and VO_n polyhedra predominate in the low B₂O₃-containing SrO-borovanadate glasses as B substitutes into the V sites of the various VO_n polyhedra and only when the concentration of B₂O₃ exceeds the SrO content do BO_n structures appear. This qualitative picture of three distinct structural groupings for Sr-vanadate and Sr-borovanadate glasses is consistent with the proposed glass structure on previous IR and extended X-ray absorption fine structure (EXAFS) studies on these types of glasses. The conductivity results were analyzed with reference to theoretical models existing in the literature and the analysis shows that the conductivity data are consistent with Mott's nearest neighbor hopping model. Analysis of the conductivity data shows that they are consistent with Mott's nearest neighbor hopping model. However, both Mott VRH and Greaves models are suitable to explain the data. Schnakenberg's generalized polaron hopping model is also consistent with temperature dependence of activation energy. However, various model parameters such as density of states, hopping energy, etc. obtained from the best fits were not found to be in accordance with the prediction of the Mott model.     

Phase separation, ferromagnetism and magnetic irreversibility in La1−xSrxMn1−yFeyO3

Magnetic susceptibility, χ(T), is investigated in ceramic La_1−xSr_xMn_1−yFe_yO₃ (LSMFO) samples with x=0.3 and y=0.15−0.25. A ferromagnetic (FM) transition observed in LSMFO is accompanied with an appreciable decrease of the transition temperature with increasing y, which is connected to breaking of the FM double-exchange interaction by doping with Fe. Strong magnetic irreversibility, observed in low (B=10 G) field, gives evidence for frustration of the magnetic state of LSMFO. The FM transition, which is expanded with increasing B, is more pronounced in the samples with y=0.15-0.20 and broadens considerably at y=0.25, where the irreversibility is increased. Well above the transition, χ(T) exhibits a Curie-Weiss asymptotic behavior, yielding very large values of the effective Bohr magneton number per magnetic ion, incompatible with those of Mn or Fe single ions. At y=0.15 and 0.20 a critical behavior of χ⁻¹(T)∼(T/T_C−1)^γ in the region of the FM transition is characterized by influence of two different magnetic systems, a 3D percolative one with γ₌γ_p≈1.8 and T_C=T_C^(p), and a non-percolative 3D Heisenberg spin system, with γ=γ_H≈1.4 and T_C=T_C^(H), where T_C^(p)<T_C^(H). At y=0.25 the percolative contribution to the critical behavior of χ(T) is not observed. The dependence of χ on T and y gives evidence for phase separation, with onset already near the room temperature, leading to generation of nanosize FM particles in the paramagnetic host matrix of LSMFO. The ferromagnetism of LSMFO is attributable to percolation over the system of such particles and generation of large FM clusters, whereas the frustration is governed presumably by a system of smaller weakly-correlated magnetic units, which do not enter the percolative FM clusters.     

Structure and superconductivity of Mg1−xPbxB2

A series of polycrystalline samples of Mg_1−xPb_xB₂ (0≤x≤0.10) were prepared by a solid state reaction method and their structure, superconducting transition temperature and transport properties were investigated by means of X-ray diffraction (XRD) and resistivity measurements. Mg_1−xPb_xB₂ compounds were shown to adopt an isostructural AlB2-type hexagonal structure in a relatively small range of lead concentration, x≤0.01. The crystalline lattice constants were evaluated and were found to exhibit slight length compression as x increases. The superconducting transition temperature (T_c) steadily decreases with Pb doping. It is suggested that the mechanism of superconductivity reduction by lead doping can be attributed to the chemical pressure effect.     

Increase in Tc and spin glass transition in La0.9Ca0.1Mn1−yCryO3 (y=0, 0.1 and 0.2)

We report on the structural, frequency dependent ac susceptibility, dc magnetization and magnetoresistance (MR) measurements on polycrystalline samples of La_0.9Ca_0.1Mn_1−yCr_yO₃ (y=0, 0.1 and 0.2) prepared by sol-gel technique. For y=0, a paramagnetic to ferromagnetic transition is observed at T_c=136 K. Both for y=0.1 and 0.2, T_c increases from 136 to 180 K. For y=0, the imaginary part of the ac susceptibility shows a broad transition at T_f<T_c which does not depend very much on the frequency. However, for y=0.1 and 0.2, the frequency dependence resembles that of a spin glass. Though all the three samples show a semi-conducting behavior between 300 and 5 K, a negative MR is observed corresponding to T_c and T_f. The value of MR decreases for the Cr substituted samples.     

Electronic transport and magnetic studies of La1−xCax−0.08Sr0.04Ba0.04MnO3

Lanthanum based mixed valence manganite system La_1−xCa_x−0.08Sr_0.04Ba_0.04MnO₃ (LCSBMO; x=0.15, 0.24 and 0.33) synthesized through the sol-gel route is systematically investigated in this paper. The electronic transport and magnetic susceptibility properties are analyzed and compared, apart from the study of unit cell structure, microstructure and composition. Second order phase transition is observed in all the samples and significant difference is observed between the insulator to metal transition temperature (T_MI) and paramagnetic (PM) to ferromagnetic (FM) transition temperature (T_C). In contrast to the insulating FM behaviour usually observed in La_1−xCa_xMnO₃ (LCMO) for x=0.15, a clear insulator to metal transition is observed for LCSBMO for the same percentage of lanthanum. The temperature dependent resistivity of polycrystalline pellets, when obeying the well studied law ρ=ρ_o+ρ₂T² for T<T_MI, is observed to differ significantly in the values of ρ_o and ρ₂, with the electrical conductivity increasing with x. The variable range hopping model has been found to fit resistivity data better than the small polaron model for T>T_MI. AC magnetic susceptibility study of the polycrystalline powders of the manganite system shows the highest PM to FM transition of 285 K for x=0.33.     

EDXRF measurements on gold diffusion-doped Bi1.8Pb0.35Sr1.9Ca2.1Cu3Oy

Gold (Au) diffusion in superconducting Bi_1.8Pb_0.35Sr_1.9Ca_2.1Cu₃O_y was investigated over the temperature range 500-800 °C by the energy dispersive X-ray fluorescence (EDXRF) technique. It is found that the Au diffusion coefficient decreases as the diffusion-annealing temperature decreases. The temperature dependences of Au diffusion coefficient in grains and over grain boundaries are described by the relations D₁=6.7×10⁻⁵exp(−1.19 eV/k_BT) and D₂=9.7×10⁻⁴exp(−1.09 eV/k_BT), respectively. The diffusion doping of Bi-2223 by Au causes a significant increase of the lattice parameter c by about 0.19%. For the Au-diffused samples, dc electrical resistivity and transport critical current density measurements indicated the critical transition temperature increased from 100 to 104 K and the critical current density increased from 40 to 125 A cm⁻², in comparison with those of undoped samples. From scanning electron microscope (SEM) and X-ray diffraction (XRD) measurements it is observed that Au doping of the sample also improved the surface morphology and increased the ratio of the high-T_c phase to the low-T_c phase. The possible reasons for the observed improvement in microstructure and superconducting properties of the samples due to Au diffusion are also discussed.     

Effects of excess oxygen content on the hole-carrying CuO2-layers in Tl2(Ba1−xSrx)2Ca2Cu3Oy superconducting oxides

The effects of oxygen doping on the hole-carrying CuO₂-layers in Tl₂(Ba_1−xSr_x)₂Ca₂Cu₃O_y were studied by combined chemical and valence analysis, T_c measurements and neutron diffraction. The highest T_c is characterized by an optimal excess oxygen content, Δy, dichotomizing the under- and over-doped regions for each Sr concentration. While the average Tl valence is close to 3.0 and independent of Δy, the average Cu valence shows a linear dependence with Δy. An increase of the flatness of the CuO₂ plane, characterized by the O(2)-Cu(2)-O(2) bond angle of ∼176°, was observed at the optimal Δy.     

Electrical behavior of nano-polycrystalline (La1−yKy)0.7Ba0.3MnO3 manganites

We present a study of the structural and electrical behavior of nano-polycrystalline mixed barium and alkali substituted lanthanum-based manganite, (La_1−yK_y)_0.7Ba_0.3MnO₃ with y=0.0-0.3. The samples were synthesized by the polymerization complex sol-gel method. The powder X-ray diffraction (XRD) data of the samples show a single-phase character with space group. The magnetic and electrical transport properties of the nano-polycrystalline samples have been investigated in the temperature range 50-300 K and a magnetic field up to 10 kOe. The metal-insulator transition temperature T_p of all the samples decreased with potassium doping, and also, it increased slightly with the application of magnetic field. The low field magnetoresistance, which is absent in the single-crystalline perovskite, was observed and increased with decreasing temperature. Comparing the experimental resistivity data with the theoretical models shows that the high temperature electrical behavior of these samples is in accordance with the adiabatic small polaron-hopping model. In the metal-ferromagnetic region the resistivity is found to be quite well described by ρ=ρ₀+ρ₂T²+ρ_4.5T^4.5.     

Dielectric and optical behaviors in relaxor ferroelectric Pb(In1/2Nb1/2)1−xTixO3 crystal

Dielectric permittivities (ε′,ε″) have been measured as functions of temperature (140-535 K) and frequency (500 Hz-2.0 MHz) in a (001)-cut Pb(In_1/2Nb_1/2)_0.7Ti_0.3O₃ (PINT30%) single crystal grown by the modified Bridgman method with Pb(Mg_1/3Nb_2/3)_0.71Ti_0.29O₃ (PMNT29%) seed crystal. A diffused phase transition was observed in the temperature region of ∼430-460 K with strong frequency dispersion. Above the Burns temperature T_B≅510 K, the dielectric permittivity was found to follow the Curie-Weiss behavior, ε′=C/(T−T_C), with parameters C=3.9×10⁵ and T_C=472 K. Below T_B≅510 K, polar nanoclusters are considered to appear and are responsible for the diffused dielectric anomaly. Optical transmission, refractive indices, and the Cauchy equations were obtained as a function of wavelength at room temperature. The unpoled crystal shows almost no birefringence, indicating that the average structural symmetry is optically isotropic. The crystal exhibits a broad transparency in the wavelength range of ∼0.4-6.0 μm.     

The effect of oxygen stoichiometry on electrical transport and magnetic properties of La0.9Te0.1MnOy

The effect of the variation of oxygen content on structural, magnetic and transport properties in the electron-doped manganites La_0.9Te_0.1MnO_y has been investigated. All samples show a rhombohedral structure with the space group The Curie temperature T_C decreases and the paramagnetic-ferromagnetic (PM-FM) transition becomes broader with the reduction of oxygen content. The resistivity of the annealed samples increases slightly with a small reduction of oxygen content. Further reduction in the oxygen content, the resistivity maximum increases by six orders of magnitude compared with that of the as-prepared sample, and the ρ(T) curves of samples with y=2.86 and y=2.83 display the semiconducting behavior (dρ/dT<0) in both high-temperature PM phase and low-temperature FM phase, which is considered to be related to the appearance of superexchange ferromagnetism and the localization of carriers. The results are discussed in terms of the combined effects of the increase in the Mn²⁺/(Mn²⁺+Mn³⁺) ratio, the partial destruction of double exchange interaction, and the localization of carriers due to the introduction of oxygen vacancies in the Mn-O-Mn network.     

Microstructure and magnetocaloric effect in cast LaFe11.5Si1.5Bx (x=0.5, 1.0)

Phase formation, structure, and the magnetocaloric effect (MCE) in as-cast LaFe_11.5Si_1.5B_x (x=0.5, 1.0) compounds have been studied. The Curie temperatures, T_C, are ∼211 and 230 K for x=0.5 and 1.0, respectively, which are higher than that of annealed LaFe_11.5Si_1.5 (T_C=183 K), while the maximum magnetic entropy changes at the respective T_C under a magnetic field change of 0-5 T are 7.8 and 5.8 J/(kg K). Wavelength dispersive spectrometry (WDS) analysis shows that only a small fraction of boron atoms is dissolved in the NaZn₁₃-type structure phase, and that the compositions of the as-cast LaFe_11.5Si_1.5B_x (x=0.5, 1.0) alloys are much different from the intended nominal compositions. These as-cast alloys exhibit second-order magnetic phase transitions and low MCEs. However, based on the relative cooling power, the as-cast LaFe_11.5Si_1.5B_x alloys are promising candidates for magnetic refrigerants over a wide temperature range.     

Magnetic field induced order–order phase transition in magnetocaloric systems Mn2−xFexAs0.5P0.5 and MnFeAsyP1−y

An analysis is presented of experimental and theoretical results of the MnFeAs_yP_1−y (0.15≤y≤0.66) and Mn_2−xFe_xAs_0.5P_0.5 (0.5≤x≤1.0) systems to identify main traits that underlie the mechanism of formation of different antiferromagnetic (AF) phases in the two systems. The discrepancy between the calculated from first principles and experimental values of the magnetic moment in the ferromagnetic phase with cation substitution in the system Mn_2−xFe_xAs_0.5P_0.5 is due to the appearance of a canted magnetic structure. In this case, the emergence of an AF phase with decreasing iron concentration precedes a significant change in the electronic d-band filling. In the model of the spiral structure in the system of itinerant electrons it is shown that the stabilization of the AF phase with decreasing arsenic concentration, while maintaining the number of d-electrons, is a consequence of changes in the shape of the density of electronic states that occur with a decrease in unit-cell volume.     

Small polaron migration in LixMn2O4: From first principles calculations

Migration of small polarons in λ-MnO₂, Li_0.5Mn₂O₄ and LiMn₂O₄ is studied via first principles calculations. Migration energy barriers of single small polaron migrations in λ-MnO₂, Li_0.5Mn₂O₄ and LiMn₂O₄ are 0.22 eV, 0.45 eV and 0.35 eV, respectively. The energy level changes of Mn-3d states along the polaron migration path are analyzed in detail. Results indicate that the activation energy barrier of polaron migration is strongly associated with the energy level shift of Mn-3dz² orbital, which is dependent on the short range structural arrangement of Mn³⁺/Mn⁴⁺ in the crystal. The electrical conduction properties of Li_xMn₂O₄ at room temperature are then discussed.     

Structural, magnetotransport and morphological studies of Sb-doped La2/3Ba1/3MnO3 ceramic perovskites

We report here the structural, magnetotransport and morphological studies of Sb-doped La_2/3Ba_1/3Mn_1−xSb_xO₃ perovskite manganites. Pristine material La_2/3Ba_1/3MnO₃ (LBMO) shows two insulator-metal (I-M) transitions in the electrical resistivity-temperature (ρ-T) behavior. While the higher temperature transition (T_P1) at ∼340 K is reminiscent of the usual I-M transition in manganites, the lower temperature transition (T_P2) at ∼250 K has been ascribed to the grain boundary (GB) effects arising out of the ionic size mismatch between the ions present at the rare-earth site (La³⁺ and Ba²⁺). With Sb-doping T_P1 shifts to lower temperatures while T_P2 remains invariant up to 3% and shifts to lower temperature for 5%. Room temperature electrical resistivity and the peak values also increase successively with Sb-doping. Scanning electron micrographs of the samples exhibit a gradual increase in their grain sizes with Sb indicating a gradual decrease in the GB density. Shift of T_P1 with doping is explained on the basis of a competition between double-exchange and super-exchange mechanisms. The overall electrical resistivity increases and the shift in the electrical resistivity hump (T_P2) with Sb-doping is found related to be gradually decreasing GB density and the ensuing lattice strain increase at the GBs. The intrinsic magnetoresistance (MR) gets suppressed and extrinsic MR gets enhanced with Sb-doping. At T>T_P1, the electrical resistivity is found to follow the adiabatic polaron hopping model whereas the electron-magnon scattering is found to dominate in the metallic regime (T<T_P1).